WorldWideScience

Sample records for possessing isomeric mniii10mnii2o16cl2

  1. Xylene isomerization

    KAUST Repository

    Bilaus, Rakan Sulaiman; Pinnau, Ingo

    2016-01-01

    at isomenzation conditions and producing an isomerized product comprising a higher proportion of p-xylene than in the feed mixture, wherein the catalyst comprises an acidic sulfonated catalytic membrane. Xylene isomenzation can also be coupled with a p

  2. Xylene isomerization

    KAUST Repository

    Bilaus, Rakan Sulaiman

    2016-06-23

    A process for producing xylenes, in particular para-xylene that is less energy intensive than conventional processes is provided. In an embodiment the process comprises contacting a feed mixture in an isomenzation zone with a catalyst at isomenzation conditions and producing an isomerized product comprising a higher proportion of p-xylene than in the feed mixture, wherein the catalyst comprises an acidic sulfonated catalytic membrane. Xylene isomenzation can also be coupled with a p-xylene extraction process, where the raffinate (p-xylene deprived stream) from the extraction process is fed to an isomenzation reactor to produce p-xylene. In an embodiment, the process can comprise: a) providing a feed stream comprising a mixture of xylene isomers including p-xylene; b) extracting p-xylene from the feed stream using a separator to separate the feed stream into a p-xylene rich stream and a p-xylene deprived stream; and c) delivering the p-xylene deprived stream to an isomenzation unit, the isomenzation unit including an acidic sulfonated catalytic membrane, and using the isomenzation unit to produce an isomerized product comprising a higher proportion of p-xylene than in the p-xylene deprived stream delivered to the isomenzation unit. In any one or more aspects, the isomenzation unit can be operated at a temperature in the range of less than 350°, for example about 20°C to about 200°C.

  3. Isomeric Targets and Beams

    International Nuclear Information System (INIS)

    Oganesyan, Yu.Ts.; Karamyan, S.A.

    1994-01-01

    One of the main topics of modern nuclear physics is the investigation of exotic nuclei including hyper-nuclei, trans fermium elements, proton and neutron rich isotopes near drip lines as well as high-spin excited states and states with anomalous deformation. The isomerism of nuclei is closely related with such phenomena as the alignment of single-particle orbitals, the coexistence of various deformations and the manifestation of intruder-levels from neighbouring shells. The investigation of electromagnetic and nuclear interactions of isomers could give important information on their shell structure and its role in the mechanism of nuclear reactions. For such experiments one can either make isomeric targets (sufficiently long-lived) or use the methods of acceleration of isomeric nuclei. Recently, an exotic 16 + four-quasiparticle isomer of 178 Hf m 2 was produced in a micro weight quantity and the first nuclear reactions on it were successfully observed. The talk describes these experiments as well as new ideas for the continuation of the studies and some advantageous ways for the isomeric beams production by the method of direct acceleration or by the secondary beam method. 35 refs., 15 figs., 8 tabs

  4. 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)

  5. 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)

  6. The protection of possession

    Directory of Open Access Journals (Sweden)

    Popov Danica

    2011-01-01

    Full Text Available Protection in disputes for the protection of possession can be attained through the following actions a for dispossession (interdictum recuperande possessionis and b with an action for the disturbance of possession (interdictum retinendae possessionis. The general feature of these disputes is that there is only discussion on the facts and not a legal matters. Subject matter jurisdiction for the resolution of such disputes belongs to the court of general jurisdiction, while the dispute itself is a litigation. The special rule of proceedings of action for disturbance are: provisionality of the protection of possession; urgency in proceedings; initiation of the proceedings; limiting of objection; prescribing temporary measures; rendering a ruling in the form of order; appeals which may be filed within a short deadline and which does not have suspensive effect (do not delay the execution of the order; revision is not allowed etc.

  7. Experimental grounds for nuclear shape isomerism

    International Nuclear Information System (INIS)

    Makarenko, V.E.

    1995-11-01

    Experimental data on fission isomeric states of actinide nuclei - half lives, energies, quantum numbers, decay branches and spectroscopic properties - are discussed. Quite a few results find their explanation in the framework of nuclear shape isomerism hypothesis being the in-thing for about thirty years. Others seem to be the hints to the quasiparticle nature of fission isomers. The problem could be solved by direct measurement of nuclear spin for isomeric states. (author). 44 refs, 1 tab

  8. Quantum optimal control of ozone isomerization

    International Nuclear Information System (INIS)

    Artamonov, Maxim; Ho, Tak-San; Rabitz, Herschel

    2004-01-01

    We present a feasibility study of ozone isomerization based on a recent ab initio potential energy surface and a model Hamiltonian constructed by holding the bond lengths constant and using the valence angle as the isomerization coordinate. Optimal control theory is used to find an electric field that drives isomerization with a yield of 95% to the symmetric metastable triangular form of ozone. A frequency filter is applied as an additional spectral constraint limiting the field bandwidth. A post-facto analysis is performed showing a degree of inherent robustness of the isomerization yield to field noise

  9. Kinetic and mass transfer studies on the isomerization of cellulose hydrolyzate using immobilized Streptomyces cells

    Energy Technology Data Exchange (ETDEWEB)

    Ghose, T K; Chand, S

    1978-01-01

    Streptomyces cells possessing glucose isomerase activity, heat-treated and confined within polyester sacs have been used in batch/continuous isomerization of enzymatically hydrolyzed microcrystalline cellulose. Conversion data at different concentrations of substrate closely follow the reactor performance equation based on the reaction kinetics. The effect of external film and pore diffusional resistances were experimentally found to be negligible. The dispersion effects in the packed bed column have been evaluated by pulse input tracer analysis. Continuous operation of the column to isomerize cellulose hydrolyzate (2.0 M glucose) showed an exponential deactivation of enzyme activity with a half-life of 447 h.

  10. Experiments with neutron-rich isomeric beams

    International Nuclear Information System (INIS)

    Rykaczewski, K.; Lewitowicz, M.; Pfuetzner, M.

    1998-01-01

    A review of experimental results obtained on microsecond-isomeric states in neutron-rich nuclei produced in fragmentation reactions and studied with SISSI-Alpha-LISE3 spectrometer system at GANIL Caen is given. The perspectives of experiments based on secondary reactions with isomeric beams are presented

  11. A new fundamental type of conformational isomerism

    Science.gov (United States)

    Canfield, Peter J.; Blake, Iain M.; Cai, Zheng-Li; Luck, Ian J.; Krausz, Elmars; Kobayashi, Rika; Reimers, Jeffrey R.; Crossley, Maxwell J.

    2018-06-01

    Isomerism is a fundamental chemical concept, reflecting the fact that the arrangement of atoms in a molecular entity has a profound influence on its chemical and physical properties. Here we describe a previously unclassified fundamental form of conformational isomerism through four resolved stereoisomers of a transoid (BF)O(BF)-quinoxalinoporphyrin. These comprise two pairs of enantiomers that manifest structural relationships not describable within existing IUPAC nomenclature and terminology. They undergo thermal diastereomeric interconversion over a barrier of 104 ± 2 kJ mol-1, which we term `akamptisomerization'. Feasible interconversion processes between conceivable synthesis products and reaction intermediates were mapped out by density functional theory calculations, identifying bond-angle inversion (BAI) at a singly bonded atom as the reaction mechanism. We also introduce the necessary BAI stereodescriptors parvo and amplo. Based on an extended polytope formalism of molecular structure and stereoisomerization, BAI-driven akamptisomerization is shown to be the final fundamental type of conformational isomerization.

  12. Easy Synthesis of Two Positional Isomeric Tetrazole Libraries

    NARCIS (Netherlands)

    Wang, Yuanze; Patil, Pravin; Dömling, Alexander

    2016-01-01

    A fast and efficient synthesis of libraries of positional isomeric 1H-tetrazoles and 5H-tetrazoles, for the purpose of testing binding hypothesis of isomeric tetrazoles in fragment-based drug discovery, is described.

  13. Formation, isomerization, and derivatization of keggin tungstoaluminates.

    Science.gov (United States)

    Jennifer J. Cowan; Alan J. Bailey; Robert A. Heintz; Bao T. Do; Kenneth I. Hardcastle; Craig L. Hill; Ira A. Weinstock

    2001-01-01

    Trends in the stability of ¥á and ©¬-Keggin heteropolytungstates of the second-row main-group heteroatoms Al(III), Si(IV), and P(V) are elaborated by data that establish the roles of kinetic and thermodynamic control in the formation and isomerization of Keggin tungstoaluminates. Slow, room-temperature co-...

  14. Isomeric periodic mesoporous organosilicas with controllable properties

    NARCIS (Netherlands)

    Vercaemst, C.; Ide, I.; Friedrich, H.; de Jong, K.P.; Verpoort, F.; van der Voort, P.

    2009-01-01

    The synthesis procedure for isomeric periodic mesoporous organosilicas with E-configured ethenylene bridges was investigated using the homemade pure E-isomer of 1,2-bis(triethoxysilyl)ethene. The pH, aging temperature and the presence of cosolvents played a key role in obtaining well-ordered

  15. Trimethylphosphide isomerization in lanthanum ions presence

    International Nuclear Information System (INIS)

    Zacharias, M.A.; Massabni, A.M.G.

    1984-01-01

    The integration between the trimethilphosphide and the lanthanum ions carry to the formation of solid complexes in a relation of 6:1 where the ligand is the phosphonate what is resultant of the isomerization of trimetylphosphite. By the RMN -1 H and infra-red spectra the products were characterized. (L.M.J.) [pt

  16. Iodine-Catalyzed Isomerization of Dimethyl Muconate

    Energy Technology Data Exchange (ETDEWEB)

    Settle, Amy E [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Berstis, Laura R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Zhang, Shuting [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Rorrer, Nicholas [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Hu, Haiming [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Richards, Ryan [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Beckham, Gregg T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Crowley, Michael F [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Vardon, Derek R [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2018-04-12

    cis,cis-Muconic acid is a platform biobased chemical that can be upgraded to drop-in commodity and novel monomers. Among the possible drop-in products, dimethyl terephthalate can be synthesized via esterification, isomerization, Diels-Alder cycloaddition, and dehydrogenation. The isomerization of cis,cis-dimethyl muconate (ccDMM) to the trans,trans-form (ttDMM) can be catalyzed by iodine; however, studies have yet to address (i) the mechanism and reaction barriers unique to DMM, and (ii) the influence of solvent, potential for catalyst recycle, and recovery of high-purity ttDMM. To address this gap, we apply a joint computational and experimental approach to investigate iodine-catalyzed isomerization of DMM. Density functional theory calculations identified unique regiochemical considerations due to the large number of halogen-diene coordination schemes. Both transition state theory and experiments estimate significant barrier reductions with photodissociated iodine. Solvent selection was critical for rapid kinetics, likely due to solvent complexation with iodine. Under select conditions, ttDMM yields of 95% were achieved in <1 h with methanol, followed by high purity recovery (>98%) with crystallization. Lastly, post-reaction iodine can be recovered and recycled with minimal loss of activity. Overall, these findings provide new insight into the mechanism and conditions necessary for DMM isomerization with iodine to advance the state-of-the-art for biobased chemicals.

  17. Crystal structure of isomeric boron difluoride acetylnaphtholates

    International Nuclear Information System (INIS)

    Bukvetskij, B.V.; Fedorenko, E.V.; Mirochnik, A.G.; Karasev, V.E.

    2006-01-01

    Crystal structures of luminescent isomeric acetylnaphtholates of boron difluoride are investigated. Full X-ray structural analysis is done at 293 K. Coordinated of atoms, bond angles, bond lengths, interatomic distances are determined. Results of comparative evaluations of the isomers are represented [ru

  18. Cat's claw oxindole alkaloid isomerization induced by common extraction methods

    Directory of Open Access Journals (Sweden)

    Samuel Kaiser

    2013-01-01

    Full Text Available Cat's claw oxindole alkaloids are prone to isomerization in aqueous solution. However, studies on their behavior in extraction processes are scarce. This paper addressed the issue by considering five commonly used extraction processes. Unlike dynamic maceration (DM and ultrasound-assisted extraction, substantial isomerization was induced by static maceration, turbo-extraction and reflux extraction. After heating under reflux in DM, the kinetic order of isomerization was established and equations were fitted successfully using a four-parameter Weibull model (R² > 0.999. Different isomerization rates and equilibrium constants were verified, revealing a possible matrix effect on alkaloid isomerization.

  19. Is isomerism a risk factor for intestinal volvulus?

    Science.gov (United States)

    Landisch, Rachel M; Loomba, Rohit S; Salazar, Jose H; Buelow, Matthew W; Frommelt, Michele; Anderson, Robert H; Wagner, Amy J

    2018-03-06

    Isomerism, or heterotaxy syndrome, affects many organ systems anatomically and functionally. Intestinal malrotation is common in patients with isomerism. Despite a low reported risk of volvulus, some physicians perform routine screening and prophylactic Ladd procedures on asymptomatic patients with isomerism who are found to have intestinal malrotation. The primary aim of this study was to determine if isomerism is an independent risk factor for volvulus. Kid's Inpatient Database data from 1997 to 2012 was utilized for this study. Characteristics of admissions with and without isomerism were compared with a particular focus on intestinal malrotation, volvulus, and Ladd procedure. A logistic regression was conducted to determine independent risk factors for volvulus with respect to isomerism. 15,962,403 inpatient admissions were included in the analysis, of which 7970 (0.05%) patients had isomerism, and 6 patients (0.1%) developed volvulus. Isomerism was associated with a 52-fold increase in the odds of intestinal malrotation by univariate analysis. Of 251 with isomerism and intestinal malrotation, only 2.4% experienced volvulus. Logistic regression demonstrated that isomerism was not an independent risk factor for volvulus. Isomerism is associated with an increased risk of intestinal malrotation but is not an independent risk factor for volvulus. Prognosis study. Level III. Copyright © 2018 Elsevier Inc. All rights reserved.

  20. Characterizing gamma fields using isomeric activation ratios

    Science.gov (United States)

    Venkataraman, Ramkumar; Fleming, Ronald F.

    1994-12-01

    Isomeric activities were induced in indium by gamma irradiation in three different gamma fields, through the reactions 115In(γ, γ') 115mIn and 113In(γ, γ') 113mIn. The irradiation fields were (i) the 15 kCi 60Co source available in the University, (ii) the spent fuel gamma irradiator in the pool of the University's Ford Nuclear Reactor (FNR) and (iii) south face of the core of the FNR during routine shut downs. Isomeric activation ratios can serve to characterize gamma fields, provided the response functions of the two (γ, γ') reactions sample different energy regimes of the gamma spectrum present in the irradiation fields. The response of an isomeric activation detector, in turn, depends on the number of activation energy levels of the nuclide and the probabilities with which the activation levels de-populate to the isomeric level. The reaction rate ratio RIn115m/ RIn113m was measured in the three gamma fields. The measured ratios were (i) 1.210 ± 0.011 in the 60Co source, (ii) 1.314 ± 0.060 in the spent fuel gamma irradiator and (iii) 1.298 ± 0.039 in a location alongside the FNR core during routine shut downs. The measured reaction rate ratios are not only close to each other, but close to unity as well. This indicates that the excitation functions for the reactions 115In(γ, γ') 115mIn and 113In(γ, γ') 113mIn have similar shapes and that for the nuclides 115In and 113In, the number of activation energy levels and the probabilities with which they populate the isomeric levels are very similar to each other. Thus, the ratio RIn115m/ RIn113m will not yield any information regarding the shape of gamma spectrum in the field of measurement. However by choosing (γ, γ') reactions with different shapes for the excitation functions one can measure a set of isomeric activation ratios that characterize a given gamma field.

  1. Isomerization of C[sub 4] alkenes

    Science.gov (United States)

    Smith, L.A. Jr.

    1984-11-13

    A method is described for isomerizing isobutene or n-butene to produce a mixture of isobutene and normal butene, and polymerizing at least a portion thereof to produce isobutene/n-butene co-dimer, which comprises feeding at least 80 weight % of either the isobutene or n-butene to a catalytic distillation reactor containing a fixed bed acidic cation exchange resin catalyst packing which provides both the catalyst sites and distillation sites for the reaction products, isomerizing a portion of the isobutene or n-butene to produce a mixture of isobutene and n-butene and reacting at least a portion of the isobutene and n-butene to form co-dimer of isobutene and n-butene, whereby an overhead fraction containing any unreacted isobutene and n-butene and a bottoms fraction containing co-dimer is produced. The result of the reaction is substantially the same regardless whether the feed is isobutene or n-butene. Other aspects of the invention, include combinations of procedures to produce high purity isobutene and n-butene. Either isobutene or n-butene product (depending on the desired product) can be recycled as feed, thus substantially carrying out the isomerization to extinction and total conversion to the desired product. 1 fig.

  2. Individual ball possession in soccer.

    Directory of Open Access Journals (Sweden)

    Daniel Link

    Full Text Available This paper describes models for detecting individual and team ball possession in soccer based on position data. The types of ball possession are classified as Individual Ball Possession (IBC, Individual Ball Action (IBA, Individual Ball Control (IBC, Team Ball Possession (TBP, Team Ball Control (TBC und Team Playmaking (TPM according to different starting points and endpoints and the type of ball control involved. The machine learning approach used is able to determine how long the ball spends in the sphere of influence of a player based on the distance between the players and the ball together with their direction of motion, speed and the acceleration of the ball. The degree of ball control exhibited during this phase is classified based on the spatio-temporal configuration of the player controlling the ball, the ball itself and opposing players using a Bayesian network. The evaluation and application of this approach uses data from 60 matches in the German Bundesliga season of 2013/14, including 69,667 IBA intervals. The identification rate was F = .88 for IBA and F = .83 for IBP, and the classification rate for IBC was κ = .67. Match analysis showed the following mean values per match: TBP 56:04 ± 5:12 min, TPM 50:01 ± 7:05 min and TBC 17:49 ± 8:13 min. There were 836 ± 424 IBC intervals per match and their number was significantly reduced by -5.1% from the 1st to 2nd half. The analysis of ball possession at the player level indicates shortest accumulated IBC times for the central forwards (0:49 ± 0:43 min and the longest for goalkeepers (1:38 ± 0:58 min, central defenders (1:38 ± 1:09 min and central midfielders (1:27 ± 1:08 min. The results could improve performance analysis in soccer, help to detect match events automatically, and allow discernment of higher value tactical structures, which is based on individual ball possession.

  3. Thermal E/ Z Isomerization in First Generation Molecular Motors.

    Science.gov (United States)

    Kuwahara, Shunsuke; Suzuki, Yuri; Sugita, Naoya; Ikeda, Mari; Nagatsugi, Fumi; Harada, Nobuyuki; Habata, Yoichi

    2018-04-20

    Determination of a thermal E/ Z isomerization barrier of first generation molecular motors is reported. Stable ( E)-1a directly converts to stable ( Z)-1c without photochemical E/ Z isomerization. The activation Gibbs energy of the isomerization was determined to be 123 kJ mol -1 by circular dichroism spectral changes. Density functional theory calculations show that ( Z)-1c is ∼11.4 kJ mol -1 more stable than ( E)-1a.

  4. Designing bifunctional alkene isomerization catalysts using predictive modelling

    NARCIS (Netherlands)

    Landman, I.R.; Paulson, E.R.; Rheingold, A.L.; Grotjahn, D.B.; Rothenberg, G.

    2017-01-01

    Controlling the isomerization of alkenes is important for the manufacturing of fuel additives, fine-chemicals and pharmaceuticals. But even if isomerization seems to be a simple unimolecular process, the factors that govern catalyst performance are far from clear. Here we present a set of models

  5. Isomeric Detergent Comparison for Membrane Protein Stability

    DEFF Research Database (Denmark)

    Cho, Kyung Ho; Hariharan, Parameswaran; Mortensen, Jonas S.

    2016-01-01

    and utility, particularly for eukaryotic membrane proteins and membrane protein complexes. Thus, a number of new agents have been devised; some have made significant contributions to membrane protein structural studies. However, few detergent design principles are available. In this study, we prepared meta...... and ortho isomers of the previously reported para-substituted xylene-linked maltoside amphiphiles (XMAs), along with alkyl chain-length variation. The isomeric XMAs were assessed with three membrane proteins, and the meta isomer with a C12 alkyl chain was most effective at maintaining solubility....../stability of the membrane proteins. We propose that interplay between the hydrophile–lipophile balance (HLB) and alkyl chain length is of central importance for high detergent efficacy. In addition, differences in inter-alkyl-chain distance between the isomers influence the ability of the detergents to stabilise membrane...

  6. The qualified possession turn into ownership

    Directory of Open Access Journals (Sweden)

    Popov Danica

    2011-01-01

    Full Text Available Possession is prima facie evidence of ownership. Possession is ninetents of the law, means that possession is good against all other, except the true owner. The possession ripens into ownership if it is qualified and by effluxion of time. In Serbian law there are two kinds of adverse possession ripens into ownership. The first one is named ordinary and second one extraordinary adverse possession. Ordinary possession need to be legal, conscientious and genuine. Extraordinary possession is only conscientious, but in a wide sense. Adverse possession destroys the title of the owner and vests it in possessor. An occupation of land inconsistent with the right of the true owner: the possession of those against whom a right action has accured to the true owner. It is actual possession in the absence of possession by the rightful owner and without lawful title. If the adverse possession continues, the effect at the expiration of the prescribed period is that not only the remedy but the title of former owner is extinguished. The person in adverse possession gains a new possessory title which cannot, normally exceed in extent of duration the interest of the former owner.

  7. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

    Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

  8. Insights in the Rhodium-Catalyzed Tandem Isomerization-Hydroformylation of 10-Undecenitrile: Evidence for a Fast Isomerization Regime

    Directory of Open Access Journals (Sweden)

    Lucas Le Goanvic

    2018-04-01

    Full Text Available The tandem isomerization-hydroformylation of 10-undecenitrile (1 into the corresponding linear aldehyde (2 with a Rh-biphephos system was studied and the formation of internal olefin isomers (1-int-x was monitored over time. The existence of an “isomerization phenomenon” was evidenced, where fast isomerization of 1 into up to 70% of 1-int-x followed by fast back-isomerization of 1-int-x into 1 and, in turn, into 2 occurs. This fast dynamic isomerization regime is favored at high syngas pressure (40 bar and low biphephos-to-Rh ratio (5–10, and it is best observed at relatively high catalyst loadings ([1]0/[Rh] ≤ 3000. The latter regime is indeed evanescent, and gives place to a second stage in which isomerization of internal olefins (and eventual conversion into 2 proceeds much more slowly. The results are tentatively rationalized by the formation of an unstable species that promotes dynamic isomerization and which slowly vanishes or collapses into a Rh-biphephos species which is the one responsible for hydroformylation.

  9. Synthesis and Characterisation of Eight Isomeric Bis(2-pyridyloxynaphthalenes

    Directory of Open Access Journals (Sweden)

    Peter J. Steel

    2006-09-01

    Full Text Available Eight isomeric bis(2-pyridyloxynaphthalenes have been prepared from reactions of 2-bromopyridine with the appropriate dihydroxynaphthalene and the products fully characterised by 1- and 2-D NMR spectroscopy.

  10. Isomerizations of the Nitromethane Radical Cation in the Gas Phase

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars; Elbel, Susanne

    1986-01-01

    The concurrent isomerizations of the nitromethane radical cation to its aci-nitromethane and methylnitrite isomers, respectively, has been established based on metastable ion studies and collision activation mass spectrometry. The energy diagram for the ionized nitromethane/aci-nitromethane tauto......The concurrent isomerizations of the nitromethane radical cation to its aci-nitromethane and methylnitrite isomers, respectively, has been established based on metastable ion studies and collision activation mass spectrometry. The energy diagram for the ionized nitromethane...

  11. Study of the photochemical isomerization of ergosterol

    International Nuclear Information System (INIS)

    Mermet-Bouvier, Rene

    1972-01-01

    The photochemical reaction scheme of Ergosterol-Vitamin D 2 was studied. The schemes proposed in published literature are described together with earlier methods used for the analysis and determination. The method used is then discussed. In the first part, the factors concerning the changes occurring in molecular systems exposed to radiation, and the formalism used, are examined. Investigations of linear molecular systems and their applications to the reaction scheme of Ergosterol-Vitamin D 2 are discussed. The properties which enable the last three reaction schemes proposed in the literature to be distinguished are described. In the second part, the experimental analytical methods and the determinations made of the different isomers formed are presented. Chromatographic techniques (thin films, columns, gaseous phase) suitable for separating the various isomeric species are used. The existence of 8 isomers was established as well as a transformation occurring in one of them. The ultraviolet and infrared spectra were obtained. A reaction scheme is proposed (in which all the quantum yield values are given) from comparisons between the calculated and experimental values of the eigenvalue of the absolute minimum value λ m and the eigenvector corresponding to V m . (author) [fr

  12. Improving gasoline quality produced from MIDOR light naphtha isomerization unit

    Directory of Open Access Journals (Sweden)

    M.F. Mohamed

    2017-03-01

    Full Text Available Isomerization process became one of the best gasoline production sources, as it gives a high octane product while saving environment from pollution impacts. This paper presents a practical study that aims to improve the gasoline quality and economic income of an existing light naphtha isomerization unit used for octane improvement. The study included selecting the optimum combination of isomerization unit equipment that gives better product specifications for a specified feed. Eight scenarios were studied and simulated to predict the product specs. The original studied unit is MIDOR light naphtha isomerization unit at Alexandria-Egypt that recycles the unconverted hexane (C6. The other studied scenarios were adding fractionators for separating feed iso-pentanes, and recycling unconverted pentanes, hexanes and/or combinations of these fractionators. The results show a change in octane number of gasoline product for a specific feed. Once through process with no extra fractionators has lower octane number of 81 while that with de-iso-pentanizer–de-pentanizer and de-hexanizer produces gasoline with 92.3 octane number. Detailed economic study was done to calculate the return on investment “ROI” for each process option based on equipment, utilities, feed and product prices. Once through simple isomerization unit had the lowest ROI of 14.3% per year while the combination of De-iso-pentanizer with the De-hexanizer had the best ROI of 26.6% per year.

  13. 50 CFR 648.164 - Possession restrictions.

    Science.gov (United States)

    2010-10-01

    ... Atlantic Bluefish Fishery § 648.164 Possession restrictions. (a) No person shall possess more than 15 bluefish in, or harvested from, the EEZ unless that person is the owner or operator of a fishing vessel issued a bluefish commercial permit or is issued a bluefish dealer permit. Persons aboard a vessel that...

  14. Radiochemical study of isomerization of free butyl cations

    International Nuclear Information System (INIS)

    Sinotova, E.N.; Nefedov, V.D.; Skorokhodov, S.S.; Arkhipov, Yu.M.

    1987-01-01

    Ion-molecular reactions of free butyl cations, generated by nuclear chemical method, with carbon monoxide containing small quantities of ethanol vapors are studied. Carbon monoxide was used to fix instable butyl cations in the form of corresponding acyl ions. Ester of α-methyl-butyric acid appears to be the only product of free butyl cation interaction with carbon monoxide in the presence of ethanol vapors. That means, that up to the moment of butyl cation reaction with carbon monoxide, the primary butyl cations are almost completely isomerized into secondary in agreement with results of previous investigations. This allows one to study free butyl cation isomerization process according to ion-molecular reaction product isomeric composition

  15. Isomeric states in 253No and 253Fm

    International Nuclear Information System (INIS)

    Antalic, S.; Kalaninova, Z.; Saro, S.; Venhart, M.; Hessberger, F.P.; Ackermann, D.; Heinz, S.; Kindler, B.; Khuyagbaatar, J.; Kojouharov, I.; Kuusiniemi, P.; Lommel, B.; Mann, R.; Sulignano, B.; Hofmann, S.; Leino, M.; Nishio, K.; Streicher, B.

    2011-01-01

    Nuclear structure and decay of isomeric states in 253 No were investigated. The isotope was produced by the reaction 48 Ca + 207 Pb. The excitation energy of the known single-particle isomeric state (5/2 + [622]) was measured by delayed coincidences between γ-rays and implanted evaporation residues and was placed into the level scheme. In addition, decay of a high-lying multi-quasiparticle isomer in 253 No was studied using e - -γ coincidence measurements. A rotational band populated by its de-excitation was identified in 253 No. A new isomeric state in 253 Fm was observed and a partial-level scheme for this isotope is suggested. In addition γ transitions from excited levels are reported for 253 Md. (orig.)

  16. Isomerization Intermediates In Solution Phase Photochemistry Of Stilbenes

    Science.gov (United States)

    Doany, F. E.; Hochstrasser, R. M.; Greene, B. I.

    1985-04-01

    Picosecond and subpicosecond spectroscopic studies have revealed evidence for an isomerization intermediate between cis and trans in the photoinduced isomerism of both stilbene and biindanyledene ("stiff" stilbene). In stiff stilbene, a transient absorption at 351 nm displays time evolution and viscosity dependence consistent with absorption by a twisted intermediate ("phantom" state) with a lOps lifetime. An analagous bottleneck state with a life-time of 4ps is also consistent with the ground state recovery dynamics of t-stilbene following excitation of c-stilbene when monitored with 0.1ps resolution.

  17. Evaluation of isomeric excitation functions in neutron induced reactions

    International Nuclear Information System (INIS)

    Grudzevich, O.; Ignatyuk, A.; Zolotarev, K.

    1992-01-01

    The possibilities of isomer levels experimental excitation functions description with theoretical models are discussed. It is shown that the experimental data in many cases can be described by theoretical models quite well without parameter fitting. However, large discrepancies are observed for some reactions. In our opinion, these discrepancies are due to uncertainties of discrete level schemes, schemes of gamma-transitions between levels and spin dependence of level density. Small values of isomeric ratios (< 0.1) have been described with the largest errors. The simple formulae for energy dependence of isomeric ratio for (n,g) reaction has been proposed. (author). 53 refs, 10 figs, 8 tabs

  18. cis–trans Isomerization of silybins A and B

    Directory of Open Access Journals (Sweden)

    Michaela Novotná

    2014-05-01

    Full Text Available Methods were developed and optimized for the preparation of the 2,3-cis- and the 10,11-cis-isomers of silybin by the Lewis acid catalyzed (BF3∙OEt2 isomerization of silybins A (1a and B (1b (trans-isomers. The absolute configuration of all optically pure compounds was determined by using NMR and comparing their electronic circular dichroism data with model compounds of known absolute configurations. Mechanisms for cis–trans-isomerization of silybin are proposed and supported by quantum mechanical calculations.

  19. POSSESSION, REVIEW FROM CULTURAL AND PSYCHIATRY

    Directory of Open Access Journals (Sweden)

    Ni Ketut Sri Diniari

    2013-03-01

    Full Text Available Possession is a culture related syndrome, commonly found in Indonesia including Bali. We can see this event in religion and cultural ceremony and at other times at school, home, and in society. This syndrome consist of temporary loss of self identification and environment awareness; in several events a person acts as if he/she was controlled by other being, magic force, spirit or ‘other forces’. There are still several different opinions about trance-possession, whether it is related to certain culture or is a part of mental disorder. DSM-IV-TR and PPDGJ-III defined trance-possession as mental disorder (dissociative for involuntary possession, if it is not a common activity, and if it is not a part of religion or cultural event. (MEDICINA 2012;43:37-40.

  20. Subself theory and reincarnation/possession.

    Science.gov (United States)

    Lester, David

    2004-12-01

    A subself model of the mind is used to account for multiple personality, possession, the spirit controls of mediums, reincarnation, and the auditory hallucinations of schizophrenics, with suggestions for empirical research.

  1. The Impact of Banning Juvenile Gun Possession.

    OpenAIRE

    Marvell, Thomas B

    2001-01-01

    A 1994 federal law bans possession of handguns by persons under 18 years of age. Also in 1994, 11 states passed their own juvenile gun possession bans. Eighteen states had previously passed bans, 15 of them between 1975 and 1993. These laws were intended to reduce homicides, but arguments can be made that they have no effect on or that they even increase the homicide rate. This paper estimates the laws' impacts on various crime measures, primarily juvenile gun homicide victimizations and suic...

  2. Evaluation of excitation functions for isomeric levels in neutron reactions

    International Nuclear Information System (INIS)

    Grudzevich, O.T.; Zelenetskij, A.V.; Zolotarev, K.I.; Kornilov, N.V.; Pashchenko, A.B.

    1993-07-01

    The authors consider the use of theoretical models to describe experimental excitation functions for isomeric levels in neutron reactions and to predict the cross-sections when no experimental data are available. It is shown that, in many cases, experimental data can be described quite satisfactorily by calculations without adjustment of parameters. For threshold reactions at a neutron energy of ∼ 14 MeV the agreement between calculated and experimental isomeric ratios is ∼ 20%, and is determined mainly by errors in the experimental ratios. However, for some reactions there are considerable differences between experimental and calculated data, which are due, in the authors' opinion, to uncertainties in the schemes of the low-lying levels and of gamma transitions between levels and to the spin dependence of level density. The small isomeric ratio values R<0.1 are described with the lowest accuracy. A formula is suggested for the energy dependence of the isomeric ratio in the (n,γ) reaction. (author)

  3. cis-trans Isomerization of silybins A and B

    Czech Academy of Sciences Publication Activity Database

    Novotná, Michaela; Gažák, Radek; Biedermann, David; Di Meo, F.; Marhol, Petr; Kuzma, Marek; Bednárová, Lucie; Fuksová, Kateřina; Trouillas, P.; Křen, Vladimír

    -, č. 10 (2014), s. 1047-1063 ISSN 1860-5397 R&D Projects: GA ČR GAP207/10/0288; GA MŠk LH13097; GA MŠk(CZ) LD13041 Institutional support: RVO:61388971 ; RVO:61388963 Keywords : isomerization * silibinin * silybin Subject RIV: CC - Organic Chemistry Impact factor: 2.762, year: 2014

  4. Isomerization of β-carotene by titanium tetrachloride catalyst

    Indian Academy of Sciences (India)

    TECS

    2007-05-04

    May 4, 2007 ... antioxidant because of the presence of a long chain of conjugated carbon-carbon double bonds. ... such as extraction, chromatography etc. It has been reported that the chlorinated solvents can promote isomerization of trans conjugated polyenes such as β-carotene during extraction.5. Also, the isomeriza-.

  5. Isomerization of 2-phospha-4-silabicyclo[1.10]butane

    NARCIS (Netherlands)

    Slootweg, J.C.; Ehlers, A.W.; Lammertsma, K.

    2004-01-01

    In analogy with the valence isomerism of the hydrocarbons bicyclobutane, 1,3-butadiene and cyclobutene, the rearrangements for 2-phospha-4-sila- bicyclo[1.1.0]butane were studied at the B3LYP/6-311+G** level of theory. The monocyclic 1,2-dihydro-1,2-phosphasilete is shown to be the thermodynamically

  6. Possession divestment by sales in later life.

    Science.gov (United States)

    Ekerdt, David J; Addington, Aislinn

    2015-08-01

    Residential relocation in later life is almost always a downsizing, with many possessions to be divested in a short period of time. This article examines older movers' capacities for selling things, and ways that selling attenuates people's ties to those things, thus accomplishing the human dis-possession of the material convoy. In qualitative interviews in 79 households in the Midwestern United States, older adults reported their experience with possession sales associated with residential relocation. Among this group, three-quarters of the households downsized by selling some belongings. Informal sales seemed the least fraught of all strategies, estate sales had mixed reviews, and garage sales were recalled as laborious. Sellers' efforts were eased by social relations and social networks as helpers and buyers came forward. As selling proceeded, sentiment about possessions waned as their materiality and economic value came to the fore, easing their detachment from the household. Possession selling is challenging because older adults are limited in the knowledge, skills, and efforts that they can apply to the recommodification of their belongings. Selling can nonetheless be encouraged as a divestment strategy as long as the frustrations and drawbacks are transparent, and the goal of ridding is kept in view. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. The Failed Image and the Possessed

    DEFF Research Database (Denmark)

    Suhr, Christian

    2015-01-01

    This article asks if the recurrent queries regarding the value of images in visual anthropology could find new answers by exploring responses to visual media in neo-orthodox Islam. It proposes that the visual display of the photographic image shares a curious resemblance to the bodies of people...... possessed by invisible spirits called jinn. The image as a failed example or model of reality works like the possessed body as an amplifier of invisibility pointing towards that which cannot be seen, depicted visually, or represented in writing. This suggests a negative epistemology in which images obtain...

  8. Left cardiac isomerism in the Sonic hedgehog null mouse.

    Science.gov (United States)

    Hildreth, Victoria; Webb, Sandra; Chaudhry, Bill; Peat, Jonathan D; Phillips, Helen M; Brown, Nigel; Anderson, Robert H; Henderson, Deborah J

    2009-06-01

    Sonic hedgehog (Shh) is a secreted morphogen necessary for the production of sidedness in the developing embryo. In this study, we describe the morphology of the atrial chambers and atrioventricular junctions of the Shh null mouse heart. We demonstrate that the essential phenotypic feature is isomerism of the left atrial appendages, in combination with an atrioventricular septal defect and a common atrioventricular junction. These malformations are known to be frequent in humans with left isomerism. To confirm the presence of left isomerism, we show that Pitx2c, a recognized determinant of morphological leftness, is expressed in the Shh null mutants on both the right and left sides of the inflow region, and on both sides of the solitary arterial trunk exiting from the heart. It has been established that derivatives of the second heart field expressing Isl1 are asymmetrically distributed in the developing normal heart. We now show that this population is reduced in the hearts from the Shh null mutants, likely contributing to the defects. To distinguish the consequences of reduced contributions from the second heart field from those of left-right patterning disturbance, we disrupted the movement of second heart field cells into the heart by expressing dominant-negative Rho kinase in the population of cells expressing Isl1. This resulted in absence of the vestibular spine, and presence of atrioventricular septal defects closely resembling those seen in the hearts from the Shh null mutants. The primary atrial septum, however, was well formed, and there was no evidence of isomerism of the atrial appendages, suggesting that these features do not relate to disruption of the contributions made by the second heart field. We demonstrate, therefore, that the Shh null mouse is a model of isomerism of the left atrial appendages, and show that the recognized associated malformations found at the venous pole of the heart in the setting of left isomerism are likely to arise from

  9. Digital possessions after a romantic break up

    NARCIS (Netherlands)

    Herron, Daniel; Moncur, Wendy; van den Hoven, Elise

    2016-01-01

    With technology becoming more pervasive in everyday life, it is common for individuals to use digital media to support the enactment and maintenance of romantic relationships. Partners in a relationship may create digital possessions frequently. However, after a relationship ends, individuals

  10. POSSESSION VERSUS POSITION: STRATEGIC EVALUATION IN AFL

    Directory of Open Access Journals (Sweden)

    Darren M. O'Shaughnessy

    2006-12-01

    Full Text Available In sports like Australian Rules football and soccer, teams must battle to achieve possession of the ball in sufficient space to make optimal use of it. Ultimately the teams need to score, and to do that the ball must be brought into the area in front of goal - the place where the defence usually concentrates on shutting down space and opportunity time. Coaches would like to quantify the trade-offs between contested play in good positions and uncontested play in less promising positions, in order to inform their decision-making about where to put their players, and when to gamble on sending the ball to a contest rather than simply maintain possession. To evaluate football strategies, Champion Data has collected the on-ground locations of all 350,000 possessions and stoppages in the past two seasons of AFL (2004, 2005. By following each chain of play through to the next score, we can now reliably estimate the scoreboard "equity" of possessing the ball at any location, and measure the effect of having sufficient time to dispose of it effectively. As expected, winning the ball under physical pressure (through a "hard ball get" is far more difficult to convert into a score than winning it via a mark. We also analyse some equity gradients to show how getting the ball 20 metres closer to goal is much more important in certain areas of the ground than in others. We conclude by looking at the choices faced by players in possession wanting to maximise their likelihood of success

  11. Isomeric rations study for the α + 70 Ge

    International Nuclear Information System (INIS)

    Hora Villano, M.H. da.

    1984-12-01

    Isomeric ratios for 73 Se F,I produced in the reaction α + 70 Ge with incidence laboratory energy ranging from 8 to 28 MeV, have been measured using off-line γ-ray spectroscopy. Relative formation cross-section for isomeric and ground states were obtained with NAT Ge targets. Compound nucleus statistical analyses were performed using computer codes Alice and Julian. Unlike to Alice code, the Julian code predictions agreed quite well with the experimental results. This agreement may be explained by the inclusion of the γ competition in the deexcitation channels of the compound nucleus and by the correct level density calculation of the emission probabilities in the Julian code. Finally angular momentum populations for isomers formations in the reaction 70 Ge(α, n) 73 have been determined. (author)

  12. Determination of the production rate of low intensity isomeric transitions

    International Nuclear Information System (INIS)

    Lakosi, L.; Veres, A.; Tam, N.C.; Pavlicsek, I.

    1992-01-01

    Flat 2π and cylindrical 4π multiwire proportional counters were built for counting for low energy internal conversion electrons from the nuclear isomers 83m Kr, 103m Rh and 189m Os, induced by irradiation with high intensity 60 Co and 4 MeV bremsstrahlung sources. The β-decay of 176m Lu was recorded by a plastic scintillator. In this way higher sensitivities were attained than by detecting γ-rays or characteristic X-rays associated with the isomeric transitions, and the excitation of 189m Os by low energy 137 Cs and 300 kV X-ray sources also became detectable. Comparatively large isomeric activities produced by linac irradiation were standardizing by a Ge spectrometer for calibrating proportional and scintillation counting. (orig.)

  13. Study of the isomeric states of 66As

    International Nuclear Information System (INIS)

    Czajkowski, S.; Blank, B.; Andriamonje, S.; Attallah, F.; Boue, F.; Davi, F.; Del Moral, R.; Fleury, A.; Musquere, A.; Pravikoff, M.S.; Dufour, J-P; Grzywacz, R.; Janas, Z.; Karny, M.; Pfuetzner, M.; Donzaud, C.; Grewe, A.; Heinz, A.; Junghans, A.; Lewitowicz, M.; Sauvestre, J-E.

    1997-01-01

    The most neutron-deficient isotopes in the N = Z region are an important source of information on the neutron-proton interaction far off stability. The isotopes in this region are characterized by an extreme sensitivity of the deformation to the isospin variations. Here the structure of deformed shells are favoring the high spin states the lifetime of which being sufficient long to be observed after flight time of the order of the microsecond. The study of the decay of this isomeric states permits to approach the structure of the first excited levels of this isotopes. Recent experiments at GANIL with the SISSI - LISE 3 spectrometer were performed to study the neutron deficient nucleus 66 As. This nucleus was produced in the fragmentation of 70 MeV/u 78 Kr primary beam in a nickel target. Two new isomeric states have been observed. From the observed γ transitions a decay scheme is proposed

  14. Surface study of mixtures containing cyclic ethers and isomeric chlorobutanes

    International Nuclear Information System (INIS)

    Royo, F.M.; Villares, A.; Martin, S.; Giner, B.; Lafuente, C.

    2007-01-01

    Experimental surface tensions and the corresponding surface tensions deviations for the mixtures containing 1,3-dioxolane or 1,4-dioxane and 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane or 2-chloro-2-methylpropane, measured with a drop volume tensiometer, are reported at the temperatures of 298.15 K and 313.15 K. The excess surface concentrations of isomeric chlorobutanes are also evaluated using a monolayer model

  15. Deconstructing field-induced ketene isomerization through Lagrangian descriptors.

    Science.gov (United States)

    Craven, Galen T; Hernandez, Rigoberto

    2016-02-07

    The time-dependent geometrical separatrices governing state transitions in field-induced ketene isomerization are constructed using the method of Lagrangian descriptors. We obtain the stable and unstable manifolds of time-varying transition states as dynamic phase space objects governing configurational changes when the ketene molecule is subjected to an oscillating electric field. The dynamics of the isomerization reaction are modeled through classical trajectory studies on the Gezelter-Miller potential energy surface and an approximate dipole moment model which is coupled to a time-dependent electric field. We obtain a representation of the reaction geometry, over varying field strengths and oscillation frequencies, by partitioning an initial phase space into basins labeled according to which product state is reached at a given time. The borders between these basins are in agreement with those obtained using Lagrangian descriptors, even in regimes exhibiting chaotic dynamics. Major outcomes of this work are: validation and extension of a transition state theory framework built from Lagrangian descriptors, elaboration of the applicability for this theory to periodically- and aperiodically-driven molecular systems, and prediction of regimes in which isomerization of ketene and its derivatives may be controlled using an external field.

  16. Taking Possession: Rituals, Space and Authority

    Directory of Open Access Journals (Sweden)

    Jennifer Mara DeSilva

    2016-12-01

    Full Text Available In early modern Europe authority over communities, both people and spaces, was visualized through ritual gestures and processions. Communities gathered to witness ceremonial entries that drew on accepted forms of gestures and speech identifying individuals and articulating their place in the urban power relationship. Ceremonial entries by rulers, ambassadors, bishops, and other office-holders drew on ritual acts projecting messages of possession in order to establish reputations of prestige and authority. This introductory essay draws on cultural anthropology and recent historiography to build a framework for understanding rituals of possession that went beyond the tradition triumphal entry to incorporate substitutes, new modes of prestigious display, and attend to conflicts. By “taking possession” of communities, offices, and spaces using accepted ritual forms, early moderns initiated conversations about authority and power that were far more flexible in their scope, practice, and participants than expected.

  17. Using {sup 233}U-doped crystals to access the few-eV isomeric transition in {sup 229}Th

    Energy Technology Data Exchange (ETDEWEB)

    Stellmer, Simon; Schreitl, Matthias; Kazakov, Georgy A.; Sterba, Johannes H.; Schumm, Thorsten [Vienna Center for Quantum Science and Technology (VCQ) and Atominstitut, TU Wien, Vienna (Austria)

    2016-07-01

    The isotope {sup 229}Th possesses an exceptionally low-lying isomeric state at an energy of only a few eV. While direct laser excitation of the isomer is a tantalizing future prospect, the stage is not yet set for nuclear laser spectroscopy: too little is known about the energy, lifetime, and internal conversion pathways of the isomer. Alternative routes to populate the isomer are needed for further investigations. We use the alpha decay {sup 233}U →{sup 229g,m}Th to populate the isomer with a probability of 2%. The {sup 233}U is embedded into VUV-transparent crystals, as the isomer transition is expected around 160 nm. The wavelength of the gamma ray, emitted upon de-excitation of the isomer into the ground state, is measured with a spectrometer. Calculations show that the isomer emission is not obscured by radioluminescence of the crystal. We report on the current status of the experiment.

  18. Tracer kinetic investigations on isomerization and synthesis of /sup 8/C-aromates. II. Isomerization of ethylbenzene by means of heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dermietzel, J; Roesseler, M; Jockisch, W; Wienhold, C [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung; Franke, H; Klempin, J; Barz, H J [VEB Petrolchemisches Kombinat Schwedt (German Democratic Republic)

    1978-01-01

    The mechanism of ethylbenzene isomerization on Pt/Al/sub 2/O/sub 3/ catalysts by means of /sup 14/C labelled compounds has been investigated, measuring the isotope distribution between ring and alkyl carbon atoms. The results suggest that ethylbenzene isomerizes via structure rearrangement involving ring carbon atoms. A similar mechanism takes place in xylene isomerization under increased hydrogen partial pressure, while under normal pressure 1,2-methyl group shifting is dominating. All three xylenes are formed from ethylbenzene by parallel reactions.

  19. Combined Function of Brønsted and Lewis Acidity in the Zeolite-Catalyzed Isomerization of Glucose to Fructose in Alcohols

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Riisager, Anders; Taarning, Esben

    2016-01-01

    Glucose conversion via fructose to useful chemicals and fuels has attracted considerable attention. Isomerization of glucose to fructose can proceed along several different reaction pathways involving different sugar intermediates and isomeric forms. Presently, the roles of the substrate isomeric...

  20. Pion condensation and density isomerism in nuclear matter

    International Nuclear Information System (INIS)

    Hecking, P.; Weise, W.

    1979-01-01

    The possible existence of density isomers in nuclear matter, induced by pion condensation, is discussed; the nuclear equation of state is treated within the framework of the sigma model. Repulsive short-range baryon-baryon correlations, the admixture of Δ (1232) isobars and finite-range pion-baryon vertex form factors are taken into account. The strong dependence of density isomerism on the high density extrapolation of the equation of state for normal nuclear matter is also investigated. We find that, once finite range pion-baryon vertices are introduced, the appearance of density isomers becomes unlikely

  1. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

  2. Geometrical Optimization Approach to Isomerization: Models and Limitations.

    Science.gov (United States)

    Chang, Bo Y; Shin, Seokmin; Engel, Volker; Sola, Ignacio R

    2017-11-02

    We study laser-driven isomerization reactions through an excited electronic state using the recently developed Geometrical Optimization procedure. Our goal is to analyze whether an initial wave packet in the ground state, with optimized amplitudes and phases, can be used to enhance the yield of the reaction at faster rates, driven by a single picosecond pulse or a pair of femtosecond pulses resonant with the electronic transition. We show that the symmetry of the system imposes limitations in the optimization procedure, such that the method rediscovers the pump-dump mechanism.

  3. Isomeric island in the vicinity of 66Fe

    International Nuclear Information System (INIS)

    Daugas, J. M.; Belier, G.; Girod, M.; Goutte, H.; Meot, V.; Perru, O.; Roig, O.; Sauvestre, J. E.; Sawicka, M.; Pfuetzner, M.; Zylicz, J.; Matea, I.; Giovinazzo, J.; Grawe, H.; Becker, F.; Mayet, P.; Grzywacz, R.; Achouri, N. L.; Angelique, J. C.; Baiborodin, D.

    2006-01-01

    An island of isomers have recently been observed on both sides of the N=40 shell below the Ni isotopes. Isomeric states in the 65Fe and 67Fe allow the knowledge of the single particle structure around the νg9/2 shell. Moreover, the excitation energy of the first 2+ and 4+ states in the 68Fe have been established by β-γ correlation. The evolution of the structure of the Fe isotopes going far away from the valley of stability is, for the first time, given for N>40

  4. Male homosexuality and spirit possession in Brazil.

    Science.gov (United States)

    Fry, P

    1985-01-01

    This paper examines the relationship between male homosexuality and the Afro-Brazilian possession cults in Belém do Parà. After a discussion of the literature follows a description of the cults' beliefs, rites and social organization. Male sex roles are then discussed and the two categories, bicha and man, analyzed. It is noted that there is no term which is equivalent to the western category of "homosexual" in this taxonomic system. After putting forward folk explanations for the presence of many bichas in the cults, an analysis is put forward of the social rewards available to bichas within these cults, and the structural relationship between homosexuality and these regions in terms of their congruent marginality vis-à-vis "normal society."

  5. Predicative possession in Medieval Slavic Bible translations Predicative Possession in Early Biblical Slavic

    Directory of Open Access Journals (Sweden)

    Julia McAnallen

    2011-08-01

    Full Text Available Late Proto-Slavic (LPS had an inventory of three constructions for expressing predicative possession. Using the earliest Slavic Bible translations from Old Church Slavic (OCS, and to a lesser degree Old Czech, a number of conclusions can be drawn about the status of predicative possession for LPS. The verb iměti ‘have’ was the most frequent and least syntactically and semantically restricted predicative possessive construction (PPC. Existential PPCs with a dative possessor appear primarily with kinship relations, abstract possessums, and in a number of other fixed construction types; existential PPCs with the possessor in an u + genitive prepositional phrase primarily appear with concrete and countable possessums. Both existential PPCs call for an animate, most often pronominal, possessor. The u + genitive was the rarest type of PPC in LPS, though it had undoubtedly grammaticalized as a PPC.

  6. Xylose Isomerization with Zeolites in a Two-Step Alcohol–Water Process

    DEFF Research Database (Denmark)

    Paniagua, Marta; Shunmugavel, Saravanamurugan; Melián Rodriguez, Mayra

    2015-01-01

    Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol–water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl...

  7. Control of structural isomerism in noncovalent hydrogen-bonded assemblies using peripheral chiral information

    NARCIS (Netherlands)

    Prins, L.J.; Jolliffe, K.A.; Hulst, A.J.R.L.; Timmerman, P.; Reinhoudt, David

    2000-01-01

    The results of a systematic study of the structural isomerism in more than 30 noncovalent hydrogen-bonded assemblies are described. These dynamic assemblies, composed of three calix[4]arene dimelamines and six barbiturates/cyanurates, can be present in three isomeric forms with either D3, C3h, or Cs

  8. Iridium-Catalyzed Dynamic Kinetic Isomerization: Expedient Synthesis of Carbohydrates from Achmatowicz Rearrangement Products.

    Science.gov (United States)

    Wang, Hao-Yuan; Yang, Ka; Bennett, Scott R; Guo, Sheng-rong; Tang, Weiping

    2015-07-20

    A highly stereoselective dynamic kinetic isomerization of Achmatowicz rearrangement products was discovered. This new internal redox isomerization provided ready access to key intermediates for the enantio- and diastereoselective synthesis of a series of naturally occurring sugars. The nature of the de novo synthesis also enables the preparation of both enantiomers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Analysis of Optimal Process Flow Diagrams of Light Naphtha Isomerization Process by Mathematic Modelling Method

    OpenAIRE

    Chuzlov, Vyacheslav Alekseevich; Molotov, Konstantin

    2016-01-01

    An approach to simulation of hydrocarbons refining processes catalytic reactors. The kinetic and thermodynamic research of light naphtha isomerization process was conducted. The kinetic parameters of hydrocarbon feedstock chemical conversion on different types of platinum-content catalysts was established. The estimation of efficiency of including different types of isomerization technologies in oil refinery flow diagram was performed.

  10. Green Synthesis of Carvenone by Montmorillonite-Catalyzed Isomerization of 1,2-Limonene Oxide

    DEFF Research Database (Denmark)

    Nguyen, Thao-Tran Thi; Chau, Duy-Khiem Nguyen; Duus, Fritz

    2013-01-01

    Montmorillonite was considered as a good heterogeneous catalyst for the isomerization of 1,2-limonene oxide into car-venone under solvent-free condition. Both conventional heating and green activations were tested in this research. The microwave-assisted isomerization afforded carvenone in high...

  11. Analysis of Optimal Process Flow Diagrams of Light Naphtha Isomerization Process by Mathematic Modelling Method

    Directory of Open Access Journals (Sweden)

    Chuzlov Vjacheslav

    2016-01-01

    Full Text Available An approach to simulation of hydrocarbons refining processes catalytic reactors. The kinetic and thermodynamic research of light naphtha isomerization process was conducted. The kinetic parameters of hydrocarbon feedstock chemical conversion on different types of platinum-content catalysts was established. The estimation of efficiency of including different types of isomerization technologies in oil refinery flow diagram was performed.

  12. Tandem ring-closing metathesis/isomerization reactions for the total synthesis of violacein

    DEFF Research Database (Denmark)

    Petersen, Mette Terp; Nielsen, Thomas Eiland

    2013-01-01

    A series of 5-substituted 2-pyrrolidinones was synthesized through a one-pot ruthenium alkylidene-catalyzed tandem RCM/isomerization/nucleophilic addition sequence. The intermediates resulting from RCM/isomerization showed reactivity toward electrophiles in aldol condensation reactions which...

  13. 50 CFR 20.38 - Possession of live birds.

    Science.gov (United States)

    2010-10-01

    ... 50 Wildlife and Fisheries 6 2010-10-01 2010-10-01 false Possession of live birds. 20.38 Section 20... WILDLIFE AND PLANTS (CONTINUED) MIGRATORY BIRD HUNTING Possession § 20.38 Possession of live birds. Every migratory game bird wounded by hunting and reduced to possession by the hunter shall be immediately killed...

  14. Excitation functions and isomeric ratios for the isomeric pair sup(106m)Ag and sup(106g)Ag in the 107Ag (d,t) reaction

    International Nuclear Information System (INIS)

    Lalli, M.E.; Wasilevsky de Lammirato, C.; Herreros, O.R.; Nassiff, S.J.

    1976-09-01

    Excitation functions and isomeric cross section ratios have been measured for the 107 Ag (d,t), reaction in which the isomeric pair sup(106m/106g)Ag is produced. Thick-target yields have been determined for different irradiation times and as a function of deuteron energy. Stacked silver foils with aluminium foils as monitors were bombarded with deuterons up to 27 MeV and the activities of products measured with a calibrated Ge(Li) counter. (author) [es

  15. Process for paraffin isomerization of a distillate range hydrocarbon feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Chen, N.Y.; Garwood, W.E.; McCullen, S.B.

    1993-01-19

    Various catalytic processes have been proposed to isomerize n-paraffins so as to lower the pour point of distillate range hydrocarbon feedstocks. However, many available feedstocks contain nitrogen impurities which tend to poison conventional paraffin isomerization catalysts. A process has been developed to obviate or alleviate this problem. According to the invention, the paraffin-containing feedstock is contacted with a crystalline aluminosilicate zeolite catalyst having pore openings defined by a ratio of sorption of n-hexane to o-xylene of over 3 vol % and the ability to crack 3-methylpentane in preference to 2,3 dimethylbutane under defined conditions. The zeolite catalyst includes a Group VIII metal and has a zeolite SiO[sub 2]/Al[sub 2]O[sub 3] ratio of at least 20:1. The contacting is carried out at 199-454 C and a pressure of 100-1,000 psig, preferably 250-600 psig. The group of medium pore zeolites which can be used in the process of the invention includes ZSM-22, ZSM-23, and ZSM-35. The Group VIII metals used in the catalyst are preferably selected from Pt, Pd, Ir, Os, Rh, and Ru and the metal is preferably incorporated into the zeolite by ion exchange up to a metal content of preferably 0.1-3 wt %. Experiments are described to illustrate the invention. 1 tab.

  16. Computational Studies of Bridging Structures and Isomerism in Substituted Disilynes.

    Science.gov (United States)

    Serafin, Lukasz M; Law, Mark M; van Mourik, Tanja

    2013-06-11

    The substituted disilyne molecules, Si2Li2 and Si2HX, where X = Li, F, and Cl, have been investigated using the high-level CCSD(T) and CCSD(T)-F12 ab initio methods. The calculations have found or confirmed the existence of several isomeric forms and transition states for each molecule. Optimized geometries, relative energies, and harmonic vibration frequencies are reported. Bridging structures exist in all cases. Comparisons are made with existing literature results for the related Si2H2, C2X2, and C2HX isomerizing systems. Additionally, CCSD(T) and CCSD(T)-F12 calculations were performed for Si2H2, for which experimental spectroscopic data are available. Results calculated with CCSD(T)-F12 and the cc-pVTZ-F12 basis set are of comparable quality as those computed with CCSD(T) and the much larger cc-pV(6+d)Z basis set, at much less computational cost. We recommend the CCSD(T)-F12/cc-pVTZ-F12 level of theory as a very attractive alternative to conventional CCSD(T).

  17. Low-lying isomeric levels in Cu75

    Science.gov (United States)

    Daugas, J. M.; Faul, T.; Grawe, H.; Pfützner, M.; Grzywacz, R.; Lewitowicz, M.; Achouri, N. L.; Angélique, J. C.; Baiborodin, D.; Bentida, R.; Béraud, R.; Borcea, C.; Bingham, C. R.; Catford, W. N.; Emsallem, A.; de France, G.; Grzywacz, K. L.; Lemmon, R. C.; Lopez Jimenez, M. J.; de Oliveira Santos, F.; Regan, P. H.; Rykaczewski, K.; Sauvestre, J. E.; Sawicka, M.; Stanoiu, M.; Sieja, K.; Nowacki, F.

    2010-03-01

    Isomeric low-lying states were identified and investigated in the Cu75 nucleus. Two states at 61.8(5)- and 128.3(7)-keV excitation energies with half-lives of 370(40)- and 170(15)-ns were assigned as Cu75m1 and Cu75m2, respectively. The measured half-lives combined with the recent spin assignment of the ground state allow one to deduce tentatively spin and parity of the two isomers and the dominant multipolarities of the isomeric transitions with respect to the systematics of the Cu isotopes. Shell-model calculations using an up-to-date effective interaction reproduce the evolution of the 1/2-, 3/2-, and 5/2- states for the neutron-rich odd-mass Cu isotopes when filling the νg9/2. The results indicate a significant change in the nuclear structure in this region, where a single-particle 5/2- state coexists with more and more collective 3/2- and 1/2- levels at low excitation energies.

  18. Destabilization in the isomeric nitrobenzonitriles: an experimental thermochemical study

    International Nuclear Information System (INIS)

    Roux, Maria Victoria; Jimenez, Pilar; Davalos, Juan Z.; Temprado, Manuel; Liebman, Joel F.

    2003-01-01

    The enthalpies of combustion and of sublimation, respectively, of the three isomeric nitrobenzonitriles have been measured: o-, {(-3456.3±2.9), (88.1±1.4)} kJ·mol -1 ; m-, {(-3442.8±3.3), (92.8±0.3)} kJ·mol -1 ; p-, {(-3448.2±3.6), (91.1±1.3)} kJ·mol -1 . In turn, from these values, the standard molar enthalpies of formation for the condensed and gaseous state, respectively, have been derived: o-, {(130.1±3.1), (218.2±3.4)} kJ·mol -1 ; m-, {(116.5±3.5), (209.3±3.5)} kJ·mol -1 ; p-, {(122.0±3.8), (213.1±4.0)} kJ·mol -1 . Destabilization energies associated with the presence of the two electron-withdrawing groups have been determined, for o-, m-, and p-nitrobenzonitrile, {(17.6±4.1), (8.7±4.2), and (12.5±4.6)} kJ·mol -1 , respectively, and are consistent with those obtained for the corresponding sets of isomeric methyl benzenedicarboxylates, dicyanobenzenes, dinitrobenzenes, and (neutral and ionized) nitrobenzoic acids

  19. Catalyst compositions useful for olefin isomerization and disproportionation

    International Nuclear Information System (INIS)

    Drake, C.A.

    1987-01-01

    A process is described for the double bond isomerization of an aliphatic olefinic hydrocarbon feed which comprises contacting the feed under isomerization conditions with a catalyst prepared by: (a) impregnating an alumina support having a surface area of at least 200 m/sup 2//g and a pore volume of at least 0.45 cm/sup 3//g with: 1 up to 20 wt. % of at least one magnesium compound convertible to the oxide, based on the weight of support and calculated as the metal; 0 up to 5 wt. % of at least one alkali metal compound convertible to the oxide, based on the weight of support and calculated as the metal; and 0 up to 5 wt. % of at least one zirconium compound convertible to the oxide, based on the weight of support and calculated as the metal; and (b) heating the alumina support impregnated in accordance with step (a) in an oxygen-containing atmosphere under conditions suitable to convert at least a portion of the magnesium, alkali metal, and zirconium compounds to the oxide form

  20. 22 CFR 72.14 - Nominal possession; property not normally taken into physical possession.

    Science.gov (United States)

    2010-04-01

    ... possession. (a) When a consular officer take articles of a decedent's personal property from a foreign... Department discharging the consular officer of any responsibility for the articles transferred. (b) A... effects; (2) Motor vehicles, airplanes or watercraft; (3) Toiletries, such as toothpaste or razors; (4...

  1. β-γ and isomeric decay spectroscopy of 168Dy

    Directory of Open Access Journals (Sweden)

    Zhang G.X.

    2018-01-01

    Full Text Available This contribution will report on the experimental work on the level structure of 168Dy. The experimental data have been taken as part of the EURICA decay spectroscopy campaign at RIBF, RIKEN in November 2014. In the experiment, a 238U primary beam is accelerated up to 345 MeV/u with an average intensity of 12 pnA. The nuclei of interest are produced by in-flight fission of 238U impinging on Be target with a thickness of 5 mm. The excited states of 168Dy have been populated through the decay from a newly identified isomeric state and via the β decay from 168Tb. In this contribution, scientific motivations, experimental procedure and some preliminary results for this study are presented.

  2. β-γ and isomeric decay spectroscopy of 168Dy

    Science.gov (United States)

    Zhang, G. X.; Watanabe, H.; Kondev, F. G.; Lane, G. J.; Regan, P. H.; Söderström, P.-A.; Walker, P. M.; Kanaoka, H.; Korkulu, Z.; Lee, P. S.; Liu, J. J.; Nishimura, S.; Wu, J.; Yagi, A.; Ahn, D. S.; Alharbi, T.; Baba, H.; Browne, F.; Bruce, A. M.; Carroll, R. J.; Chae, K. Y.; Dombradi, Zs.; Doornenbal, P.; Estrade, A.; Fukuda, N.; Griffin, C.; Ideguchi, E.; Inabe, N.; Isobe, T.; Kanaya, S.; Kojouharov, I.; Kubo, T.; Kubono, S.; Kurz, N.; Kuti, I.; Lalkovski, S.; Lee, C. S.; Lee, E. J.; Lorusso, G.; Lotay, G.; Moon, C.-B.; Nishizuka, I.; Nita, C. R.; Odahara, A.; Patel, Z.; Phong, V. H.; Podolyák, Zs.; Roberts, O. J.; Sakurai, H.; Schaffner, H.; Shand, C. M.; Shimizu, Y.; Sumikama, T.; Suzuki, H.; Takeda, H.; Terashima, S.; Vajta, Zs.; Valiente-Dóbon, J. J.; Xu, Z. Y.

    2018-05-01

    This contribution will report on the experimental work on the level structure of 168Dy. The experimental data have been taken as part of the EURICA decay spectroscopy campaign at RIBF, RIKEN in November 2014. In the experiment, a 238U primary beam is accelerated up to 345 MeV/u with an average intensity of 12 pnA. The nuclei of interest are produced by in-flight fission of 238U impinging on Be target with a thickness of 5 mm. The excited states of 168Dy have been populated through the decay from a newly identified isomeric state and via the β decay from 168Tb. In this contribution, scientific motivations, experimental procedure and some preliminary results for this study are presented.

  3. Theoretical study of isomerization and decomposition of propenal

    International Nuclear Information System (INIS)

    Chin, Chih-Hao; Lee, Shih-Huang

    2011-01-01

    We investigated the dynamics of isomerization and multi-channel dissociation of propenal (CH 2 CHCHO), methyl ketene (CH 3 CHCO), hydroxyl propadiene (CH 2 CH 2 CHOH), and hydroxyl cyclopropene (cyclic-C 3 H 3 -OH) in the ground potential-energy surface using quantum-chemical calculations. Optimized structures and vibrational frequencies of molecular species were computed with method B3LYP/6-311G(d,p). Total energies of molecules at optimized structures were computed at the CCSD(T)/6-311+G(3df,2p) level of theory. We established the potential-energy surface for decomposition to CH 2 CHCO + H, CH 2 CH + HCO, CH 2 CH 2 /CH 3 CH + CO, CHCH/CH 2 C + H 2 CO, CHCCHO/CH 2 CCO + H 2 , CHCH + CO + H 2 , CH 3 + HCCO, CH 2 CCH + OH, and CH 2 CC/cyclic-C 3 H 2 + H 2 O. Microcanonical rate coefficients of various reactions of trans-propenal with internal energies 148 and 182 kcal mol -1 were calculated using Rice-Ramsperger-Kassel-Marcus and Variational transition state theories. Product branching ratios were derivable using numerical integration of kinetic master equations and the steady-state approximation. The concerted three-body dissociation of trans-propenal to fragments C 2 H 2 + CO + H 2 is the prevailing channel in present calculations. In contrast, C 3 H 3 O + H, C 2 H 3 + HCO and C 2 H 4 + CO were identified as major channels in the photolysis of trans-propenal. The discrepancy between calculations and experiments in product branching ratios indicates that the three major photodissociation channels occur mainly on an excited potential-energy surface whereas the other channels occur mainly on the ground potential-energy surface. This work provides profound insight in the mechanisms of isomerization and multichannel dissociation of the system C 3 H 4 O.

  4. Ti-Catalyzed Selective Isomerization of Terminal Mono-substituted Olefins

    International Nuclear Information System (INIS)

    Lee, Hyung Soo; Lee, Gab Yong

    2005-01-01

    The isomerization of olefins occurs either by a metal hydride addition-elimination or by a π-allyl metal hydride intermediate. HCo(CO) 4 , [(C 2 H 4 ) 2 RhCl] 2 , Ni[P(OEt) 3 ] 4 , and PtCl 2 (PPh 3 ) 2 -SnCl 2 are effective catalysts for isomerization of olefins via a metal hydride addition-elimination mechanism, 3,4 and Fe 3 (CO) 12 catalyzed isomerization of 3-ethyl-1-pentene and isomerization of 1-heptene catalyzed by (PhCN) 2 PdCl 2 occur via a π-allyl metal hydride mechanism. The cis/trans ratio of 2-butene obtained from isomerization of 1-butene by RhH(CO)(PPh 3 ) 3 has also been investigated. The skeletal isomerization of olefins catalyzed by (R 3 P) 2 NiCl 2 is developed such as conversion of cis-1,4-hexadiene to trans-2-methyl-1,3-pentadiene. Titanium complexes serve as an effective catalysts for a variety of reactions such as hydroalumination, hydroboration, and hydrogenation of unsaturated hydrocarbons. We have been interested in the selective reactions of unsaturated hydrocarbons by using titanium and zirconium compounds. The reagent system composed of LiAlH 4 /Cp 2 TiCl 2 ≤ 2 in the molar ratio promotes the isomerization of 1-octene, but the detailed reaction for isomerization of olefins has not been reported. We report here a selective isomerization of olefins with low valent titanium complex generated from Cp 2 TiCl 2 (Cp=cyclopentadienyl) and LiAlH 4

  5. Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols.

    Science.gov (United States)

    Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément

    2014-12-03

    Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.

  6. New isomeric states in 152,154,156Nd produced by spontaneous fission of 252Cf

    International Nuclear Information System (INIS)

    Gautherin, C.; Houry, M.; Korten, W.; Le Coz, Y.; Lucas, R.; Phan, X.H.; Theisen, C.; Belier, G.; Girod, M.; Meot, V.; Peru, S.; Astier, A.; Ducroux, L.; Meyer, M.; Redon, N.

    1998-01-01

    Isomeric states have been observed in fission-fragments produced by spontaneous fission of 252 Cf. These states are found in neutron rich nuclei of different structure and deformations. About 50 isomeric nuclei have been observed using coincidences between γ-rays identified in EUROGAM II and fission fragments detected in photovoltaic cells (SAPhIR). Lifetimes in the range from 20 ns to 2μs have been measured. Presented calculations based on HFB+D1S force on new measured isomeric states in the 152,154,156 Nd show evidence for K-isomers. (orig.)

  7. Isomerization of glucose into fructose by environmentally friendly Fe/β zeolite catalysts.

    Science.gov (United States)

    Xu, Siquan; Zhang, Lei; Xiao, Kehao; Xia, Haian

    2017-06-29

    Herein, the environmentally friendly Fe/β zeolite for glucose isomerization to fructose in aqueous media was reported for the first time. The effects of various reaction conditions including reaction temperature, reaction time, catalyst dosage, etc. on the isomerization reaction over Fe/β zeolite were studied in detail. Under the optimized conditions, yield of fructose higher than 20% were obtained. Moreover, the Fe/β zeolite catalysts were stable and remained constant catalytic activity after five consecutive runs. The possible active Fe species for isomerization of glucose in Fe/β zeolite is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Possession States: Approaches to Clinical Evaluation and Classification

    Directory of Open Access Journals (Sweden)

    S. McCormick

    1992-01-01

    Full Text Available The fields of anthropology and sociology have produced a large quantity of literature on possession states, physicians however rarely report on such phenomena. As a result clinical description of possession states has suffered, even though these states may be more common and less deviant than supposed. Both ICD-10 and DSM-IV may include specific criteria for possession disorders. The authors briefly review Western notions about possession and kindred states and present guidelines for evaluation and classification.

  9. Direct Measurement of the Isomerization Barrier of the Isolated Retinal Chromophore

    DEFF Research Database (Denmark)

    Dilger, Jonathan; Musbat, Lihi; Sheves, Mordechai

    2015-01-01

    Isomerizations of the retinal chromophore were investigated using the IMS-IMS technique. Four different structural features of the chromophore were observed, isolated, excited collisionally, and the resulting isomer and fragment distributions were measured. By establishing the threshold activatio...

  10. Glucose Isomerization by Enzymes and Chemo-catalysts: Status and Current Advances

    DEFF Research Database (Denmark)

    Li, Hu; Yang, Song; Saravanamurugan, Shunmugavel

    2017-01-01

    of isomerization of aldoses in terms of yields, catalysts, solvents, catalytic systems, etc., by both enzymatic and chemo-catalytic approaches. Among aldose ketose interconversion reactions, fructose production by glucose isomerization to make high-fructose corn syrup (HFCS) is an industrially important and large....../intermediate fructose. This review focuses on how both enzyme and chemo-catalysts are being useful for the isomerization of glucose to fructose. Specifically, development of Lewis acid containing zeolites for glucose isomerization is reviewed in detail, including mechanism, isotopic labeling, and computational studies....... biocatalytic process today, and a large number of studies have been reported on the process development. In parallel, also alternative chemo-catalytic systems have emerged, as enzymatic conversion has drawbacks, though they are typically more selective and produce fructose under mild reaction conditions...

  11. Mechanistic features of isomerizing alkoxycarbonylation of methyl oleate

    KAUST Repository

    Roesle, Philipp

    2012-10-24

    The weakly coordinated triflate complex [(P̂P)Pd(OTf)] +(OTf)- (1) (P̂P = 1,3-bis(di-tert- butylphosphino)propane) is a suitable reactive precursor for mechanistic studies of the isomerizing alkoxcarbonylation of methyl oleate. Addition of CH 3OH or CD3OD to 1 forms the hydride species [(P ̂P)PdH(CH3OH)]+(OTf)- (2-CH3OH) or the deuteride [(P̂P)PdD(CD 3OD)]+(OTf)- (2D-CD3OD), respectively. Further reaction with pyridine cleanly affords the stable and isolable hydride [(P̂P)PdH(pyridine)]+(OTf) - (2-pyr). This complex yields the hydride fragment free of methanol by abstraction of pyridine with BF3OEt2, and thus provides an entry to mechanistic observations including intermediates reactive toward methanol. Exposure of methyl oleate (100 equiv) to 2D-CD 3OD resulted in rapid isomerization to the thermodynamic isomer distribution, 94.3% of internal olefins, 5.5% of α,β-unsaturated ester and <0.2% of terminal olefin. Reaction of 2-pyr/BF3OEt 2 with a stoichiometric amount of 1-13C-labeled 1-octene at -80 °C yields a 50:50 mixture of the linear alkyls [(P ̂P)Pd13CH2(CH2) 6CH3]+ and [(P̂P)PdCH 2(CH2)6 13CH3] + (4a and 4b). Further reaction with 13CO yields the linear acyls [(P̂P)Pd13C(=O)12/13CH 2(CH2)6 12/13CH3(L)] + (5-L; L = solvent or 13CO). Reaction of 2-pyr/BF 3·OEt2 with a stoichiometric amount of methyl oleate at -80 °C also resulted in fast isomerization to form a linear alkyl species [(P̂P)PdCH2(CH2) 16C(=O)OCH3]+ (6) and a branched alkyl stabilized by coordination of the ester carbonyl group as a four membered chelate [(P̂P)PdCH{(CH2)15CH 3}C(=O)OCH3]+ (7). Addition of carbon monoxide (2.5 equiv) at -80 °C resulted in insertion to form the linear acyl carbonyl [(P̂P)PdC(=O)(CH2)17C(=O)OCH 3(CO)]+ (8-CO) and the five-membered chelate [(P ̂P)PdC(=O)CH{(CH2)15CH3}C(=O) OCH3]+ (9). Exposure of 8-CO and 9 to 13CO at -50 °C results in gradual incorporation of the 13C label. Reversibility of 7 + CO ⇄ 9 is also evidenced by ΔG = -2.9 kcal mol-1 and

  12. Effects of alkali or acid treatment on the isomerization of amino acids.

    Science.gov (United States)

    Ohmori, Taketo; Mutaguchi, Yuta; Doi, Katsumi; Ohshima, Toshihisa

    2012-10-01

    The effect of alkali treatment on the isomerization of amino acids was investigated. The 100×D/(D+L) values of amino acids from peptide increased with increase in the number of constituent amino acid residues. Furthermore, the N-terminal amino acid of a dipeptide was isomerized to a greater extent than the C-terminal residue. Copyright © 2012. Published by Elsevier B.V.

  13. Thermal decomposition and isomerization of cis-permethrin and beta-cypermethrin in the solid phase.

    Science.gov (United States)

    González Audino, Paola; Licastro, Susana A; Zerba, Eduardo

    2002-02-01

    The stability to heart of cis-permethrin and beta-cypermethrin in the solid phase was studied and the decomposition products identified. Samples heated at 210 degrees C in an oven in the dark showed that, in the absence of potassium chlorate (the salt present in smoke-generating formulations of these pyrethroids), cis-permethrin was not isomerized, although in the presence of that salt, decomposition was greater and thermal isomerization occurred. Other salts of the type KXO3 or NaXO3, with X being halogen or nitrogen, also led to a considerable thermal isomerization. Heating the insecticides in solution in the presence of potassium chlorate did not produce isomerization in any of the solvents assayed. Salt-catalysed thermal cis-trans isomerization was also found for other pyrethroids derived from permethrinic or deltamethrinic acid but not for those derived from chrysanthemic acid. The main thermal degradation processes of cis-permethrin and beta-cypermethrin decomposition when potassium chlorate was present were cyclopropane isomerization, ester cleavage and subsequent oxidation of the resulting products. Permethrinic acid, 3-phenoxybenzyle chloride, alcohol, aldehyde and acid were identified in both cases, as well as 3-phenoxybenzyl cyanide from beta-cypermethrin. A similar decomposition pattern occurred after combustion of pyrethroid fumigant formulations.

  14. Molecular and excited state properties of isomeric scarlet disperse dyes

    Science.gov (United States)

    Lim, Jihye; Szymczyk, Malgorzata; Mehraban, Nahid; Ding, Yi; Parrillo-Chapman, Lisa; El-Shafei, Ahmed; Freeman, Harold S.

    2018-06-01

    This work was part of an investigation aimed at characterizing the molecular and excited state properties of currently available disperse dyes developed to provide stability to extensive sunlight exposures when adsorbed on poly(ethylene terephthalate) (PET) fibers. Having completed the characterization of yellow, magenta, and cyan disperse dyes for PET-based fabrics used outdoors, our attention turned to the colors designed to enhance the color gamut of a standard 4-member (cyan/yellow/magenta/black) color set. The present study pertained specifically to the characterization of commercially available scarlet dyes. In this regard, HPLC analysis showed that a scarlet product used for PET coloration was mainly a 70/30 mixture of dyes, and the use of HRMS and single crystal X-ray diffraction analyses indicated that these two dyes were azo compounds derived from isomeric pyridine-based couplers which differed in the location of the primary amino (sbnd NH2) and anilino (sbnd NHPh) groups attached to the pyridine ring. One dye structure has the sbnd NHPh group para to the azo group (Sc2), while the other has that group in the ortho position (Sc3). The presence of either ortho substituent provides photostabilization through intramolecular H-bonding with the azo moiety. Further, results from molecular modeling studies showed that the lower excited state oxidation potential of Sc3 relative to that of Sc2 allows Sc3 to function as an energy quencher for the excited state of Sc2 - through thermodynamically favorable electron transfer.

  15. Isomeric shift compensation when using resonance detectors in Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Irkaev, S.M.; Semenkin, V.A.; Sokolov, M.M.

    1981-01-01

    Method for compensation of isomeric shift of lines observed during operation of resonance detectors being part of spectrometers of nuclear gamma resonance is suggested. A flowsheet of device permitting to realize the method described is given. The method is based on using the Doppler effect. A source of resonance radiation is moved at a constant velocity, which is choosen so as to compensate energy shift of lines of the source and convertors of the resonance detector. The absorber under investigation is put in motion with a constant acceleration. The resonance detector signals are amplified selected according to amplitude by a discriminator and come to the input of multichannel analyzer operating in the regime of subsequent scaling. Analysis of experimental spectra obtained at velocities of source movement from 0 to +3 mm/s shows that value of resonance absorption effect drops as increasing energy shift in the source-converter system. It is concluded that application of the method described will permit to considerably extend the field of application of resonance detectors in the Moessbauer spectroscopy and investigate in practice all the isotopes having converted transitions [ru

  16. A VUV detection system for the direct photonic identification of the first excited isomeric state of "2"2"9Th

    International Nuclear Information System (INIS)

    Seiferle, B.; Von der Wense, L.; Thirolf, P.G.; Laatiaoui, M.

    2016-01-01

    With an expected energy of 7.6(5) eV, "2"2"9Th possesses the lowest excited nuclear state in the landscape of all presently known nuclei. The energy corresponds to a wavelength of about 160 nm and would conceptually allow for an optical laser excitation of a nuclear transition. We report on a VUV optical detection system that was designed for the direct detection of the isomeric ground-state transition of "2"2"9Th. "2"2"9"("m") Th ions originating from a "2"3"3U α-recoil source are collected on a micro electrode that is placed in the focus of an annular parabolic mirror. The latter is used to parallelize the UV fluorescence that may emerge from the isomeric ground-state transition of "2"2"9Th. The parallelized light is then focused by a second annular parabolic mirror onto a CsI-coated position-sensitive MCP detector behind the mirror exit. To achieve a high signal-to-background ratio, a small spot size on the MCP detector needs to be achieved. Besides extensive ray-tracing simulations of the optical setup, we present a procedure for its alignment, as well as test measurements using a D_2 lamp, where a focal-spot size of ∼100 μm has been achieved. Assuming a purely photonic decay, a signal-to-background ratio of ∼7000:1 could be achieved. (authors)

  17. A Novel Technique that Enables Efficient Conduct of Simultaneous Isomerization and Fermentation (SIF) of Xylose

    Science.gov (United States)

    Rao, Kripa; Chelikani, Silpa; Relue, Patricia; Varanasi, Sasidhar

    Of the sugars recovered from lignocellulose, D-glucose can be readily converted into ethanol by baker's or brewer's yeast (Saccharomyces cerevisiae). However, xylose that is obtained by the hydrolysis of the hemicellulosic portion is not fermentable by the same species of yeasts. Xylose fermentation by native yeasts can be achieved via isomerization of xylose to its ketose isomer, xylulose. Isomerization with exogenous xylose isomerase (XI) occurs optimally at a pH of 7-8, whereas subsequent fermentation of xylulose to ethanol occurs at a pH of 4-5. We present a novel scheme for efficient isomerization of xylose to xylulose at conditions suitable for the fermentation by using an immobilized enzyme system capable of sustaining two different pH microenvironments in a single vessel. The proof-of-concept of the two-enzyme pellet is presented, showing conversion of xylose to xylulose even when the immobilized enzyme pellets are suspended in a bulk solution whose pH is sub-optimal for XI activity. The co-immobilized enzyme pellets may prove extremely valuable in effectively conducting "simultaneous isomerization and fermentation" (SIF) of xylose. To help further shift the equilibrium in favor of xylulose formation, sodium tetraborate (borax) was added to the isomerization solution. Binding of tetrahydroxyborate ions to xylulose effectively reduces the concentration of xylulose and leads to increased xylose isomerization. The formation of tetrahydroxyborate ions and the enhancement in xylulose production resulting from the complexation was studied at two different bulk pH values. The addition of 0.05 M borax to the isomerization solution containing our co-immobilized enzyme pellets resulted in xylose to xylulose conversion as high as 86% under pH conditions that are suboptimal for XI activity. These initial findings, which can be optimized for industrial conditions, have significant potential for increasing the yield of ethanol from xylose in an SIF approach.

  18. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water.

    Science.gov (United States)

    Moliner, Manuel; Román-Leshkov, Yuriy; Davis, Mark E

    2010-04-06

    The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (150 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].

  19. Thermal isomerization of regiospecifically 10B-labeled icosahedral carboranes

    International Nuclear Information System (INIS)

    Edvenson, G.M.; Gaines, D.F.

    1990-01-01

    Thermal treatment of regiospecifically 10 B-enriched (96%) 3-( 10 B)-1,2-C 2 n B 9 H 12 and 2-( 10 B)-1,7-C 2 n B 9 H 12 ( n B = boron with normal isotopic abundances) followed by 10 B and 11 B NMR analysis reveal that (1) 3-( 10 B)-1,2-C 2 n B 9 H 12 undergoes rearrangements that completely scramble the enriched boron atom, (2) these rearrangements occur at a rate faster than the conversion of 1,2-C 2 B 10 H 12 to 1,7-C 2 B 10 H 12 , (3) the 1,7-C 2 B 10 H 12 that is formed does not re-form 1,2-C 2 B 10 H 12 at a detectable rate, and (4) at temperatures at which 1,2-C 2 B 10 H 12 forms 1,7-C 2 B 10 H 12 at a significant rate, the latter undergoes no further rearrangements. The movement of 10 B at 350 degree C in 1,2-C 2 B 10 H 12 is compared to the movement predicted by various isomerization mechanisms. The mechanism that appears to give the closest agreement involves a 12-vertex nido intermediate. It was found that a number of previously considered mechanisms, including simple exchange between two boron sites, triangular face rotation in an icosahedron, diamond-square-diamond twist, and rotation of pentagonal pyramids, are extensions of the nido intermediate mechanism. The synthesis and thermal rearrangement of 3-F-3-( 10 B)-1,2-C 2 n B 9 H 11 demonstrate that independent intramolecular fluorine migration does not occur during rearrangement. 27 refs., 7 figs

  20. Possession experiences in dissociative identity disorder: a preliminary study.

    Science.gov (United States)

    Ross, Colin A

    2011-01-01

    Dissociative trance disorder, which includes possession experiences, was introduced as a provisional diagnosis requiring further study in the Diagnostic and Statistical Manual of Mental Disorders (4th ed.). Consideration is now being given to including possession experiences within dissociative identity disorder (DID) in the Diagnostic and Statistical Manual of Mental Disorders (5th ed.), which is due to be published in 2013. In order to provide empirical data relevant to the relationship between DID and possession states, I analyzed data on the prevalence of trance, possession states, sleepwalking, and paranormal experiences in 3 large samples: patients with DID from North America; psychiatric outpatients from Shanghai, China; and a general population sample from Winnipeg, Canada. Trance, sleepwalking, paranormal, and possession experiences were much more common in the DID patients than in the 2 comparison samples. The study is preliminary and exploratory in nature because the samples were not matched in any way.

  1. The development of isomerization catalysts for production of high-octane products

    Energy Technology Data Exchange (ETDEWEB)

    Pedrosa, A.M. Garrido; Melo, D.M.A.; Araujo, A.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Quimica; Souza, M.J.B.; Silva, A.O.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Engenharia Quimica

    2004-07-01

    In current petroleum industry, paraffins larger than C5 are used for catalytic reform. The catalytic reform is one of the most important processes for petroleum refine in reason of all reactions they drive to production of high-octane products. Reformate has high-octane products, but they contain 60% aromatics. Isomerization of C5- C7 can improve the octane number. The octane number of n-heptane is zero and increases after isomerization. For tri branched C7, the octane number reaches 113, which is higher than that of benzene. So, isomerization of C5-C7 is suggested to be a reasonable way to replace or partly replace the catalytic reforming process. It can decrease aromatics content with enhancement of octane number. Liquid acid catalysts were widely used in chemical industry in past decades. However, they face strong environmental challenges. The heavy corrosion of the reactor system is one of the main problems. Thus, solid acid catalysts are investigated for the isomerization reactions. The aim of this work is to develop a catalysts for the production of reformate products. Isomerization is catalyzed by metal-acid bifunctional catalysts. The metal components aid in hydrogenation, while the support, such as, zirconium, clays or zeolites, is the acidic component. (author)

  2. Dehydrogenation and concurrent isomerization of n-butenes on mixed tin and antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Irvine, E.A.; Taylor, D.

    1978-01-01

    The dehydrogenation and concurrent isomerization of n-butenes on mixed tin and antimony oxide catalysts which had been outgassed at 698/sup 0/K were carried out in the presence of oxygen at 474/sup 0/K, and the initial approximately zero-order rates of 1,3-butadiene formation and rates of isomerization were used as a measure of catalytic activity to construct activity patterns as a function of catalyst composition. A comparison of the patterns with those for the isomerization of 3,3-dimethyl-1-butene and for the selective oxidation of propane on the same catalysts indicated that the dehydrogenation of 1-butene involves a m-allyl intermediate, but isomerization occurs through carbonium ion formation. For the cis- and trans-isomers, both reactions apparently occurred via a common allyl (but not m-allyl) intermediate. Dehydrogenation to butadiene decreased in the order 1-butene > cis-2-butene trans-2-butene and was maximum at 10% antimony for 1-butene and 21% antimony for 2-butene. Isomerization was always slower than dehydrogenation and showed two maEima, at 21 (or 27%) and at 75% antimony.

  3. Cryo-EM structure of isomeric molluscan hemocyanin triggered by viral infection.

    Directory of Open Access Journals (Sweden)

    Hongtao Zhu

    Full Text Available Hemocyanins (Hcs of arthropods and mollusks function not only as oxygen transporters, but also as phenoloxidases (POs. In invertebrates, PO is an important component in the innate immune cascade, where it functions as the initiator of melanin synthesis, a pigment involved in encapsulating and killing of pathogenic microbes. Although structures of Hc from several species of invertebrates have been reported, the structural basis for how PO activity is triggered by structural changes of Hc in vivo remains poorly understood. Here, we report a 6.8 Å cryo-electron microscopy (cryo-EM structure of the isomeric form of hemocyanin, which was isolated from Abalone Shriveling syndrome-associated Virus (AbSV infected abalone (Halitotis diversicolor, and build a pseudoatomic model of isomeric H. diversicolor hemocyanin 1 (HdH1. Our results show that, compared with native form of HdH1, the architecture of isomeric HdH1 turns into a more relaxed form. The interactions between certain functional units (FUs present in the native form of Hc either decreased or were totally abolished in the isomeric form of Hc. As a result of that, native state Hc switches to its isomeric form, enabling it to play its role in innate immune responses against invading pathogens.

  4. High spin states and isomeric decays in doubly-odd 208Fr

    International Nuclear Information System (INIS)

    Kanjilal, D.; Bhattacharya, S.; Goswami, A.; Kshetri, R.; Raut, R.; Saha, S.; Bhowmik, R.K.; Gehlot, J.; Muralithar, S.; Singh, R.P.; Jnaneswari, G.; Mukherjee, G.; Mukherjee, B.

    2010-01-01

    Neutron deficient isotopes of francium (Z=87, N∼121-123) as excited nuclei were produced in the fusion-evaporation reaction: 197 Au( 16 O, xn) 213-x Fr at 100 MeV. The γ rays from the residues were observed through the high sensitivity Germanium Clover detector array INGA. The decay of the high spin states and the isomeric states of the doubly-odd 208 Fr nuclei, identified from the known sequence of ground state transitions, were observed. The half-lives of the E γ =194(2) keV isomeric transition, known from earlier observations, was measured to be T 1/2 =233(18) ns. A second isomeric transition at E γ =383(2) keV and T 1/2 =33(7) ns was also found. The measured half-lives were compared with the corresponding single particle estimates, based on the level scheme obtained from the experiment.

  5. Structural and spectral comparisons between isomeric benzisothiazole and benzothiazole based aromatic heterocyclic dyes

    Science.gov (United States)

    Wang, Yin-Ge; Wang, Yue-Hua; Tao, Tao; Qian, Hui-Fen; Huang, Wei

    2015-09-01

    A pair of isomeric heterocyclic compounds, namely 3-amino-5-nitro-[2,1]-benzisothiazole and 2-amino-6-nitrobenzothiazole, are used as the diazonium components to couple with two N-substituted 4-aminobenzene derivatives. As a result, two pairs of isomeric aromatic heterocyclic azo dyes have been produced and they are structurally and spectrally characterized and compared including single-crystal structures, electronic spectra, solvatochromism and reversible acid-base discoloration, thermal stability and theoretically calculations. It is concluded that both benzisothiazole and benzothiazole based dyes show planar molecular structures and offset π-π stacking interactions, solvatochromism and reversible acid-base discoloration. Furthermore, benzisothiazole based aromatic heterocyclic dyes exhibit higher thermal stability, larger solvatochromic effects and maximum absorption wavelengths than corresponding benzothiazole based ones, which can be explained successfully by the differences of their calculated isomerization energy, dipole moment and molecular band gaps.

  6. Special features of isomeric ratios in nuclear reactions induced by various projectile particles

    Energy Technology Data Exchange (ETDEWEB)

    Danagulyan, A. S.; Hovhannisyan, G. H., E-mail: hov-gohar@ysu.am; Bakhshiyan, T. M.; Martirosyan, G. V. [Yerevan State University (Armenia)

    2016-05-15

    Calculations for (p, n) and (α, p3n) reactions were performed with the aid of the TALYS-1.4 code. Reactions in which the mass numbers of target and product nuclei were identical were examined in the range of A = 44–124. Excitation functions were obtained for product nuclei in ground and isomeric states, and isomeric ratios were calculated. The calculated data reflect well the dependence of the isomeric ratios on the projectile type. A comparison of the calculated and experimental data reveals, that, for some nuclei in a high-spin state, the calculated data fall greatly short of their experimental counterparts. These discrepancies may be due to the presence of high-spin yrast states and rotational bands in these nuclei. Calculations involving various level-density models included in the TALYS-1.4 code with allowance for the enhancement of collective effects do not remove the discrepancies in the majority of cases.

  7. Possible evidence for shape isomeric γ-decay in μ- atoms of 238U

    International Nuclear Information System (INIS)

    Fromm, W.D.; Ortlepp, H.-G.; Polikanov, S.M.; Schmidt, U.; Zorin, G.N.; Arlt, R.; Musiol, G.

    1977-01-01

    A search for the γ-decay of the shape isomer in muonic 238 U excited by radiationless transitions has been performed. Seven delayed transitions in the energy region of 700 to 3200 keV have been observed with a large Ge(Li) detector. Two transitions with Esub(γ)=2215 and 3131 keV have been attributed to the decay of the shape isomeric state into levels in the first well. The isomeric shift of the second minimum Esub(II) approximately 600 keV in the presence of the muon and the decrease of the lifetime of the shape isomer to tau=12+-2 ns give arguments in favour of the connection of shape isomerism with large quadrupole deformations. (Auth.)

  8. High-spin μs isomeric states in 96 Ag

    International Nuclear Information System (INIS)

    Becerril, A. D.; Lorusso, G.; Amthor, A. M.; Brown, B. A.; Estrade, A.; Guess, C. J.; Hitt, G. W.; Meharchand, R.; Schatz, H.; Smith, K.; Zegers, R. G. T.; Baumann, T.; Bazin, D.; Ginter, T.; Hausmann, M.; Minamisono, K.; Portillo, M.; Stolz, A.; Berryman, J. S.; Crawford, H. L.

    2011-01-01

    The isomeric and β decays of the N=Z+2 nucleus 96 Ag were investigated at the National Superconducting Cyclotron Laboratory. A cascade of γ-ray transitions originating from the deexcitation of a microsecond isomer was observed for the first time and was found in coincidence with two previously known transitions with energies of 470 and 667 keV. The isomeric half-life was determined as 1.45(7) μs, more precise than previously reported. The existence of a second, longer-lived microsecond isomer, associated with a 743-keV γ transition, is also proposed here. Shell model results within the (p 3/2 p 1/2 f 5/2 g 9/2 ) model space, using the jj44b interaction, reproduced level energies and isomeric decay half-lives reasonably well.

  9. Synthesis, structure and isomerism of three-bridge exo-nido-osmacarborane clusters

    International Nuclear Information System (INIS)

    Kolomnikova, G.D.; Petrovskij, P.V.; Sorokin, P.V.; Dolgushin, F.M.; Yanovskij, A.I.; Chizhevskij, I.T.

    2001-01-01

    The structure and isomerism of exo-nido-osmacarboranes prepared by reaction between coordination-unsaturated complex OsCl 2 (PPh 3 ) 3 (Ph-phenyl) in benzene at 20 deg C and K + -salts of nido-dicarbaundecarborate anions were studied by the methods of 1 H and 11 B NMR (including usual and two-dimensional spectra) and X-ray diffraction analysis. It was ascertained that in the compounds prepared osmium-containing group is bound with nido-carborane ligand via three-center bonds, open pentagonal plane of carborane ligand being retained in the isomers. In it nature isomerism in the compounds mentioned is geometrical cis-trans-isomerism [ru

  10. Glucose isomerization in simulated moving bed reactor by Glucose isomerase

    Directory of Open Access Journals (Sweden)

    Eduardo Alberto Borges da Silva

    2006-05-01

    Full Text Available Studies were carried out on the production of high-fructose syrup by Simulated Moving Bed (SMB technology. A mathematical model and numerical methodology were used to predict the behavior and performance of the simulated moving bed reactors and to verify some important aspects for application of this technology in the isomerization process. The developed algorithm used the strategy that considered equivalences between simulated moving bed reactors and true moving bed reactors. The kinetic parameters of the enzymatic reaction were obtained experimentally using discontinuous reactors by the Lineweaver-Burk technique. Mass transfer effects in the reaction conversion using the immobilized enzyme glucose isomerase were investigated. In the SMB reactive system, the operational variable flow rate of feed stream was evaluated to determine its influence on system performance. Results showed that there were some flow rate values at which greater purities could be obtained.Neste trabalho a tecnologia de Leito Móvel Simulado (LMS reativo é aplicada no processo de isomerização da glicose visando à produção de xarope concentrado de frutose. É apresentada a modelagem matemática e uma metodologia numérica para predizer o comportamento e o desempenho de unidades reativas de leito móvel simulado para verificar alguns aspectos importantes para o emprego desta tecnologia no processo de isomerização. O algoritmo desenvolvido utiliza a abordagem que considera as equivalências entre as unidades reativas de leito móvel simulado e leito móvel verdadeiro. Parâmetros cinéticos da reação enzimática são obtidos experimentalmente usando reatores em batelada pela técnica Lineweaver-Burk. Efeitos da transferência de massa na conversão de reação usando a enzima imobilizada glicose isomerase são verificados. No sistema reativo de LMS, a variável operacional vazão da corrente de alimentação é avaliada para conhecer o efeito de sua influência no

  11. Impacts of daily intakes on the isomeric profiles of perfluoroalkyl substances (PFASs) in human serum.

    Science.gov (United States)

    Shan, Guoqiang; Wang, Zhi; Zhou, Lianqiu; Du, Pin; Luo, Xiaoxiao; Wu, Qiannian; Zhu, Lingyan

    2016-01-01

    Perfluoroalkyl substances (PFASs) have been well studied in human daily intake for assessment of potential health risks. However, little is known about the isomeric compositions of PFASs in daily intake and their impacts on isomeric profiles in humans. In this study, we investigated the occurrence of PFASs with isomeric analysis in various human exposure matrices including foodstuffs, tap water and indoor dust. Perfluorooctanesulfonate (PFOS) and/or perfluorooctanoate (PFOA) were predominant in these exposure matrices collected in Tianjin, China. In fish and meat, linear (n-) PFOA was enriched with a percentage of 92.2% and 99.6%, respectively. Although n-PFOS was higher in fish (84.8%) than in technical PFOS (ca. 70%), it was much lower in meat (63.1%) and vegetables (58.5%). Dietary intake contributed >99% of the estimated daily intake (EDI) for the general population. The isomeric profiles of PFOA and PFOS in human serum were predicted based on the EDI and a one-compartment, first-order pharmacokinetic model. The isomeric percentage of n-PFOA in the EDI (98.6%) was similar to that in human serum (predicted: 98.2%, previously measured: 99.7%) of Tianjin residents. The results suggest direct PFOA intake plays an important role in its isomeric compositions in humans. For PFOS, the predicted n-PFOS (69.3%) was much higher than the previously measured values (59.2%) in human serum. This implies that other factors, such as indirect exposure to PFOS precursors and multiple excretion pathways, may contribute to the lower percentage of n-PFOS in humans than of technical PFOS. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. NaSO2Ph Induced Exclusive Isomerization of 1,2-Allenyl Sulfoxides to 2-Alkynylic Phenyl Sulfoxides

    Institute of Scientific and Technical Information of China (English)

    傅春玲; 麻生明

    2005-01-01

    The clean isomerization of 1,2-allenyl sulfoxides in the presence of NaSO2Ph afforded 2-alkynylic phenyl sulfoxides in good yields and selectivities. Although strong base-catalyzed isomerization of allenes to alkynes is known, the mechanism for the current reaction is interesting for the obvious reason that NaSOEPh is a weak base.

  13. 20 CFR 404.1093 - Possession of the United States.

    Science.gov (United States)

    2010-04-01

    ... DISABILITY INSURANCE (1950- ) Employment, Wages, Self-Employment, and Self-Employment Income Self-Employment... figuring your net earnings from self-employment, the term possession of the United States shall be deemed...

  14. Mental illness complicated by the santeria belief in spirit possession.

    Science.gov (United States)

    Alonso, L; Jeffrey, W D

    1988-11-01

    Santeria, a religious system that blends African and Catholic beliefs, is practiced by many Cuban Americans. One aspect of this system is the belief in spirit possession. Basic santeria beliefs and rituals, including the fiesta santera (a gathering at which some participants may become possessed), are briefly described, and four cases in which the patients' belief in possession played a role in their mental illness are presented. The belief in possession can complicate the diagnosis and treatment of mental illness, but it should not be considered a culture-bound syndrome. Rather, it may be a nonspecific symptom of a variety of mental illnesses and should be evaluated in the context of the patient's overall belief system and ability to carry out usual activities.

  15. Constitutional Law: Right of Privacy--Possession of Marijuana

    Science.gov (United States)

    Rohrer, David E.

    1976-01-01

    The Alaska Supreme Court in Ravin v. State accepted the defendant's contention that the prohibition of possession of marihuana infringed on his constitutional right to privacy. The significance of the case is discussed. (LBH)

  16. The epistemological significance of possession entering the DSM.

    Science.gov (United States)

    Stephenson, Craig

    2015-09-01

    The discourse of the American Psychiatric Association's DSM reflects the inherently dialogic or contradictory nature of its stated mandate to demonstrate both 'nosological completeness' and cultural 'inclusiveness'. Psychiatry employs the dialogic discourse of the DSM in a one-sided, positivistic manner by identifying what it considers universal mental disease entities stripped of their cultural context. In 1992 the editors of the Diagnostic and Statistical Manual of Mental Disorders proposed to introduce possession into their revisions. A survey of the discussions about introducing 'possession' as a dissociative disorder to be listed in the DSM-IV indicates a missed epistemological break. Subsequently the editors of the DSM-5 politically 'recuperated' possession into its official discourse, without acknowledging the anarchic challenges that possession presents to psychiatry as a cultural practice. © The Author(s) 2015.

  17. Criminalization of 'Possession of Unexplained Property' and the ...

    African Journals Online (AJOL)

    Worku_Y

    government operating costs, increases government spending for wages and ... revenues by plundering revenue generating agencies such as tax collection, ..... a) the assets under the ownership or possession of himself and his family; and.

  18. Consequences of acid strength for isomerization and elimination catalysis on solid acids.

    Science.gov (United States)

    Macht, Josef; Carr, Robert T; Iglesia, Enrique

    2009-05-13

    We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic

  19. Excitation of isomeric states 1h11/2 in (γ, n) reactions

    International Nuclear Information System (INIS)

    Tonchev, A.P.; Gangrskij, Yu.P.; Belov, A.G.

    1995-01-01

    The cross sections of (γ, n) reactions were measured for ground and isomeric states 1h 11/2 in 16 isotopes of Pd, Cd, Sn, Te, Ba, Ce, Nd and Sm. The energy of γ-rays was placed in the region of Giant Dipole Resonance. An activation method of measurements has been used. IR dependence of neutron and proton number in nucleus was detected and of excitation energy of residual nucleus as well. Different factors influencing the values of the isomeric ratios are discussed. 20 refs., 5 figs., 2 tabs

  20. Isomeric ratio measurements for the radiative neutron capture 176Lu(n,γ at DANCE

    Directory of Open Access Journals (Sweden)

    Denis-Petit D.

    2017-01-01

    Full Text Available The isomeric ratios for the neutron capture reaction 176Lu(n,γ to the Jπ = 5/2−, 761.7 keV, T1/2 = 32.8 ns and the Jπ = 15/2+, 1356.9 keV, T1/2 = 11.1 ns levels of 177Lu, have been measured for the first time with the Detector for Advanced Neutron Capture Experiments (DANCE at the Los Alamos National Laboratory. These measured isomeric ratios are compared with TALYS calculations.

  1. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water

    OpenAIRE

    Moliner, Manuel; Román-Leshkov, Yuriy; Davis, Mark E.

    2010-01-01

    The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containin...

  2. Efficient Isomerization of Glucose to Fructose over Zeolites in Consecutive Reactions in Alcohol and Aqueous Media

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Paniagua, Marta; Melero, Juan A

    2013-01-01

    glucose isomerization to fructose and subsequent reaction with methanol to form methyl fructoside (step 1), followed by hydrolysis to re-form fructose after water addition (step 2). NMR analysis with (13)C-labeled sugars confirmed this reaction pathway. Conversion of glucose for 1 h at 120 °C with H......-USY (Si/Al = 6) gave a remarkable 55% yield of fructose after the second reaction step. A main advantage of applying alcohol media and a catalyst that combines Brønsted and Lewis acid sites is that glucose is isomerized to fructose at low temperatures, while direct conversion to industrially important...

  3. High-pressure liquid chromatographic determination of chlorphenesin carbamate and the beta-isomeric carbamate.

    Science.gov (United States)

    Beyer, W F

    1976-12-01

    A high-pressure liquid chromatographic assay was developed for the determination of chlorphenesin carbamate and its beta-isomeric carbamate. A single 4-mm i.d. X 30-cm column, prepacked with 10 micrometer fully porous silica gel particles, is used with 3% methanol in 50% water-saturated butyl chloride as the mobile phase. The procedure separates chlorphenesin carbamate from several possible impurities in addition to the beta-isomeric carbamate. The assay was applied to bulk drug and compressed tablets. The relative standard deviations for the assays of chlorphenesin carbamate and the beta-isomer are approximately 1 and 2%, respectively.

  4. Preparing isomerically pure beams of short-lived nuclei at JYFLTRAP

    Energy Technology Data Exchange (ETDEWEB)

    Eronen, T. [Department of Physics, University of Jyvaeskylae, P.O. Box 35 (YFL), FIN-40014 (Finland)], E-mail: tommi.eronen@jyu.fi; Elomaa, V.-V.; Hager, U.; Hakala, J.; Jokinen, A.; Kankainen, A.; Rahaman, S.; Rissanen, J.; Weber, C.; Aystoe, J. [Department of Physics, University of Jyvaeskylae, P.O. Box 35 (YFL), FIN-40014 (Finland)

    2008-10-15

    A new procedure to prepare isomerically clean samples of short-lived ions with a mass resolving power of more than 1 x 10{sup 5} has been developed at the JYFLTRAP tandem Penning trap system. The method utilises a dipolar rf-excitation of the ion motion with separated oscillatory fields in the precision trap. During a subsequent retransfer to the purification trap, the contaminants are rejected and as a consequence, the remaining bunch is isomerically cleaned. This newly-developed method is suitable for very high-resolution cleaning and is at least a factor of five faster than the methods used so far in Penning trap mass spectrometry.

  5. Determination of the active site and mechanism for alkene isomerization in Cu(II) exchnaged Y-type zeolite

    Energy Technology Data Exchange (ETDEWEB)

    John, C S; Leach, H F

    1977-01-01

    An ESR study of 1-butene isomerization at 315/sup 0/-375/sup 0/C, 3,3-dimethyl-1-butene isomerization to 2,3-dimethyl-1- and -2-butene at 293/sup 0/K, and deuterium redistribution in 3,3-dideuteriopropene at 363/sup 0/-396/sup 0/K showed the presence of two copper(II) species in different environments, which reacted with the olefins at different rates. Although activation energies for the three reactions differed and only dideuteriopropene showed an induction period, a similar mechanism is proposed in all cases, involving preliminary reduction of copper(II), with the rates of reduction and isomerization differing from olefin to olefin. Apparently, the active site for the isomerization is a Broensted acid generated by the reduction, and the isomerization follows an associative (proton addition-elimination) mechanism with a carbonium ion intermediate. Spectra, graphs, diagram, and 12 references.

  6. Anticonvulsant effects of isomeric nonimidazole histamine H3 receptor antagonists

    Directory of Open Access Journals (Sweden)

    Sadek B

    2016-11-01

    , in which 3-piperidinopropan-1-ol in ligand 2 was replaced by (4-(3-(piperidin-1-ylpropoxyphenylmethanol, and its (S-enantiomer (4 significantly and in a dose-dependent manner reduced convulsions or exhibited full protection in MES and PTZ convulsions model, respectively. Interestingly, the protective effects observed for the (R-enantiomer (3 in MES model were significantly greater than those of the standard H3R inverse agonist/antagonist pitolisant, comparable with those observed for PHT, and reversed when rats were pretreated with the selective H3R agonist R-(α-methyl-histamine. Comparisons of the observed antagonistic in vitro affinities among the ligands 1–6 revealed profound stereoselectivity at human H3Rs with varying preferences for this receptor subtype. Moreover, the in vivo anticonvulsant effects observed in this study for ligands 1–6 showed stereoselectivity in different convulsion models in male adult rats. Keywords: histamine, H3 receptor, isomeric antagonists, anticonvulsant activity, stereo­selectivity

  7. Possessive Pronouns in European Portuguese and Old French

    Directory of Open Access Journals (Sweden)

    Matilde Miguel

    2002-12-01

    Full Text Available The aim of this paper is to bring European Portuguese (EP data into light, showing that, in spite of the lack of morphological evidence, the syntactic behaviour of possessives, across EP dialects, shows evidences for a tripartite possessive system (Cardinaletti, 1998; Cardinaletti & Starke, 1999. It will be argued that the syntactic position of possessives parallels the positions assumed for EP sentential subjects in non interrogative contexts: [Spec, AgrsP], [Spec, TP] and [Spec, VP]. As a matter of fact, depending on their syntactic properties and assuming, as null hypothesis, that the nominal head moves to Numb'º', possessives may occur in [Spec, AgrsNP], [Spec, NumbP] and [Spec, NP]. Furthermore, would it be so, this dialectal variation would be useful in order to understand the changes that have occurred in other romance languages in previous stages. It might be the case that the loss of weak possessive forms (“mien” in French parallels, among other things, the lack of sentential subjects in [Spec, TP].

  8. The goalkeeper influence on ball possession effectiveness in futsal

    Directory of Open Access Journals (Sweden)

    Vicente-Vila Pedro

    2016-06-01

    Full Text Available The aim of this study was to identify which variables were the best predictors of success in futsal ball possession when controlling for space and task related indicators, situational variables and the participation of the goalkeeper as a regular field player or not (5 vs. 4 or 4 vs. 4. The sample consisted of 326 situations of ball possession corresponding to 31 matches played by a team from the Spanish Futsal League during the 2010–2011, 2011–2012 and 2012–2013 seasons. Multidimensional qualitative data obtained from 10 ordered categorical variables were used. Data were analysed using chi-square analysis and multiple logistic regression analysis. Overall, the highest ball possession effectiveness was achieved when the goalkeeper participated as a regular field player (p<0.01, the duration of the ball possession was less than 10 s (p<0.01, the ball possession ended in the penalty area (p<0.01 and the defensive pressure was low (p<0.01. The information obtained on the relative effectiveness of offensive playing tactics can be used to improve team’s goal-scoring and goal preventing abilities.

  9. Elucidation of structural isomers from the homogeneous rhodium-catalyzed isomerization of vegetable oils.

    Science.gov (United States)

    Andjelkovic, Dejan D; Min, Byungrok; Ahn, Dong; Larock, Richard C

    2006-12-13

    The structural isomers formed by the homogeneous rhodium-catalyzed isomerization of several vegetable oils have been elucidated. A detailed study of the isomerization of the model compound methyl linoleate has been performed to correlate the distribution of conjugated isomers, the reaction kinetics, and the mechanism of the reaction. It has been shown that [RhCl(C8H8)2]2 is a highly efficient and selective isomerization catalyst for the production of highly conjugated vegetable oils with a high conjugated linoleic acid (CLA) content, which is highly desirable in the food industry. The combined fraction of the two major CLA isomers [(9Z,11E)-CLA and (10E,12Z)-CLA] in the overall CLA mixture is in the range from 76.2% to 93.4%. The high efficiency and selectivity of this isomerization method along with the straightforward purification process render this approach highly promising for the preparation of conjugated oils and CLA. Proposed improvements in catalyst recovery and reusability will only make this method more appealing to the food, paint, coating, and polymer industries in the future.

  10. Changes in Atmospheric Butanes and Pentanes and Their Isomeric Ratios in the Continental United States

    Science.gov (United States)

    Rossabi, Sam; Helmig, Detlev

    2018-04-01

    Nonmethane hydrocarbons have been used as tracers in research on emissions and atmospheric oxidation chemistry. This research investigates source region mixing ratio trends of the nonmethane hydrocarbons i-butane, n-butane, i-pentane, and n-pentane, and the (i/n) isomeric ratios of these compounds between 2001 and 2015. Data collected at Photochemical Assessment Monitoring Stations, mandated by the U.S. Environmental Protection Agency in ozone nonattainment areas, and data collected at Global Greenhouse Gas Reference Network sites within the National Oceanic and Atmospheric Administration network, and analyzed at the Institute of Arctic and Alpine Research at the University of Colorado-Boulder, were examined. Among all considered species, linear regression analyses on concentration time series had negative slopes at 81% of sites, indicating predominantly declining butane and pentane atmospheric concentrations. Mostly negative slopes (78% of sites) were found for the (i/n) butane and pentane isomeric ratios, including all six and seven statistically significant (i/n) butane and pentane trends, respectively. Over the 15 year investigation period and averaged over all sites, total relative changes were 30 and 45% for the (i/n) ratios of butanes and pentanes, respectively, with a relative increase in the prominence of the n-isomers. Most likely causes include changing isomeric ratios in gasoline sector emissions, and increasing influence of oil and natural gas industry emissions. Changes in concentrations and isomeric ratios depend on proximity of contributing emission sources to measurement sites.

  11. Left atrial isomerism associated with asplenia: prenatal echocardiographic detection of complex congenital cardiac malformations

    NARCIS (Netherlands)

    Stewart, P. A.; Becker, A. E.; Wladimiroff, J. W.; Essed, C. E.

    1984-01-01

    Complex congenital heart disease with suspected isomerism of the atria was diagnosed in two fetuses of 20 and 29 weeks' gestation using two-dimensional and M-mode scanning techniques. The first pregnancy was terminated at 21 weeks' gestation and stillbirth occurred at 31 weeks' gestation in the

  12. Resolution of isomeric new designer stimulants using gas chromatography - Vacuum ultraviolet spectroscopy and theoretical computations

    Czech Academy of Sciences Publication Activity Database

    Škultéty, L'udovít; Fryčák, P.; Qiu, CL.; Smuts, J.; Shear-Laude, L.; Lemr, Karel; Mao, J.X.; Kroll, P.; Schug, K. A.; Szewczak, A.; Vaught, C.; Lurie, I.; Havlíček, Vladimír

    2017-01-01

    Roč. 971, JUNE 8 (2017), s. 55-67 ISSN 0003-2670 R&D Projects: GA MŠk(CZ) LO1509 Institutional support: RVO:61388971 Keywords : Gas phase absorption * Time-dependent density functional theory * Isomeric drugs Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 4.950, year: 2016

  13. Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ligare, Marshall R.; Baker, Erin M.; Laskin, Julia; Johnson, Grant E.

    2017-01-01

    Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

  14. Phase space conduits for reaction in multidimensional systems : HCN isomerization in three dimensions

    NARCIS (Netherlands)

    Waalkens, Holger; Burbanks, Andrew; Wiggins, Stephen

    2004-01-01

    The three-dimensional hydrogen cyanide/isocyanide isomerization problem is taken as an example to present a general theory for computing the phase space structures which govern classical reaction dynamics in systems with an arbitrary (finite) number of degrees of freedom. The theory, which is

  15. The Isomerization of (-)-Menthone to (+)-Isomenthone Catalyzed by an Ion-Exchange Resin

    Science.gov (United States)

    Ginzburg, Aurora L.; Baca, Nicholas A.; Hampton, Philip D.

    2014-01-01

    A traditional organic chemistry laboratory experiment involves the acid-catalyzed isomerization of (-)-menthone to (+)-isomenthone. This experiment generates large quantities of organic and aqueous waste, and only allows the final ratio of isomers to be determined. A "green" modification has been developed that replaces the mineral acid…

  16. The isomerization of allylrhodium intermediates in the rhodium-catalyzed nucleophilic allylation of cyclic imines.

    Science.gov (United States)

    Hepburn, Hamish B; Lam, Hon Wai

    2014-10-20

    Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Promotion or suppression of glucose isomerization in subcritical aqueous straight- and branched-chain alcohols.

    Science.gov (United States)

    Gao, Da-Ming; Kobayashi, Takashi; Adachi, Shuji

    2015-01-01

    The influence of water-miscible alcohols (methanol, 1-propanol, 2-propanol, and t-butyl alcohol) on the isomerization of glucose to fructose and mannose was investigated under subcritical aqueous conditions (180-200 °C). Primary and secondary alcohols promoted the conversion and isomerization of glucose to afford fructose and mannose with high and low selectivity, respectively. On the other hand, the decomposition (side-reaction) of glucose was suppressed in the presence of the primary and secondary alcohols compared with that in subcritical water. The yield of fructose increased with increasing concentration of the primary and secondary alcohols, and the species of the primary and secondary alcohols tested had little effect on the isomerization behavior of glucose. In contrast, the isomerization of glucose was suppressed in subcritical aqueous t-butyl alcohol. Both the conversion of glucose and the yield of fructose decreased with increasing concentration of t-butyl alcohol. In addition, mannose was not detected in reactions using subcritical aqueous t-butyl alcohol.

  18. Linkage isomerism in trimeric and polymeric 2,3-cis-procyanindins

    Science.gov (United States)

    Richard W. Hemingway; Lai Yeap Foo; Lawrence J. Porter

    1982-01-01

    Procyanindins polymers consist of chains of 5,7,3',4'-tetrahydroxyflavan-3-ol units linked by C(4)-C(6) or C(4)-C(8) bonds.1 Whereas the procyanidin-B group of dimers are known to exist as pairs of isomers with common flavan-3-ol units, but different interflavanoid linkages,2,3 the extent of such isomerism in...

  19. Polymeric proanthocyanidins: Interflavanoid linkage isomerism in (epicatechin-4)-(epicatechin-4)-catechin procyanidins

    Science.gov (United States)

    Richard W. Hemingway; L. Yeap Foo; L. J. Porter

    1981-01-01

    Procyanidin trimers have been isolated from a variety of plants,1-3 but their structures remain unresolved. We have now isolated three configurational isomers of (epicatechin-4)-(epicatechin-4)-catechin from Pinus taeda L. (loblolly pine) phloem which exhibit isomerism of the interflavanoid linkages.

  20. Palladium Hydride Promoted Stereoselective Isomerization of Unactivated Di(exo)methylenes to Endocyclic Dienes

    OpenAIRE

    Jung, Michael E.; Lee, Gloria S.; Pham, Hung V.; Houk, K. N.

    2014-01-01

    The exomethylenes of 2,6-disubstituted bicyclo[3.3.1]nonan-9-ones 2 are readily isomerized over a palladium catalyst under an atmosphere of hydrogen to predominantly form the isomer 3 with C 2 symmetry with very little formation of the analogous product with C s symmetry. A hydrogen source is essential to effect the rearrangement.

  1. Isomeric Diruthenium Complexes Bridged by Deprotonated Indigo in cis and trans Configuration

    Czech Academy of Sciences Publication Activity Database

    Chatterjee, M.; Ghosh, P.; Beyer, K.; Paretzki, A.; Fiedler, Jan; Kaim, W.; Lahiri, G. K.

    2018-01-01

    Roč. 13, č. 1 (2018), s. 118-125 ISSN 1861-4728 Institutional support: RVO:61388955 Keywords : isomerism * ruthenium * spectroelectrochemistry * structure Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.083, year: 2016

  2. Photochromic ruthenium sulfoxide complexes: evidence for isomerization through a conical intersection.

    Science.gov (United States)

    McClure, Beth Anne; Mockus, Nicholas V; Butcher, Dennis P; Lutterman, Daniel A; Turro, Claudia; Petersen, Jeffrey L; Rack, Jeffrey J

    2009-09-07

    The complexes [Ru(bpy)(2)(OS)](PF(6)) and [Ru(bpy)(2)(OSO)](PF(6)), where bpy is 2,2'-bipyridine, OS is 2-methylthiobenzoate, and OSO is 2-methylsulfinylbenzoate, have been studied. The electrochemical and photochemical reactivity of [Ru(bpy)(2)(OSO)](+) is consistent with an isomerization of the bound sulfoxide from S-bonded (S-) to O-bonded (O-) following irradiation or electrochemical oxidation. Charge transfer excitation of [Ru(bpy)(2)(OSO)](+) in MeOH results in the appearance of two new metal-to-ligand charge transfer (MLCT) maxima at 355 and 496 nm, while the peak at 396 nm diminishes in intensity. The isomerization is reversible at room temperature in alcohol or propylene carbonate solution. In the absence of light, solutions of O-[Ru(bpy)(2)(OSO)](+) revert to S-[Ru(bpy)(2)(OSO)](+). Kinetic analysis reveals a biexponential decay with rate constants of 5.66(3) x 10(-4) s(-1) and 3.1(1) x 10(-5) s(-1). Cyclic voltammograms of S-[Ru(bpy)(2)(OSO)](+) are consistent with electron-transfer-triggered isomerization of the sulfoxide. Analysis of these voltammograms reveal E(S)(o)' = 0.86 V and E(O)(o)' = 0.49 V versus Ag/Ag(+) for the S- and O-bonded Ru(3+/2+) couples, respectively, in propylene carbonate. We found k(S-->O) = 0.090(15) s(-1) in propylene carbonate and k(S-->O) = 0.11(3) s(-1) in acetonitrile on Ru(III), which is considerably slower than has been reported for other sulfoxide isomerizations on ruthenium polypyridyl complexes following oxidation. The photoisomerization quantum yield (Phi(S-->O) = 0.45, methanol) is quite large, indicating a rapid excited state isomerization rate constant. The kinetic trace at 500 nm is monoexponential with tau = 150 ps, which is assigned to the excited S-->O isomerization rate. There is no spectroscopic or kinetic evidence for an O-bonded (3)MLCT excited state in the spectral evolution of S-[Ru(bpy)(2)(OSO)](+) to O-[Ru(bpy)(2)(OSO)](+). Thus, isomerization occurs nonadiabatically from an S-bonded (or eta(2

  3. New isomeric states in {sup 152,154,156}Nd produced by spontaneous fission of {sup 252}Cf

    Energy Technology Data Exchange (ETDEWEB)

    Gautherin, C.; Houry, M.; Korten, W.; Le Coz, Y.; Lucas, R.; Phan, X.H.; Theisen, C. [Commissariat l`Energie Atomique de Saclay, Gif sur Yvette (France). DSM/DAPINA/SPhN; Badimon, C.; Barreau, G.; Doan, T.P.; Pedemay, G. [Centre d`Etudes Nucleaires de Bordeaux-Gradignan, Domaine du Haut Vigneau, F-33175 Gradignan (France); Belier, G.; Girod, M.; Meot, V.; Peru, S. [Commissariat a l`Energie Atomique de Bruyeres-le-Chatel, DAM/SPN, BP12, F-91680 Bruyeres-le-Chatel (France); Astier, A.; Ducroux, L.; Meyer, M.; Redon, N. [Institut de Physique Nucleaire de Lyon, F-69622 Villeurbanne Cedex (France)

    1998-04-01

    Isomeric states have been observed in fission-fragments produced by spontaneous fission of {sup 252}Cf. These states are found in neutron rich nuclei of different structure and deformations. About 50 isomeric nuclei have been observed using coincidences between {gamma}-rays identified in EUROGAM II and fission fragments detected in photovoltaic cells (SAPhIR). Lifetimes in the range from 20 ns to 2{mu}s have been measured. Presented calculations based on HFB+D1S force on new measured isomeric states in the {sup 152,154,156}Nd show evidence for K-isomers. (orig.) With 8 figs., 27 refs.

  4. Themes in Spirit Possession in Ugandan Christianity | James ...

    African Journals Online (AJOL)

    . This paper discerns a number of common themes that run through many of these experiences. In particular, sex as a motif for deviance and evil is noted as a common feature of many of the possession stories and all contact with spirits is seen ...

  5. Gun Possession among Massachusetts Batterer Intervention Program Enrollees

    Science.gov (United States)

    Rothman, Emily F.; Johnson, Renee M.; Hemenway, David

    2006-01-01

    Batterers with access to firearms present a serious lethal threat to their partners. The purpose of this exploratory study is to estimate the prevalence of and risk markers for gun possession among Massachusetts men enrolled in batterer intervention programs. The authors found that 1.8% of the men reported having a gun in or around their home.…

  6. Licenses for possessing and applying radioactive sources, materials, etc

    International Nuclear Information System (INIS)

    Anon.

    1977-01-01

    Commercial and governmental institutions have been licensed by Dutch authorities to possess and apply radioactive sources, materials, etc. A summary is given and the list is subdivided into a number of sections such as radioactive sources, radioactive materials, X-ray equipment and technetium-generators

  7. 46 CFR 308.504 - Definition of territories and possessions.

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 8 2010-10-01 2010-10-01 false Definition of territories and possessions. 308.504 Section 308.504 Shipping MARITIME ADMINISTRATION, DEPARTMENT OF TRANSPORTATION EMERGENCY OPERATIONS WAR RISK INSURANCE War Risk Cargo Insurance I-Introduction § 308.504 Definition of territories and...

  8. Dynamics of the spirit possession phenomenon in Eastern Tanzania

    Directory of Open Access Journals (Sweden)

    Marja-Liisa Swantz

    1976-01-01

    Full Text Available The discussion on the spirit possession phenomenon is related in this study to the more general question of the role of religious institutions as part in the development process of a people living in a limited geographical area of a wider national society. It is assumed that religion, like culture in general, has its specific institutional forms as result of the historical development of a society, but at the same time religion is a force shaping that history. People's cultural resources influence their social and economic development and form a potential creative element in it'. Some of the questions to be asked are: "How are specific religious practices related to the dynamics of change in the societies in question? What is the social and religious context in which the spirit possession phenomenon occurs in them? What social and economic relations get their expression in them? To what extent is spirit possession in this case a means of exerting values and creatively overcoming a crisis or conflict which the changing social and economic relations impose on the people? The established spirit possession cults are here seen as the institutional forms of religious experience. At the same time it becomes evident that there is institutionalization in process as well as deinstitutionalization of spirit possession where it occurs outside established institutional forms. Institution is taken as a socially shared form of behaviour the significance of which is commonly recognized by those who share it. By the term spirit possession cult is meant a ritual form of spirit possession of a group which is loosely organized and without strict membership. The context of the study is four ethnic groups in Eastern Tanzania, near the coast of the Indian Ocean. The general theme of the project is The Role of Culture in the Restructuring of Tanzanian Rural Areas. The restructuring refers to a villagisation programme carried out in the whole country. People are being

  9. Molecular isomerization induced by ultrashort infrared pulses. II. Pump-dump isomerization using pairs of time-delayed half-cycle pulses.

    Science.gov (United States)

    Uiberacker, Christoph; Jakubetz, Werner

    2004-06-22

    We investigate population transfer across the barrier in a double-well potential, induced by a pair of time-delayed single-lobe half-cycle pulses. We apply this setup both to a one-dimensional (1D) quartic model potential and to a three-dimensional potential representing HCN-->HNC isomerization. Overall the results for the two systems are similar, although in the 3D system some additional features appear not seen in the 1D case. The generic mechanism of population transfer is the preparation by the pump pulse of a wave packet involving delocalized states above the barrier, followed by the essentially 1D motion of the delocalized part of wave packet across the barrier, and the eventual de-excitation by the dump pulse to localized states in the other well. The correct timing is given by the well-to-well passage time of the wave packet and its recurrence properties, and by the signs of the field lobes which determine the direction and acceleration or deceleration of the wave packet motion. In the 3D system an additional pump-pump-dump mechanism linked to wave packet motion in the reagent well can mediate isomerization. Since the transfer time and the pulse durations are of the same order of magnitude, there is also a marked dependence of the dynamics and the transfer yield on the pulse duration. Our analysis also sheds light on the pronounced carrier envelope phase dependence previously observed for isomerization and molecular dissociation with one-cycle and sub-one-cycle pulses. (c) 2004 American Institute of Physics.

  10. Distinguishing PCB Isomeric Congeners with their Gas Chromatographic and Mass Spectrometric Ortho Effect using Comprehensive Gas Chromatography

    Science.gov (United States)

    The 209 polychlorinated biphenyl (PCB) congeners and associated nine isomeric groups (nine groups of PCBs with the same degree of chlorination) have been long recorded as high endocrine disrupting chemicals in the environment. Difficult analytical problems exist, in those frequen...

  11. Communication: An accurate calculation of the S1 C2H2 cis-trans isomerization barrier height

    International Nuclear Information System (INIS)

    Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

    2016-01-01

    A high level ab initio calculation of the cis-trans isomerization barrier height in the first excited singlet electronic state of acetylene is found to agree very well with a recent experimental determination.

  12. Descending with Angels: Jinn Possession, Islamic Exorcism, and Psychiatry

    DEFF Research Database (Denmark)

    Suhr, Christian

    What is it like to be a Muslim possessed by a jinn spirit? How do you find refuge from madness and evil in a place like Denmark? In this book I explore some of the ways in which Muslims in the West have sought to protect themselves. Over several years I followed Muslim patients being treated.......” In the book I analyze how these broader social and political issues are paralleled in the invisible dynamics of jinn possession and psychosis, proposing new theoretical perspectives on religious and psychiatric healing as ritual practices for dealing with the invisible in human life....... hypervisible in public discourse through intensive state monitoring, surveillance, and media coverage. Yet their religion of Islam remains poorly understood and is frequently identified by politicians, commentators, and even healthcare specialists as the underlying invisible cause of “integration problems...

  13. The Regulation of the Possession of Weapons at Gatherings

    Directory of Open Access Journals (Sweden)

    Pieter du Toit

    2013-12-01

    Full Text Available The Dangerous Weapons Act 15 of 2013 provides for certain prohibitions and restrictions in respect of the possession of a dangerous weapon and it repeals the Dangerous Weapons Act 71 of 1968 as well as the different Dangerous Weapons Acts in operation in the erstwhile TBVC States. The Act also amends the Regulation of Gatherings Act 205 of 1993 to prohibit the possession of any dangerous weapon at a gathering or demonstration. The Dangerous Weapons Act provides for a uniform system of law governing the use of dangerous weapons for the whole of South Africa and it furthermore no longer places the onus on the individual charged with the offence of the possession of a dangerous weapon to show that he or she did not have any intention of using the firearm for an unlawful purpose. The Act also defines the meaning of a dangerous weapon. According to our court’s interpretation of the Dangerous Weapons Act 71 of 1968 a dangerous weapon was regarded as an object used or intended to be used as a weapon even if it had not been designed for use as a weapon. The Act, however, requires the object to be capable of causing death or inflicting serious bodily harm if it were used for an unlawful purpose. The possession of a dangerous weapon, in circumstances which may raise a reasonable suspicion that the person intends to use it for an unlawful purpose, attracts criminal liability. The Act also provides a useful set of guidelines to assist courts to determine if a person charged with the offence of the possession of a dangerous weapon had indeed intended to use the weapon for an unlawful purpose. It seems, however, that the Act prohibits the possession of a dangerous weapon at gatherings, even if the person carrying the weapon does not intend to use it for an unlawful purpose. The state will, however, have to prove that the accused had the necessary control over the object and the intention to exercise such control, as well as that the object is capable of

  14. Efficient assembly of polysubstituted pyrroles via a (3 + 2) cycloaddition/skeletal rearrangement/redox isomerization cascade reaction.

    Science.gov (United States)

    Yu, Yuanyuan; Wang, Chunyu; He, Xinze; Yao, Xiaotong; Zu, Liansuo

    2014-07-03

    An unprecedented cascade strategy, used in conjunction with a redox isomerization, for the synthesis of 3-allyl pyrroles is reported. In a single step, readily accessible simple starting materials are transformed into highly substituted pyrroles with high efficiency. The products obtained contain allyl substituents, which can be readily elaborated to other useful functional groups. The reaction proceeds through an unusual (3 + 2) cycloaddition/skeletal rearrangement/redox isomerization pathway.

  15. Observation of excited states and isomeric decays in doubly-odd 208Fr

    International Nuclear Information System (INIS)

    Kanjilal, D.; Bhattacharya, S.; Goswami, A.; Kshetri, R.; Raut, R.; Saha, S.; Bhowmik, R.K.; Gehlot, J.; Jnaneswari, G.; Muralithar, S.; Singh, R.P.; Mukherjee, B.; Mukherjee, G.

    2009-01-01

    The nuclei near the doubly magic 208 Pb are predicted to exhibit various interesting structural phenomena, one of which is a wealth of isomerism. However, a detailed study of high spin states of 211, 212, 213 Fr has already been done. Structure of such trans-Lead nuclei can be interpreted in terms of the shell model states, and the high spin states of these nuclei are interpreted. One of the major interests in the spectroscopic investigation of these nuclei is the role played by the i 13/2 state in creating isomeric levels which decay through transitions of higher muiltipolarity, or are hindered by the close proximity of the levels below. A systematic study of these nuclei will possibly reveal many other interesting structural features

  16. Synthesis of Isomeric Phosphoubiquitin Chains Reveals that Phosphorylation Controls Deubiquitinase Activity and Specificity

    Directory of Open Access Journals (Sweden)

    Nicolas Huguenin-Dezot

    2016-07-01

    Full Text Available Ubiquitin is post-translationally modified by phosphorylation at several sites, but the consequences of these modifications are largely unknown. Here, we synthesize multi-milligram quantities of ubiquitin phosphorylated at serine 20, serine 57, and serine 65 via genetic code expansion. We use these phosphoubiquitins for the enzymatic assembly of 20 isomeric phosphoubiquitin dimers, with different sites of isopeptide linkage and/or phosphorylation. We discover that phosphorylation of serine 20 on ubiquitin converts UBE3C from a dual-specificity E3 ligase into a ligase that primarily synthesizes K48 chains. We profile the activity of 31 deubiquitinases on the isomeric phosphoubiquitin dimers in 837 reactions, and we discover that phosphorylation at distinct sites in ubiquitin can activate or repress cleavage of a particular linkage by deubiquitinases and that phosphorylation at a single site in ubiquitin can control the specificity of deubiquitinases for distinct ubiquitin linkages.

  17. Multi-quasiparticle high-K isomeric states in deformed nuclei

    Directory of Open Access Journals (Sweden)

    Xu F. R.

    2016-01-01

    Full Text Available In the past years, we have made many theoretical investigations on multi-quasiparticle high-K isomeric states. A deformation-pairing-configuration self-consistent calculation has been developed by calculating a configuration-constrained multi-quasiparticle potential energy surface (PES. The specific single-particle orbits that define the high-K configuration are identified and tracked (adiabatically blocked by calculating the average Nilsson numbers. The deformed Woods-Saxon potential was taken to give single-particle orbits. The configuration-constrained PES takes into account the shape polarization effect. Such calculations give good results on excitation energies, deformations and other structure information about multi-quasiparticle high-K isomeric states. Many different mass regions have been investigated.

  18. [Isomeric derivatives of lupinine and epilupinine--organophosphorus inhibitors of cholinesterases].

    Science.gov (United States)

    Basova, N E; Kormilitsyn, B N; Perchenok, A Iu; Rosengart, E V; Saakov, V S; Suvorov, A A

    2012-01-01

    The isomeric-structure analysis data of anticholinesterase action of organophosphorous inhibitors with similar structure help in the search of specific effectors and detection of differences in reactivity of various animals' enzymes. This study compared the data of efficacy in respect of 4 mammal and 5 arthropoda cholinesterase preparations for 26 quinolizidine inhibitors, which molecules contain both the isomeric unbranched and branched alkoxyl radicals in the phosphoryl group, and the epimeric lupinine and epilupinine derivatives in the leaving group. The changes in the alkoxyl radical structure of inhibitor molecules act on their efficacy only with respect to the mammal enzymes ("group" inhibitor specificity). The differences between lupinine and epilupinine derivatives were revealed. Highly specific inhibitors of different enzymes were detected among the tested compounds.

  19. An isomerization-induced cage-breaking process in a molecular glass former below Tg

    International Nuclear Information System (INIS)

    Teboul, V.; Saiddine, M.; Accary, J.-B.; Nunzi, J.-M.

    2011-01-01

    A recent experimental [P. Karageorgiev, D. Neher, B. Schulz, B. Stiller, U. Pietsch, M. Giersig, L. Brehmer, Nature Mater. 4, 699 (2005)] study has found liquidlike diffusion below the glass-transition temperature in azobenzene-containing materials under irradiation. This result suggests that the isomerization-induced massive mass transport that leads to surface relief gratings formation in these materials, is induced by this huge increase of the matrix diffusion coefficient around the probe. In order to investigate the microscopic origin of the increase of the diffusion, we use molecular dynamics simulations of the photoisomerization of probe dispersed red 1 molecules dispersed inside a glassy molecular matrix. Results show that the increased diffusion is due to an isomerization-induced cage-breaking process. A process that explains the induced cooperative motions recently observed in these photoactive materials.

  20. Catalytic Isomerization of Dihydroxyacetone to Lactic Acid and Alkyl Lactates over Hierarchical Zeolites Containing Tin

    Directory of Open Access Journals (Sweden)

    Agnieszka Feliczak-Guzik

    2018-01-01

    Full Text Available Hierarchical zeolites containing tin were obtained, characterized and used in a reaction of catalytic isomerization of dihydroxyacetone (DHA to lactic acid and alkyl lactates. These catalysts are characterized by preserved crystallinity and primary microporosity with the simultaneous existence of secondary porosity regarding mesopores, which facilitates access of large molecules of reagents to active centers. Creation of additional porosity was confirmed by X-ray diffraction and low-temperature nitrogen adsorption/desorption studies. The reaction of dihydroxyacetone isomerization was conducted in different reaction media such as methanol, ethanol or water with the use of two heating methods: microwave radiation and conventional heating. The application of microwave radiation enabled to reduce the reaction time to 1 h and achieve dihydroxyacetone conversion of >90% and high yields of the desired reaction products.

  1. Measurement of millisecond half-lives of isomeric levels in some nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Garg, K C; Khurana, C S [Punjabi Univ., Patiala (India). Nuclear Science Labs.

    1976-09-01

    Half-lives of 2.7, 14.5, 17, 20, 20.4, 44 and 2230 msec, of isomeric levels in /sup 208/Bi, /sup 88/Y, /sup 75/As, /sup 24/Na, /sup 71/Ge, /sup 114/In and /sup 167/Er respectively have been measured, employing on-line irradiation system. These millisecond isomeric levels are produced by 14.7 MeV neutrons through (n,p), (n,..cap alpha..), (n,n') and (n,2n) reactions on natural target samples. A ..gamma..-ray scintillation detector coupled with NTA-512B, 1024 channel analyzer has been used to follow the decay of the millisecond activities. Deflected deuteron beam bursts have been used to reduce the long-time background to initial count ratios in the decay curves to achieve a better accuracy of measurements.

  2. Collective coordinates and an accompanying metric force in structural isomerization dynamics of molecules

    International Nuclear Information System (INIS)

    Yanao, Tomohiro; Takatsuka, Kazuo

    2003-01-01

    Structural isomerization dynamics of three- and four-atom clusters of vanishing total angular momentum is studied in terms of internal coordinates of n-body systems on the basis of a gauge theory. The so-called principal-axis hyperspherical coordinates are employed effectively as collective variables for the study of isomerization reactions. It turns out that the non-Euclidean metric on the internal space gives rise to a force, which works in response to internal motions called the democratic (kinematic) rotations in the internal space. This metric force generally tends to induce an asymmetry in mass balance of a system, and is coupled with the usual potential force to give rise to trapped motions in the vicinity of the transition states of the cluster. This observation provides a different perspective for the so-called recrossing problem in chemical reaction dynamics

  3. Emotional regulation, attachment to possessions and hoarding symptoms.

    Science.gov (United States)

    Phung, Philip J; Moulding, Richard; Taylor, Jasmine K; Nedeljkovic, Maja

    2015-10-01

    This study aimed to test which particular facets of emotion regulation (ER) are most linked to symptoms of hoarding disorder, and whether beliefs about emotional attachment to possessions (EA) mediate this relationship. A non-clinical sample of 150 participants (108 females) completed questionnaires of emotional tolerance (distress tolerance, anxiety sensitivity, negative urgency - impulsivity when experiencing negative emotions), depressed mood, hoarding, and beliefs about emotional attachment to possessions. While all emotional tolerance measures related to hoarding, when considered together and controlling for depression and age, anxiety sensitivity and urgency were the significant predictors. Anxiety sensitivity was fully mediated, and urgency partially mediated, via beliefs regarding emotional attachment to possessions. These findings provide further support for (1) the importance of anxiety sensitivity and negative urgency for hoarding symptoms, and (2) the view that individuals with HD symptoms may rely on items for emotion regulation, leading to stronger beliefs that items are integral to emotional wellbeing. © 2015 Scandinavian Psychological Associations and John Wiley & Sons Ltd.

  4. A novel base-induced isomerization gives access to unprecedented (E)-exo-glycals.

    Science.gov (United States)

    Eppe, Guillaume; Dumitrescu, Lidia; Pierrot, Olivier; Li, Tianlei; Pan, Weidong; Vincent, Stéphane P

    2013-08-26

    Bump the base: This study reports the discovery of the base-induced Z-to-E isomerization of exo-glycals bearing an electron-withdrawing group (EWG). The scope of this novel transformation regarding the carbohydrate unit is also discussed. After elucidating the mechanism, preparation of novel (E)-exo- glycals was performed (TBS = tert-butyldimethylsilyl). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Internal conversion of the (13/2+→5/2-) isomeric transition in 199Hg

    International Nuclear Information System (INIS)

    Radha Krishna, K.; Chandrasekhar Rao, M.V.S.; Sree Krishna Murty, G.; Venkateswara Rao, N.; Bhuloka Reddy, S.; Satyanarayana, G.; Sastry, D.L.; Iyer, M.R.; Sahasrabhude, S.G.

    1990-01-01

    The total conversion coefficient of the M4 transition (374 KeV) in the decay of the 13/2 + isomeric state to 5/2 - state in 199 Hg measured using the relative gamma intensity method α T is determined to be 6.34 ± 0.29 in agreement with the theory due to Rosel et al. (author). 1 tab., 3 figs., 11 refs

  6. Sugar Profile, Mineral Content, and Rheological and Thermal Properties of an Isomerized Sweet Potato Starch Syrup

    OpenAIRE

    Dominque, Brunson; Gichuhi, Peter N.; Rangari, Vijay; Bovell-Benjamin, Adelia C.

    2013-01-01

    Currently, corn is used to produce more than 85% of the world's high fructose syrup (HFS). There is a search for alternative HFS substrates because of increased food demand and shrinking economies, especially in the developing world. The sweet potato is a feasible, alternative raw material. This study isomerized a high glucose sweet potato starch syrup (SPSS) and determined its sugar profile, mineral content, and rheological and thermal properties. Rheological and thermal properties were meas...

  7. {sup 13}C-NMR studies on disulfide bond isomerization in bovine pancreatic trypsin inhibitor (BPTI)

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Mitsuhiro [Kumamoto University, Department of Structural BioImaging, Faculty of Life Sciences (Japan); Miyanoiri, Yohei [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan); Terauchi, Tsutomu [Tokyo Metropolitan University, Graduate School of Science and Engineering (Japan); Kainosho, Masatsune, E-mail: kainosho@tmu.ac.jp [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan)

    2016-09-15

    Conformational isomerization of disulfide bonds is associated with the dynamics and thus the functional aspects of proteins. However, our understanding of the isomerization is limited by experimental difficulties in probing it. We explored the disulfide conformational isomerization of the Cys14–Cys38 disulfide bond in bovine pancreatic trypsin inhibitor (BPTI), by performing an NMR line-shape analysis of its Cys carbon peaks. In this approach, 1D {sup 13}C spectra were recorded at small temperature intervals for BPTI samples selectively labeled with site-specifically {sup 13}C-enriched Cys, and the recorded peaks were displayed in the order of the temperature after the spectral scales were normalized to a carbon peak. Over the profile of the line-shape, exchange broadening that altered with temperature was manifested for the carbon peaks of Cys14 and Cys38. The Cys14–Cys38 disulfide bond reportedly exists in equilibrium between a high-populated (M) and two low-populated states (m{sub c14} and m{sub c38}). Consistent with the three-site exchange model, biphasic exchange broadening arising from the two processes was observed for the peak of the Cys14 α-carbon. As the exchange broadening is maximized when the exchange rate equals the chemical shift difference in Hz between equilibrating sites, semi-quantitative information that was useful for establishing conditions for {sup 13}C relaxation dispersion experiments was obtained through the carbon line-shape profile. With respect to the m{sub c38} isomerization, the {sup 1}H-{sup 13}C signals at the β-position of the minor state were resolved from the major peaks and detected by exchange experiments at a low temperature.

  8. Model-Based Analysis and Efficient Operation of a Glucose Isomerization Reactor Plant

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; Madsen, Ulrich; Pedersen, Sven

    2015-01-01

    efficiency. The objective of this study is the application of the developed framework on an industrial case study of a glucose isomerization (GI) reactor plant that is part of a corn refinery, with the objective to improve the productivity of the process. Therefore, a multi-scale reactor model...... is developedfor use as a building block for the GI reactor plant simulation. An optimal operation strategy is proposed on the basis of the simulation results...

  9. Isomeric cross section ratios in 55Mn(α, n)58m,gCo reaction

    International Nuclear Information System (INIS)

    Long Xianguan; He Fuqing; Peng Xiufen; Liu Mantian

    1989-01-01

    The isomeric cross section ratios in 55 Mn(α, n) 58m,g Co reaction are measured for incident alpha-particle energies ranging from 10.4 to 26.5 MeV by using activation method and stacked-foil technique. The measured values are compared with theoretical calculations performed by using Huizenga and Vandenbosch method and the values of spin cutoff factor are obtained for product nucleus 58 Co

  10. High spin states in 63Cu. 17/2+ isomeric yrast state

    International Nuclear Information System (INIS)

    Tsan Ung Chan; Bruandet, J.F.; Dauchy, A.; Giorni, A.; Glasser, F.; Morand, C.; Chambon, B.; Drain, D.

    1979-01-01

    The 63 Cu nucleus has been studied via the reaction 61 Ni(α, pnγ), using different in beam γ spectroscopy techniques. An isomeric high-spin Yrast state 17/2 + (tau = 6.1 +- 0.6ns) is located at 4498 keV. The gsub(9/2) shell must be involved to explain positive high-spin states established in this work [fr

  11. [Photoionization ion mobility spectrometry (UV-IMS) for the isomeric volatile organic compounds].

    Science.gov (United States)

    Li, Hu; Niu, Wen-qi; Wang, Hong-mei; Huang, Chao-qun; Jiang, Hai-he; Chu, Yan-nan

    2012-01-01

    The construction and performance study is reported for a newly developed ultraviolet photoionization ion mobility spectrometry (UV-IMS). In the present paper, an UV-IMS technique was firstly developed to detect eleven isomeric volatile organic compounds including the differences in the structure of carbon chain, the style of function group and the position of function group. Their reduced mobility values were determined and increased in this order: linears alcohols homemade UV-IMS was around ppb-ppm.

  12. High spin states and isomeric decays in doubly-odd {sup 208}Fr

    Energy Technology Data Exchange (ETDEWEB)

    Kanjilal, D.; Bhattacharya, S.; Goswami, A.; Kshetri, R.; Raut, R. [Nuclear and Atomic Physics Division, Saha Institute of Nuclear Physics, Kolkata 700064 (India); Saha, S., E-mail: satyajit.saha@saha.ac.i [Nuclear and Atomic Physics Division, Saha Institute of Nuclear Physics, Kolkata 700064 (India); Bhowmik, R.K.; Gehlot, J.; Muralithar, S.; Singh, R.P. [Inter University Accelerator Centre, New Delhi 110067 (India); Jnaneswari, G. [Department of Physics, Andhra University, Vishakhapatnam 530003 (India); Mukherjee, G. [Variable Energy Cyclotron Centre, Kolkata 700064 (India); Mukherjee, B. [Department of Physics, Visva Bharati, Santiniketan 731235 (India)

    2010-10-15

    Neutron deficient isotopes of francium (Z=87, N{approx}121-123) as excited nuclei were produced in the fusion-evaporation reaction: {sup 197}Au({sup 16}O, xn) {sup 213-x}Fr at 100 MeV. The {gamma} rays from the residues were observed through the high sensitivity Germanium Clover detector array INGA. The decay of the high spin states and the isomeric states of the doubly-odd {sup 208}Fr nuclei, identified from the known sequence of ground state transitions, were observed. The half-lives of the E{sub {gamma}=}194(2) keV isomeric transition, known from earlier observations, was measured to be T{sub 1/2}=233(18) ns. A second isomeric transition at E{sub {gamma}=}383(2) keV and T{sub 1/2}=33(7) ns was also found. The measured half-lives were compared with the corresponding single particle estimates, based on the level scheme obtained from the experiment.

  13. The study of a new short-life isomeric state in 38K

    International Nuclear Information System (INIS)

    Iordachescu, A.

    1976-01-01

    The 38 K nucleus having a protone and neutron hole coupled with a 40 Ca inert core has a structure analysed easily by the shell model. A new short life, high spin and highly excited isomeric state of the 38 K nucleus has been studied in detail using this model. Theoretical aspects connected with static and dynamic electromagnetic moments of the nucleus state, with the magnetic moment of the nucleus and the selection rules according to the isotopic spin are presented in the case of gamma transitions. Experimentallz/ presented in the case of gamma transitions. Experimentally, it has been used a combination between a natural pulsation of the cyclotron beam and an external pulsation by electrostatic deflexion, thus obtaining a pulsation beam of 12-26 MeV alpha particles. As targets, a series of chemical chlorine combinations have been utilized, the isomeric state being obtained by the reaction 35 Cl(α,n) 38 K, having the isomeric level (1fsub(7/2))sub(7+)sup(2). (author)

  14. Discussion of isomeric ratios in (p, n) and (d, 2n) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Bakhshiyan, T. M., E-mail: tiruhi44@mail.ru [Yerevan State University (Armenia)

    2016-01-15

    Isomeric ratios (IR) in the (p, n) and (d, 2n) reactions are considered. The dependence of IR values on the projectile type and energy, the target- and product-nucleus spin, the spin difference between the isomeric and ground states of products, and the product mass number is discussed. The isomeric ratios for 46 product nuclei (from {sup 44m,g}Sc to {sup 127m,g}Xe) obtained in reactions where target and product nuclei have identical mass numbers were calculated at energies from the reaction threshold to 50 MeV (with a step of ΔE = 1 MeV). The calculations in question were performed with the aid of the TALYS 1.4 code package. The calculated IR values were compared with their experimental counterparts available from the literature (EXFOR database). In the majority of cases, the calculated IR values agree well with the experimental data in question. It is noteworthy that the IR values obtained in (d, 2n) reactions are substantially greater than those in (p, n) reactions.

  15. Photo-isomerization and oxidation of bilirubin in mammals is dependent on albumin binding.

    Science.gov (United States)

    Goncharova, Iryna; Jašprová, Jana; Vítek, Libor; Urbanová, Marie

    2015-12-01

    The bilirubin (BR) photo-conversion in the human body is a protein-dependent process; an effective photo-isomerization of the potentially neurotoxic Z,Z-BR as well as its oxidation to biliverdin in the antioxidant redox cycle is possible only when BR is bound on serum albumin. We present a novel analytical concept in the study of linear tetrapyrroles metabolic processes based on an in-depth mapping of binding sites in the structure of human serum albumin (HSA). A combination of fluorescence spectroscopy, circular dichroism (CD) spectroscopy, and molecular modeling methods was used for recognition of the binding site for BR, its derivatives (mesobilirubin and bilirubin ditaurate), and the products of the photo-isomerization and oxidation (lumirubin, biliverdin, and xanthobilirubic acid) on HSA. The CD spectra and fluorescent quenching of the Trp-HSA were used to calculate the binding constants. The results of the CD displacement experiments performed with hemin were interpreted together with the findings of molecular docking performed on the pigment-HSA complexes. We estimated that Z,Z-BR and its metabolic products bind on two independent binding sites. Our findings support the existence of a reversible antioxidant redox cycle for BR and explain an additional pathway of the photo-isomerization process (increase of HSA binding capacity; the excess free [unbound] BR can be converted and also bound to HSA). Copyright © 2015 Elsevier Inc. All rights reserved.

  16. Spectroscopic and Theoretical Identification of Two Thermal Isomerization Pathways for Bistable Chiral Overcrowded Alkenes.

    Science.gov (United States)

    Kistemaker, Jos C M; Pizzolato, Stefano F; van Leeuwen, Thomas; Pijper, Thomas C; Feringa, Ben L

    2016-09-12

    Chiroptical molecular switches play an important role in responsive materials and dynamic molecular systems. Here we present the synthesis of four chiral overcrowded alkenes and the experimental and computational study of their photochemical and thermal behavior. By irradiation with UV light, metastable diastereoisomers with opposite helicity were generated through high yielding E-Z isomerizations. Kinetic studies on metastable 1-4 using CD spectroscopy and HPLC analysis revealed two pathways at higher temperatures for the thermal isomerization, namely a thermal E-Z isomerization (TEZI) and a thermal helix inversion (THI). These processes were also studied computationally whereby a new strategy was developed for calculating the TEZI barrier for second-generation overcrowded alkenes. To demonstrate that these overcrowded alkenes can be employed as bistable switches, photochromic cycling was performed, which showed that the alkenes display good selectivity and fatigue resistance over multiple irradiation cycles. In particular, switch 3 displayed the best performance in forward and backward photoswitching, while 1 excelled in thermal stability of the photogenerated metastable form. Overall, the alkenes studied showed a remarkable and unprecedented combination of switching properties including dynamic helicity, reversibility, selectivity, fatigue resistance, and thermal stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Preclinical Evaluation of the Synthetic Adjuvant SQS-21 and its Constituent Isomeric Saponins

    Science.gov (United States)

    Ragupathi, Govind; Damani, Payal; Deng, Kai; Adams, Michelle M.; Hang, Jianfeng; George, Constantine; Livingston, Philip O.; Gin, David Y.

    2010-01-01

    The saponin fraction QS-21 from Quillaja saponaria has been demonstrated to be a potent immunological adjuvant when mixed with keyhole limpet hemocyanin conjugate vaccines, as well as with other classes of subunit antigen vaccines. QS-21 adjuvant is composed of two isomers that include the apiose and xylose forms in a ratio of 65:35, respectively. The chemical syntheses of these two isomers in pure form have recently been disclosed. Herein we describe detailed in vivo immunological evaluations of these synthetic QS-21 isomeric constituents, employing the GD3-KLH melanoma antigen. With this vaccine construct, high antibody titers against GD3 ganglioside and KLH were elicited when GD3-KLH was co-administered with adjuvant, either as the individual separate synthetic QS-21 isomers (SQS-21-Api or SQS-21-Xyl), or as its reconstituted 65:35 isomeric mixture (SQS-21). These antibody titer levels were comparable to that elicited by vaccinations employing naturally derived QS-21 (PQS-21). Moreover, toxicities of the synthetic saponin adjuvants were also found to be comparable to that of naturally derived PQS-21. These findings demonstrate unequivocally that the adjuvant activity of QS-21 resides in these two principal isomeric forms, and not in trace contaminants within the natural extracts. This lays the foundation for future exploration of structure-function correlations to enable the discovery of novel saponins with increased potency, enhanced stability, and attenuated toxicity. PMID:20450868

  18. Thermal isomerization of azobenzenes: on the performance of Eyring transition state theory

    Science.gov (United States)

    Rietze, Clemens; Titov, Evgenii; Lindner, Steven; Saalfrank, Peter

    2017-08-01

    The thermal Z\\to E (back-)isomerization of azobenzenes is a prototypical reaction occurring in molecular switches. It has been studied for decades, yet its kinetics is not fully understood. In this paper, quantum chemical calculations are performed to model the kinetics of an experimental benchmark system, where a modified azobenzene (AzoBiPyB) is embedded in a metal-organic framework (MOF). The molecule can be switched thermally from cis to trans, under solvent-free conditions. We critically test the validity of Eyring transition state theory for this reaction. As previously found for other azobenzenes (albeit in solution), good agreement between theory and experiment emerges for activation energies and activation free energies, already at a comparatively simple level of theory, B3LYP/6-31G* including dispersion corrections. However, theoretical Arrhenius prefactors and activation entropies are in qualitiative disagreement with experiment. Several factors are discussed that may have an influence on activation entropies, among them dynamical and geometric constraints (imposed by the MOF). For a simpler model—Z\\to E isomerization in azobenzene—a systematic test of quantum chemical methods from both density functional theory and wavefunction theory is carried out in the context of Eyring theory. Also, the effect of anharmonicities on activation entropies is discussed for this model system. Our work highlights capabilities and shortcomings of Eyring transition state theory and quantum chemical methods, when applied for the Z\\to E (back-)isomerization of azobenzenes under solvent-free conditions.

  19. Concurrent Mass Measurement and Laser Spectroscopy for Unambiguous Isomeric State Assignment

    Science.gov (United States)

    Lascar, Daniel; Babcock, Carla; Henderson, Jack; Pearson, Matt

    2017-09-01

    Recent work by the TITAN group at TRIUMF on isomeric state mass measurements of odd-A, neutron-rich cadmium nuclei has shown a disconnect between experiment and theory in 127 g , mCd. The spin and parity assignments of the ground and isomeric states are assigned as 3/2+ and 11/2-, respectively, primarily via systematic arguments. Conversely, state of the art shell model and ab initio calculations show a reversal of the states, predicting a ground state of 11/2- and a 3/2+ isomer. Penning Trap Mass Spectrometry (PTMS) can measure the energy separation between the ground state and the isomer without ambiguity but cannot, on its own, comment on the spin and parity. Collinear Laser Spectroscopy (CLS) experiments have been performed on 127Cd and have elegantly demonstrated the existence of both 3/2+ and 11/2- states. What CLS cannot do, on its own, is assign an ordering to those states. If, however, a PTMS and CLS experiment could be performed concurrently using identical beams from the same facility then there exists sufficient information shared between both experiments that a definitive assignment can be made. We present a concept for a new slate of measurements using existing experimental facilities simultaneously, with shared resources, to definitively assign spin and parity for ground and isomeric states in short-lived nuclei.

  20. Yields and isomeric ratio of xenon and krypton isotopes from thermal neutron fission of 235U

    International Nuclear Information System (INIS)

    Hsu, S.S.; Lin, J.T.; Yang, C.M.; Yu, Y.W.

    1981-01-01

    The experimental cumulative yields of 85 Kr/sup m/, 87 Kr, 88 Kr, 133 Xe/sup g/, 135 Xe/sup m/, and 135 Xe/sup g/ and the independent isomeric yield of 133 Xe/sup m/ in the thermal neutron fission of 235 U have been measured by the gas chromatographic method. The independent yields of 133 Xe/sup g/, 135 Xe/sup m/, and 135 Xe/sup g/ were deduced with the aid of 133 I and 135 I data. The isomeric yield ratios of 133 Xe and 135 Xe have been computed and compared with theoretical values since they have the same high spin state J = 11/2 - and low spin ground state J = 3/2 + . The influence of the shell effect on the fission isomeric yield ratio is discussed. From the measured independent yield of Xe isotopes plus the reported data, the Xe-isotopic distribution curve has been constructed. The curve is compared with the isotopic distribution curves of Xe isotopes formed in 11.5 GeV proton interactions with 238 U and Cs isotopes formed in 24 GeV proton interactions with 238 U. Upon fitting the yield curves we find that only those products with N/Z> or =1.48 fit a curve typical of a binary fission process

  1. Peptide models of protein metastable binding sites: competitive kinetics of isomerization and hydrolysis.

    Science.gov (United States)

    Khan, S A; Sekulski, J M; Erickson, B W

    1986-09-09

    alpha 2-Macroglobulin and the complement components C3 and C4 each contain a metastable binding site that is essential for covalent attachment. Two cyclic peptides are useful models of these unusual protein sites. Five-membered lactam 1 (CH3CO-Gly-Cys-Gly-Glu-Glp-Asn-NH2) contains an internal residue of pyroglutamic acid (Glp). Fifteen-membered thiolactone 2 (CH3CO-Gly-Cys-Gly-Glu-Glu-Asn-NH2 15-thiolactone) contains a thiol ester bond between Cys-2 and Glu-5. These isomeric hexapeptides are spontaneously interconverted in water. Competing with the two isomerization reactions are three reactions involving hydrolysis of 1 and 2. These five processes were found to occur simultaneously under physiologic conditions (phosphate-buffered saline, pH 7.3, 37 degrees C). Best estimates of the five rate constants for these apparent first-order reactions were obtained by comparing the observed molar percentages of peptides 1-4 with those calculated from a set of exponential equations. Both isomerization reactions (ring expansion of 1 to 2, k1 = 6.4 X 10(-5) s-1; ring contraction of 2 to 1, k-1 = 69 X 10(-5) s-1) proceeded faster than any of the hydrolysis reactions: alpha-cleavage of 1 with fragmentation to form dipeptide 3 (k2 = 3.3 X 10(-5) s-1), gamma-cleavage of 1 with ring opening to yield mercapto acid 4 (k3 = 0.35 X 10(-5) s-1), and hydrolysis of 2 with ring opening to give 4 (k4 = 1.9 X 10(-5) s-1). The isomerization rate ratio (k1/k-1 = 10.9) agreed with the isomer ratio at equilibrium (1:2 = 11 starting from 1 and 10 starting from 2). The alpha/gamma regioselectivity ratio (k2/k3 = 9.7) for hydrolysis of the internal Glp residue of 1 was consistent with results for model tripeptides. Part of the chemistry of the protein metastable binding sites can be explained by similar isomerization and hydrolysis reactions.

  2. K isomerism and collectivity in neutron-rich rare-earth isotopes

    Science.gov (United States)

    Patel, Zena

    Neutron-rich rare-earth isotopes were produced by in-flight fission of 238U ions at the Radioactive Isotope Beam Factory (RIBF), RIKEN, Japan. In-flight fission of a heavy, high-intensity beam of 238U ions on a light target provides the cleanest secondary beams of neutron-rich nuclei in the rare-earth region of isotopes. In-flight fission is advantageous over other methods of nuclear production, as it allows for a secondary beam to be extracted, from which the beam species can be separated and identified. The excited states of nuclei are studied by delayed isomeric or beta-delayed gamma-ray spectroscopy. New K isomers were found in Sm (Z=62), Eu (Z=63), and Gd (Z=64) isotopes. The key results are discussed here. Excited states in the N=102 isotones 166Gd and 164Sm have been observed following isomeric decay for the first time. The K-isomeric states in 166Gd and 164Sm are due to 2-quasiparticle configurations. Based on the decay patterns and potential energy surface calculations, including beta6 deformation, both isomers are assigned a (6-) spin-parity. The half-lives of the isomeric states have been measured to be 950(60)ns and 600(140)ns for 166Gd and 164Sm respectively. Collective observables are discussed in light of the systematics of the region, giving insight into nuclear shape evolution. The decrease in the ground state band energies of 166Gd and 164Sm (N=102) compared to 164Gd and 162Sm (N=100) respectively, presents evidence for the predicted deformed shell closure at N=100. A 4-quasiparticle isomeric state has been discovered in 160Sm: the lightest deformed nucleus with a 4-quasiparticle isomer to date. The isomeric state is assigned an (11+) spin-parity with a measured half-life of 1.8(4)us. The (11+) isomeric state decays into a rotational band structure, based on a (6-) v5/2-[523] ⊗ v7/2+[633] bandhead, determined from the extracted gK-gR values. Potential energy surface and blocked BCS calculations were performed in the deformed midshell region

  3. CHRISTIAN SYMBOLISM IN FYODOR DOSTOEVSKY'S NOVEL "THE POSSESSED" ("DEMONS"

    Directory of Open Access Journals (Sweden)

    Sergei Leonidovich Sharakov

    2013-11-01

    Full Text Available The article raises a question of Christian symbolism in Fyodor Dostoevsky’s novel The Possessed (Demons. The introductory part identifies the purpose of a symbol in Christian poetics through the parallel with ancient symbolism. The author makes a conclusion that the functional role of a symbol in the ancient world and Christian tradition is different. Therefore, the ancient symbol involves a number of interrelated categories, such as fate, intuition or conjecture, inspiration, and predictions. Christian symbolism is based on the idea of redemption and moral innocence. Methodologically, the article is based on a cultural and historical approach, as well as on the comparative academic tradition. The overview of Dostoyevsky’s pre-materials for The Possessed (Demons enables us to suggest the use of Christian symbolism in this novel. Hence, the objective of the study is to investigate a composition of images and symbols in this piece of writing, with a special focus on the image of a chronicler since the storyline of the novel is developed through his perception. We make a supposition that there are several levels of Gospel perception in the artistic vision or consciousness of the chronicler, that form the basis of the symbolical composition of the novel. The article sequentially examines the examples of Christian symbolism, including the connection of ideas, characters and storylines of the novel with the Gospel. Then it gives evidence and reasons for the thesis that the Gospel gives the characters of the novel the grounds for shaping their destiny.

  4. Stability and isomerization reactions of phenyl cation C{sub 6}H{sub 5}{sup +} isomers

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Dandan [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yang, Xue [College of Science, Jilin Institute of Chemical Technology, Jilin 132022 (China); Zhang, Xiaomei; Shan, Shimin [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Xu, Haifeng, E-mail: xuhf@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yan, Bing, E-mail: yanbing@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China)

    2016-03-01

    Highlights: • A total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations were obtained at density functional theory. • The stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers were performed. • The structures, frequencies, thermodynamic properties of isomers were summarized. • Ring to ring or chain isomerization pathways were investigated using IRC method. • Result shows reactions contain hydrogen transfer, bond broken and reconstruction. - Abstract: As a key polyatomic molecular cation that plays a pivotal role in growth of the polycyclic aromatic hydrocarbons, phenyl cation C{sub 6}H{sub 5}{sup +} exhibits various isomers and isomerization reactions. Investigation on the structure and stability of the isomers as well as the isomerization is important for better understanding the chemical reactions involving C{sub 6}H{sub 5}{sup +} cations. In this work, we have performed a theoretical study on the stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers at density functional theory B3LYP/6-311G (d, p) level. We have obtained a total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations, most of which are reported for the first time. The geometries, vibrational frequencies, thermodynamic properties and stability of 28 out of 60 isomers have been summarized in detail. Different ring-to-ring and ring-to-chain isomerization pathways, which are connected via 28 transition states, have been investigated using the intrinsic reaction coordinate method. The results show that the isomerization reactions occur via hydrogen migration followed by bond-breaking and reconstruction.

  5. Adducin family proteins possess different nuclear export potentials.

    Science.gov (United States)

    Liu, Chia-Mei; Hsu, Wen-Hsin; Lin, Wan-Yi; Chen, Hong-Chen

    2017-05-10

    The adducin (ADD) family proteins, namely ADD1, ADD2, and ADD3, are actin-binding proteins that play important roles in the stabilization of membrane cytoskeleton and cell-cell junctions. All the ADD proteins contain a highly conserved bipartite nuclear localization signal (NLS) at the carboxyl termini, but only ADD1 can localize to the nucleus. The reason for this discrepancy is not clear. To avoid the potential effect of cell-cell junctions on the distribution of ADD proteins, HA epitope-tagged ADD proteins and mutants were transiently expressed in NIH3T3 fibroblasts and their distribution in the cytoplasm and nucleus was examined by immunofluorescence staining. Several nuclear proteins were identified to interact with ADD1 by mass spectrometry, which were further verified by co-immunoprecipitation. In this study, we found that ADD1 was detectable both in the cytoplasm and nucleus, whereas ADD2 and ADD3 were detected only in the cytoplasm. However, ADD2 and ADD3 were partially (~40%) sequestered in the nucleus by leptomycin B, a CRM1/exportin1 inhibitor. Upon the removal of leptomycin B, ADD2 and ADD3 re-distributed to the cytoplasm. These results indicate that ADD2 and ADD3 possess functional NLS and are quickly transported to the cytoplasm upon entering the nucleus. Indeed, we found that ADD2 and ADD3 possess much higher potential to counteract the activity of the NLS derived from Simian virus 40 large T-antigen than ADD1. All the ADD proteins appear to contain multiple nuclear export signals mainly in their head and neck domains. However, except for the leucine-rich motif ( 377 FEALMRMLDWLGYRT 391 ) in the neck domain of ADD1, no other classic nuclear export signal was identified in the ADD proteins. In addition, the nuclear retention of ADD1 facilitates its interaction with RNA polymerase II and zinc-finger protein 331. Our results suggest that ADD2 and ADD3 possess functional NLS and shuttle between the cytoplasm and nucleus. The discrepancy in the

  6. Immobilized cells of Candida rugosa possessing fumarase activity

    Energy Technology Data Exchange (ETDEWEB)

    Yang, L.; Zhone, L.

    1980-01-01

    Immobilized cells of C. rugosa that possessed fumarase activity were prepared by different methods; the most active immobilized cells were entrapped in polyacrylamide gels. The effects of pH temperature, and divalent cations on the fumarase activity of both immobilized and native cells were the same. Mn/sup 2 +/, Mg/sup 2 +/, Ca/sup 2 +/, and Fe/sup 2 +/ did not protect the immobilized enzyme against thermal inactivation. The activity of immobilized fumarase remained constant during 91 days of storage of 4-6 degrees. The immobilized cell column was used for the continuous production of L-malic acid from 1M fumarate at 30 degrees and pH 8.5. The immobilized column operated steadily for 2 months. Half life of the immobilized fumarase at 30 degrees was 95 days.

  7. Social forces for team coordination in ball possession game

    Science.gov (United States)

    Yokoyama, Keiko; Shima, Hiroyuki; Fujii, Keisuke; Tabuchi, Noriyuki; Yamamoto, Yuji

    2018-02-01

    Team coordination is a basic human behavioral trait observed in many real-life communities. To promote teamwork, it is important to cultivate social skills that elicit team coordination. In the present work, we consider which social skills are indispensable for individuals performing a ball possession game in soccer. We develop a simple social force model that describes the synchronized motion of offensive players. Comparing the simulation results with experimental observations, we uncovered that the cooperative social force, a measure of perception skill, has the most important role in reproducing the harmonized collective motion of experienced players in the task. We further developed an experimental tool that facilitates real players' perceptions of interpersonal distance, revealing that the tool improves novice players' motions as if the cooperative social force were imposed.

  8. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

    2018-01-16

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

  9. A system to measure isomeric state half-lives in the 10 ns to 10 μs range

    Energy Technology Data Exchange (ETDEWEB)

    Toufen, D. L., E-mail: dennis@if.usp.br [Institute of Physics, University of São Paulo, C.P. 66318, 05315-970 São Paulo, São Paulo (Brazil); Federal Institute of Education, Science and Technology of São Paulo - IFSP, 07115-000 Guarulhos, São Paulo (Brazil); Allegro, P. R. P.; Medina, N. H.; Oliveira, J. R. B.; Cybulska, E. W.; Seale, W. A.; Ribas, R. V. [Institute of Physics, University of São Paulo, C.P. 66318, 05315-970 São Paulo, São Paulo (Brazil); Linares, R. [Fluminense Federal University, 24220-900 Niterói, Rio de Janeiro (Brazil); Silveira, M. A. G. [Universitary Center of FEI, 09850-901 São Bernardo do Campo, São Paulo (Brazil)

    2014-07-15

    The Isomeric State Measurement System (SISMEI) was developed to search for isomeric nuclear states produced by fusion-evaporation reactions. The SISMEI consists of 10 plastic phoswich telescopes, two lead shields, one NaI(Tl) scintillation detector, two Compton suppressed HPGe γ-ray detectors, and a cone with a recoil product catcher. The new system was tested at the 8 UD Pelletron tandem accelerator of the University of São Paulo with the measurement of two known isomeric states: {sup 54}Fe, 10{sup +} state (E = 6527.1 (11) keV, T{sub 1/2} = 364(7) ns) and the 5/2{sup +} state of {sup 19}F (E = 197.143 (4) keV, T{sub 1/2} = 89.3 (10) ns). The results indicate that the system is capable of identifying delayed transitions, of measuring isomeric state lifetimes, and of identifying the feeding transitions of the isomeric state through the delayed γ-γ coincidence method. The measured half-life for the 10{sup +} state was T{sub 1/2} = 365(14) ns and for the 5/2{sup +} state, 100(36) ns.

  10. A system to measure isomeric state half-lives in the 10 ns to 10 μs range

    Science.gov (United States)

    Toufen, D. L.; Allegro, P. R. P.; Medina, N. H.; Oliveira, J. R. B.; Cybulska, E. W.; Seale, W. A.; Linares, R.; Silveira, M. A. G.; Ribas, R. V.

    2014-07-01

    The Isomeric State Measurement System (SISMEI) was developed to search for isomeric nuclear states produced by fusion-evaporation reactions. The SISMEI consists of 10 plastic phoswich telescopes, two lead shields, one NaI(Tl) scintillation detector, two Compton suppressed HPGe γ-ray detectors, and a cone with a recoil product catcher. The new system was tested at the 8 UD Pelletron tandem accelerator of the University of São Paulo with the measurement of two known isomeric states: 54Fe, 10+ state (E = 6527.1 (11) keV, T1/2 = 364(7) ns) and the 5/2+ state of 19F (E = 197.143 (4) keV, T1/2 = 89.3 (10) ns). The results indicate that the system is capable of identifying delayed transitions, of measuring isomeric state lifetimes, and of identifying the feeding transitions of the isomeric state through the delayed γ-γ coincidence method. The measured half-life for the 10+ state was T1/2 = 365(14) ns and for the 5/2+ state, 100(36) ns.

  11. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

    2018-01-01

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

  12. A comprehensive mechanistic picture of the isomerizing alkoxycarbonylation of plant oils

    KAUST Repository

    Roesle, Philipp

    2014-12-03

    Theoretical studies on the overall catalytic cycle of isomerizing alkoxycarbonylation reveal the steric congestion around the diphosphine coordinated Pd-center as decisive for selectivity and productivity. The energy profile of isomerization is flat with diphosphines of variable steric bulk, but the preference for the formation of the linear Pd-alkyl species is more pronounced with sterically demanding diphosphines. CO insertion is feasible and reversible for all Pd-alkyl species studied and only little affected by the diphosphine. The overall rate-limiting step associated with the highest energetic barrier is methanolysis of the Pd-acyl species. Considering methanolysis of the linear Pd-acyl species, whose energetic barrier is lowest within all the Pd-acyl species studied, the barrier is calculated to be lower for more congesting diphosphines. Calculations indicate that energy differences of methanolysis of the linear versus branched Pd-acyls are more pronounced for more bulky diphosphines, due to involvement of different numbers of methanol molecules in the transition state. Experimental studies under pressure reactor conditions showed a faster conversion of shorter chain olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced by pressure reactor and NMR studies. Multiple unsaturated fatty acids were observed to form a terminal Pd-allyl species upon reaction with the catalytically active Pd-hydride species. This process and further carbonylation are slow compared to isomerizing methoxycarbonylation of monounsaturated fatty acids, but selective.

  13. A comprehensive mechanistic picture of the isomerizing alkoxycarbonylation of plant oils.

    Science.gov (United States)

    Roesle, Philipp; Caporaso, Lucia; Schnitte, Manuel; Goldbach, Verena; Cavallo, Luigi; Mecking, Stefan

    2014-12-03

    Theoretical studies on the overall catalytic cycle of isomerizing alkoxycarbonylation reveal the steric congestion around the diphosphine coordinated Pd-center as decisive for selectivity and productivity. The energy profile of isomerization is flat with diphosphines of variable steric bulk, but the preference for the formation of the linear Pd-alkyl species is more pronounced with sterically demanding diphosphines. CO insertion is feasible and reversible for all Pd-alkyl species studied and only little affected by the diphosphine. The overall rate-limiting step associated with the highest energetic barrier is methanolysis of the Pd-acyl species. Considering methanolysis of the linear Pd-acyl species, whose energetic barrier is lowest within all the Pd-acyl species studied, the barrier is calculated to be lower for more congesting diphosphines. Calculations indicate that energy differences of methanolysis of the linear versus branched Pd-acyls are more pronounced for more bulky diphosphines, due to involvement of different numbers of methanol molecules in the transition state. Experimental studies under pressure reactor conditions showed a faster conversion of shorter chain olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced by pressure reactor and NMR studies. Multiple unsaturated fatty acids were observed to form a terminal Pd-allyl species upon reaction with the catalytically active Pd-hydride species. This process and further carbonylation are slow compared to isomerizing methoxycarbonylation of monounsaturated fatty acids, but selective.

  14. Positionally isomeric organic gelators: structure-gelation study, racemic versus enantiomeric gelators, and solvation effects.

    Science.gov (United States)

    Caplar, Vesna; Frkanec, Leo; Sijaković Vujicić, Natasa; Zinić, Mladen

    2010-03-08

    Low molecular weight gelator molecules consisting of aliphatic acid, amino acid (phenylglycine), and omega-aminoaliphatic acid units have been designed. By varying the number of methylene units in the aliphatic and omega-aminoaliphatic acid chains, as defined by descriptors m and n, respectively, a series of positionally isomeric gelators having different positions of the peptidic hydrogen-bonding unit within the gelator molecule has been obtained. The gelation properties of the positional isomers have been determined in relation to a defined set of twenty solvents of different structure and polarity and analyzed in terms of gelator versatility (G(ver)) and effectiveness (G(eff)). The results of gelation tests have shown that simple synthetic optimizations of a "lead gelator molecule" by variation of m and n, end-group polarity (carboxylic acid versus sodium carboxylate), and stereochemistry (racemate versus optically pure form) allowed the identification of gelators with tremendously improved versatility (G(ver)) and effectiveness (G(eff)). Dramatic differences in G(eff) values of up to 70 times could be observed between pure racemate/enantiomer pairs of some gelators, which were manifested even in the gelation of very similar solvents such as isomeric xylenes. The combined results of spectroscopic ((1)H NMR, FTIR), electron microscopy (TEM), and X-ray diffraction studies suggest similar organization of the positionally isomeric gelators at the molecular level, comprising parallel beta-sheet hydrogen-bonded primary assemblies that form inversed bilayers at a higher organizational level. Differential scanning calorimetry (DSC) studies of selected enantiomer/racemate gelator pairs and their o- and p-xylene gels revealed the simultaneous presence of different polymorphs in the racemate gels. The increased gelation effectiveness of the racemate compared to that of the single enantiomer is most likely a consequence of its spontaneous resolution into enantiomeric

  15. Outcomes following the Kawashima procedure for single-ventricle palliation in left atrial isomerism.

    Science.gov (United States)

    Vollebregt, Anne; Pushparajah, Kuberan; Rizvi, Maleeha; Hoschtitzky, Andreas; Anderson, David; Austin, Conal; Tibby, Shane M; Simpson, John

    2012-03-01

    Patients with left atrial isomerism and interrupted inferior vena cava palliated with a superior cavopulmonary connection or Kawashima procedure (KP) have a high incidence of developing pulmonary arteriovenous malformations. The necessity for hepatic vein redirection (HVR) and its timing remains a controversy. We aimed to assess the clinical outcome of patients with left atrial isomerism following a KP. The main end points were death, requirement for HVR and the impact of HVR on oxygen saturation. Retrospective review of 21 patients with a diagnosis of left atrial isomerism, interruption of the inferior vena cava and single-ventricle physiology managed with a KP at a single centre between January 1990 and March 2010. Twenty-one patients had a KP, with 12 subsequently undergoing HVR. There was relatively a constant monthly decrement in the proportion of patients who were free from death or HVR up until 60 months following the KP, with a dramatic increase in the hazard after this time. The Cox proportional hazards regression model demonstrated a reduced early risk for HVR or death in patients who underwent pulmonary artery banding versus arterial shunt as the primary procedure (hazard ratio: 0.10; P = 0.01), and an increased risk with bilateral superior vena cavas (SVCs) (hazard ratio: 3.4; P = 0.04) and age at KP (hazard ratio: 1.02 per month increase in age at KP; P = 0.02). HVR mortality was relatively high with 3 of 12 patients dying in the early postoperative period with profound cyanosis. The timing of HVR after the KP did not influence the postoperative rate of increase in oxygen saturation. These findings confirm that the majority of patients who undergo a KP will require HVR. Patients who are older at the time of the KP or having an initial arterial shunt or bilateral SVCs are at higher risk of HVR or death. The relatively high mortality at HVR was characterized by severe postoperative cyanosis.

  16. Dipole-resonance assisted isomerization in the electronic ground state using few-cycle infrared pulses.

    Science.gov (United States)

    Skocek, Oliver; Uiberacker, Christoph; Jakubetz, Werner

    2011-06-30

    A computational investigation of HCN → HNC isomerization in the electronic ground state by one- and few-cycle infrared pulses is presented. Starting from a vibrationally pre-excited reagent state, isomerization yields of more than 50% are obtained using single one- to five-cycle pulses. The principal mechanism includes two steps of population transfer by dipole-resonance (DR), and hence, the success of the method is closely linked to the polarity of the system and, in particular, the stepwise change of the dipole moment from reactant to transition state and on to products. The yield drops massively if the diagonal dipole matrix elements are artificially set to zero. In detail, the mechanism includes DR-induced preparation of a delocalized vibrational wavepacket, which traverses the barrier region and is finally trapped in the product well by DR-dominated de-excitation. The excitation and de-excitation steps are triggered by pulse lobes of opposite field direction. As the number of optical cycles is increased, the leading field lobes prepare a vibrational superposition state by off-resonant ladder climbing, which is then subjected to the three steps of the principal isomerization mechanism. DR excitation is more efficient from a preformed vibrational wavepacket than from a molecular eigenstate. The entire process can be loosely described as Tannor-Kosloff-Rice type transfer mechanism on a single potential surface effected by a single pulse, individual field lobes assuming the roles of pump- and dump-pulses. Pre-excitation to a transient wavepacket can be enhanced by applying a separate, comparatively weak few-cycle prepulse, in which the prepulse prepares a vibrational wavepacket. The two-pulse setup corresponds to a double Tannor-Kosloff-Rice control scheme on a single potential surface.

  17. Abnormal radioactive decays out of long-lived super- and hyper-deformed isomeric states

    International Nuclear Information System (INIS)

    Marinov, A.; Gelberg, S.; Kolb, D.

    2000-01-01

    Complete text of publication follows. Recently (1-3) long-lived isomeric states have been found in the super- and hyper-deformed wells of the potential. These isomers manifested themselves by abnormal particle decays. An isomeric state in the superdeformed well of the potential in the parent nucleus can decay by very enhanced α-particle groups to superdeformed states in the daughter (1) or by very retarded α-particles (3) and also by protons (2) to normal states in the daughters. Similarly an isomeric state in the hyper-deformed well may decay by very retarded α-particle groups to superdeformed states (3), or by very enhanced α-groups to hyper-deformed states in the daughter nucleus (4). All these very unusual decay modes have been observed experimentally (1-4). For instance, a very high energy α-group of 8.6 MeV with 40d ≤ t 1/2 ≤ 2y (retardation factor of ∼10 13 ) has been observed in 195 Hg and interpreted as a III min → II min α-transition (3). Likewise, relatively low-energy and very enhanced α-particle groups (enhancement factors of 10 5 to 10 7 ) have been seen in several actinide sources and interpreted as due to II min → II min and III min → III min transitions (4). These unusual decay modes introduce new considerations in the study of heavy and superheavy elements. For instance, if low-energy α-particle groups around 4.4 - 4.6 MeV have been seen in nature (5), they may be interpreted as due to very enhanced III min → III min transitions in the superheavy element region around Z = 108 (eka-Os) with t 1/2 ∼10 8 y rather than ∼10 15 y as expected for normal α-transitions of such energies in this region, or due to very retarded III min → II min or II min → I min decays in nuclei around Os itself. In both cases, if such activities have been seen in nature, they indicate that the existence of the II min and III min isomeric states may be important in the nucleosynthesis process. It should be mentioned that long-lived high

  18. Cascade olefin isomerization/intramolecular Diels-Alder reaction catalyzed by N-heterocyclic carbenes.

    Science.gov (United States)

    Kowalczyk, Marcin; Lupton, David W

    2014-05-19

    The addition of an N-heterocyclic carbene to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels-Alder reaction, for which mechanistic studies implicate Lewis base catalysis. Preliminary studies into the utility of the products have been undertaken with reductive and oxidative cleavage, giving materials for potential use in complex-target synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Modelling of tracer-kinetic results using xylene isomerization as an example

    International Nuclear Information System (INIS)

    Bauer, F.J.; Dermietzel, J.; Roesseler, M.; Koch, H.

    1976-01-01

    The analysis of results from differential or/and integral reactor experiments often admits the interpretation of a chemical reaction in several ways. In addition, the use of mathematical methods for the model selection and planning of experiments is rendered more difficult by great confidence intervals of the ascertained model parameters. The application of radioactively labelled molecules results in improving the knowledge of reaction mechanisms as well as the assessment of parameters obtained. This is shown on the basis of modelling the isomerization of xylene. (author)

  20. Macrocyclic effects upon isomeric Cu M and M Cu cores. Formation ...

    Indian Academy of Sciences (India)

    Administrator

    from the iminic site to the aminic site in the synthesis of 10 is explained by ... Our previous studies suggest that isomeric MIICuII ... Calcd. for C24H27Br2ClCuN4NiO8: C 35⋅28; H 3⋅33; N 6⋅86; Cu 7⋅78; Ni .... Electronic absorption spectra in .... 3. 1497(1). 1452. ⋅3(5). 2992(1). 1860(2). 3206(1). Z. 2. 2. 4. 2. 4. D calcd. /g.

  1. Isotope exchange study of nickel xanthate in presence of aniline and isomeric toluidines

    International Nuclear Information System (INIS)

    Naidu, G.R.K.; Naidu, P.R.

    1982-01-01

    Isotopic exchange behaviour of nickel xanthate is studied in the presence of aniline and three isomeric toluidines at 18degC. The effect of base concentration is also studied on the exchange rate. The results show that the complex is labile in the kinetic sense in the presence of aniline meta and para toluidines. The rate of exchange increases with and para toluidines. The rate of exchange increases with increase in concentration of the base. The complex displays inert behaviour in the presence of o-toluidine and it is ascribed to dominant steric effect. (author)

  2. Magnetic dipole moments of High-K isomeric states in Hf isotopes

    CERN Multimedia

    Walters, W; Nishimura, K; Bingham, C R

    2007-01-01

    It is proposed to make precision measurements of the magnetic moments of 5 multi-quasi-particle K-isomers in Hf nuclei by the Nuclear Magnetic Resonance of Oriented Nuclei (NMR/ON) technique using the NICOLE on-line nuclear orientation facility and exploiting the unique HfF$_{3}$ beams recently available at ISOLDE. Results will be used to extract single-particle and collective g-factors of the isomeric states and their excitations and to shed new light on their structure.

  3. β decay and isomeric properties of neutron-rich Ca and Sc isotopes

    International Nuclear Information System (INIS)

    Crawford, H. L.; Mantica, P. F.; Berryman, J. S.; Stoker, J. B.; Janssens, R. V. F.; Carpenter, M. P.; Kay, B. P.; Lauritsen, T.; Zhu, S.; Broda, R.; Cieplicka, N.; Fornal, B.; Grinyer, G. F.; Minamisono, K.; Hoteling, N.; Stefanescu, I.; Walters, W. B.

    2010-01-01

    The isomeric and β-decay properties of neutron-rich 53-57 Sc and 53,54 Ca nuclei near neutron number N=32 are reported, and the low-energy level schemes of 53,54,56 Sc and 53-57 Ti are presented. The low-energy level structures of the 21 Sc isotopes are discussed in terms of the coupling of the valence 1f 7/2 proton to states in the corresponding 20 Ca cores. Implications with respect to the robustness of the N=32 subshell closure are discussed, as well as the repercussions for a possible N=34 subshell closure.

  4. Quantum control of isomerization by robust navigation in the energy spectrum

    Energy Technology Data Exchange (ETDEWEB)

    Murgida, G. E., E-mail: murgida@tandar.cnea.gov.ar [Centro Atómico Constituyentes, GIyA, CNEA, San Martín, and Consejo Nacional de Investigaciones Científicas y Técnicas, C1033AAJ Buenos Aires (Argentina); Arranz, F. J., E-mail: fj.arranz@upm.es [Grupo de Sistemas Complejos, Universidad Politécnica de Madrid, 28040 Madrid (Spain); Borondo, F., E-mail: f.borondo@uam.es [Departamento de Química, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Instituto de Ciencias Matemáticas (ICMAT), Cantoblanco, 28049 Madrid (Spain)

    2015-12-07

    In this paper, we present a detailed study on the application of the quantum control technique of navigation in the energy spectrum to chemical isomerization processes, namely, CN–Li⇆ Li–CN. This technique is based on the controlled time variation of a Hamiltonian parameter, an external uniform electric field in our case. The main result of our work establishes that the navigation involved in the method is robust, in the sense that quite sizable deviations from a pre-established control parameter time profile can be introduced and still get good final results. This is specially relevant thinking of a experimental implementation of the method.

  5. Isomeric N-Annulated Perylene Diimide Dimers for Organic Solar Cells.

    Science.gov (United States)

    Ma, Zetong; Fu, Huiting; Meng, Dong; Jiang, Wei; Sun, Yanming; Wang, Zhaohui

    2018-04-16

    Two isomeric N-annulated perylene diimide dimers, namely, p-BDNP and m-BDNP were designed and synthesized via geometric tuning. The distinct molecular geometry and packing arrangements of isomers with almost identical optical and electrochemical properties rendered us an in-depth understanding of the molecular structure-aggregation state-photovoltaic performance relationship. Blended with the commercially available donor PCE-10, p-BDNP and m-BDNP showed distinct differences in photovoltaic performance with power conversion efficiencies (PCEs) of 5.01 % and 4.15 %, respectively. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. g-factor of the 7- isomeric state in 128Ba

    International Nuclear Information System (INIS)

    Kaur, J.; Bansal, N.; Bhati, A.K.; Sharma, V.R.; Kumar, H.; Kumar, R.; Bhowmik, R.K.; Kumar, V.

    2014-01-01

    The time differential perturbed angular distribution technique (TDPAD) has been used to measure the g-factor of the 2396 keV, 7 - isomeric state in 128 Ba. The measured value of g(7 - ) is 1.21 ± 0.01. This value is about 80% higher than the value for the expected configuration of the state and also different in sign. This clearly shows that the configuration of the state does not correspond to the pure two quasineutron configuration that was assigned to it through previous results of in-beam γ-ray spectroscopy

  7. Anesthetic implications of total anomalous systemic venous connection to left atrium with left isomerism

    Directory of Open Access Journals (Sweden)

    Parimala Prasanna Simha

    2012-01-01

    Full Text Available Total anomalous systemic venous connection (TASVC to the left atrium (LA is a rare congenital anomaly. An 11-year-old girl presented with complaints of palpitations and cyanosis. TASVC with left isomerism and noncompaction of LV was diagnosed after contrast echocardiogram and computed tomography angiogram. The knowledge of anatomy and pathophysiology is essential for the successful management of these cases. Anesthetic concerns in this case were polycythemia, paradoxical embolism and rhythm abnormalities. The patient was successfully operated by rerouting the systemic venous connection to the right atrium.

  8. Behavior of the excited deformed band and search for shape isomerism in 184Hg

    International Nuclear Information System (INIS)

    Cole, J.D.; Hamilton, J.H.; Ramayya, A.V.; Nettles, W.G.; Kawakami, H.; Spejewski, E.H.; Ijaz, M.A.; Toth, K.S.; Robinson, E.L.; Sastry, K.S.R.; Lin, J.; Avignone, F.T.; Brantley, W.H.; Rao, P.V.G.

    1976-01-01

    The new isotope 184 Tl has been identified with T 1 / 2 =11 +- 1 sec and the levels in 184 Hg investigated from its decay. The 0 + band head of a deformed band was found to drop to 375 keV in agreement with theoretical predictions. The mean life of the 375-keV 0 + level was measured to be 0.9 +- 0.3 nsec which is a factor of 10 faster than theoretically predicted for a shape-isomeric E2 transition

  9. An infrared study of the nitro—nitrito linkage isomerization in solid nitro- and nitritopentamminecobalt(III) chloride

    Science.gov (United States)

    Heyns, A. M.; de Waal, D.

    1989-01-01

    The photochemical isomerization reaction of [Co(NH 3) 5NO 2]Cl 2 to [Co(NH 3) 5ONO]Cl 2 has been studied in the solid state by means of i.r. spectroscopy. The reaction is first order with k = 2.53±0.05 × 10 -4s -1 and is much faster ( t1/2=49min) than the well-known spontaneous nitrito → nitro isomerization ( t1/2 = 6 days). The i.r. bands of both the NH 3 and ONO - -groups in the range 4000-50 cm -1 indicate minor differences between the structures of freshly and photochemically prepared [Co(NH 3) 5ONO]Cl 2. The far i.r. spectra indicate the disorder existing in the intermediate products during the isomerization processes.

  10. Determination of the isomeric fraction in a postaccelerated radioactive ion beam using the coupled decay-chain equations

    CERN Document Server

    Ekstrom, A; Dijulio, D D; Cederkall, J; Van de Walle, J

    2010-01-01

    A method based on the coupled decay-chain equations for extracting the isotopic and the isomeric composition of a postaccelerated radioactive ion beam is presented and demonstrated on a data set from a Coulomb excitation experiment. This is the first attempt of analyzing the content of a postaccelerated radioactive ion beam using this technique. The beam composition is required for an absolute normalization of the measurement. The strength of the method, as compared to present online-based methods, lies in the determination of the isomeric fraction of a partially isomeric beam using all data accumulated during the experiment. We discuss the limitations and sensitivity of the method with respect to the gamma-ray detection efficiency and the accumulated flux. (C) 2010 Elsevier B.V. All rights reserved.

  11. The Antineoplastic Effect of Nitric Oxide-Donating Acetylsalicylic Acid (NO-ASA) in Chronic Lymphocytic Leukemia (CLL) Cells is Highly Dependent on its Positional Isomerism.

    Science.gov (United States)

    Gehrke, Iris; Razavi, Regina; Poll-Wolbeck, Simon Jonas; Berkessel, Albrecht; Hallek, Michael; Kreuzer, Karl-Anton

    2011-10-01

    Chronic Lymphocytic Leukemia (CLL) is not curable in patients that are not eligible for allogeneic stem cell transplantation. Therefore, new treatment options are highly desirable. Chemically modified nonsteroidal anti-inflammatory drugs (NSAIDs), such as nitric-oxide-donating acetylsalicylic acid (NO-ASA), have been described to possess antineoplastic capacity. Recently, we could demonstrate a potent apoptosis induction in primary CLL cells in vitro and tumor growth inhibition by para-NO-ASA in a xenograft mouse model. However, little is known about the impact of positional isomerism of NO-ASA on its antineoplastic capacity in CLL. Primary CLL cells were treated with the meta-or para-isomer of NO-ASA at varying concentrations and durations. Viability was assessed flow cytometrically by annexin V-FITC/PI staining and by CellTiter-Glo luminescence cell viability assay. Caspase and PARP cleavage as well as involvement of β-catenin/Lef-1 signaling was determined by immunoblotting. For caspase inhibition, BD™ ApoBlock was used. Nude mice were xenografted with JVM3 cells and treated with meta-NO-ASA, para-NO-ASA or vehicle control. The meta-isomer was entirely ineffective in inducing CLL cell apoptosis in concentrations up to 100 μM, while para-NO-ASA acted in the low micromolar range. meta-NO-ASA, in contrast to para-NO-ASA, did not alter caspase activity. While para-NO-ASA action involved inhibition of β-catenin/Lef-1 signaling, meta-NO-ASA did not show any impact on this signaling pathway. Further, meta-NO-ASA did not significantly reduce tumor growth in a CLL xenograft mouse model, while para-NO-ASA was highly potent. We conclude that positional isomerism is crucial for the antineoplastic effect of NO-ASA in CLL. It can be suggested that the para-isomer, but not the meta-isomer, generates a chemical structure which is essential for the neoplastic effect of NO-ASA.

  12. Radiation protective agents possessing anti-oxidative properties

    Energy Technology Data Exchange (ETDEWEB)

    Anzai, Kazunori; Ueno, Emi; Yoshida, Akira; Furuse, Masako; Ikota, Nobuo [National Inst. of Radiological Sciences, Research Center for Radiation Safety, Chiba, Chiba (Japan)

    2005-11-15

    The purpose of studies is to see mechanisms of radiation protection of agents possessing anti-oxidative properties because the initial step resulting in radiation hazard is the formation of radicals by water radiolysis. Agents were commercially available or synthesized proxyl derivatives (spin prove agents), commercially available spin-trapping agents, edaravone and TMG (a tocopherol glycoside). Mice and cultured cells were X-irradiated by Shimadzu Pantak HF-320 or 320S. Survivals of cells were determined by colony assay and of mice, to which the agents were given intraperitoneally before or after X-irradiation, within 30 days post irradiation. Plasma and marrow concentrations of proxyls were estimated by electron spin resonance (ESR) spectrometry. Mechanisms of their radiation protective effects were shown different from agent to agent. TMG was found effective even post irradiation, which suggests a possibility for a new drug development. Some (spin trapping agents and TMG), virtually ineffective at the cell level, were found effective in the whole body, suggesting the necessity of studies on their disposition and metabolism. (S.I.)

  13. Radiation protective agents possessing anti-oxidative properties

    International Nuclear Information System (INIS)

    Anzai, Kazunori; Ueno, Emi; Yoshida, Akira; Furuse, Masako; Ikota, Nobuo

    2005-01-01

    The purpose of studies is to see mechanisms of radiation protection of agents possessing anti-oxidative properties because the initial step resulting in radiation hazard is the formation of radicals by water radiolysis. Agents were commercially available or synthesized proxyl derivatives (spin prove agents), commercially available spin-trapping agents, edaravone and TMG (a tocopherol glycoside). Mice and cultured cells were X-irradiated by Shimadzu Pantak HF-320 or 320S. Survivals of cells were determined by colony assay and of mice, to which the agents were given intraperitoneally before or after X-irradiation, within 30 days post irradiation. Plasma and marrow concentrations of proxyls were estimated by electron spin resonance (ESR) spectrometry. Mechanisms of their radiation protective effects were shown different from agent to agent. TMG was found effective even post irradiation, which suggests a possibility for a new drug development. Some (spin trapping agents and TMG), virtually ineffective at the cell level, were found effective in the whole body, suggesting the necessity of studies on their disposition and metabolism. (S.I.)

  14. The possession law suit, caused by forbidden immissions

    Directory of Open Access Journals (Sweden)

    Popov Danica D.

    2015-01-01

    Full Text Available In the Serbian Law and in most of jurisdictions, there are limits on exercising the right of property. The real estate owner must refrain from activities by which the use of other real estate is being impoded through the immission of execive gasses, vapors, smoke, heat noise, tremors etc. The property ownership whose is affected by immission exceeding the set limits, has the right to request a stop of immisions which exceeded the allowed volume of immissions. In article author describes various kinds of immissions. The general feature of this law suit is that there is only discussion on the facts and not for a legal matters. Subject matter jurisdiction for the resolution of such disputes belongs to the court of general jurisdiction, while the disputes itself is a litigation. The special rule of proceedings of action of disturbance are: provisionality of the protection of possession; urgency in proceedings; initiation of proceedings; limiting of objection; prescribing temporary measures; rendering a ruling in the form of order; appeals which may be filed within a short deadline and which does not have suspensive effect (do not delay the execution of the order; revision is not allowed etc.

  15. Novel β-amyloid aggregation inhibitors possessing a turn mimic.

    Science.gov (United States)

    Hamada, Yoshio; Miyamoto, Naoko; Kiso, Yoshiaki

    2015-04-01

    Amyloid β peptide, the main component of senile plaques found in the brain of Alzheimer disease (AD) patients, is a molecular target for AD therapeutic intervention. A number of potential AD therapeutics have been reported, including inhibitors of β-secretase, γ-secretase, and Aβ aggregation, and anti-amyloid agents, such as neprilysin, insulin degrading enzyme (IDE), and Aβ antibodies. Recently, we reported potent small-sized β-secretase (BACE1) inhibitors, which could serve as anti-AD drugs. However AD is a progressive disorder, where dementia symptoms gradually worsen over several decades, and therefore may require many years to get cured. One possible way to achieve a greater therapeutic effect is through simultaneous administration of multiple drugs, similar to those used in Highly Active Anti-Retroviral Therapy (HAART) used to treat AIDS. In order to overcome AD, we took a drug discovery approach to evaluate, novel β-amyloid aggregation inhibitors. Previously, we reported that a tong-type compound possessing a turn mimic as the inhibitor of HIV-1 protease dimerization. Oligomerized amyloid β peptides contain a turn structure within the molecule. Here, we designed and synthesized novel β-amyloid aggregation inhibitors with a turn-mimic template, based on the turn conformer of the oligomerized amyloid β peptides. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Photo-isomerization induced rapid photo-degradation of optical nonlinearity in cyano substituted stilbene derivative doped poled polymer

    International Nuclear Information System (INIS)

    Yan Jieyun; Liu Liying; Ji Liyong; Ye Mingxin; Xu Lei; Wang Wencheng

    2004-01-01

    We found that, although alpha'-cyano-4'-nitro-4-N, N-dimethylaminostilbene has larger hyperpolarizability than that of conventional 4'-N, N-dimethylamino-nitrostilbene, the addition of the cyano group makes it much more easy to photo-isomerize, thus destroying the molecular ordering in poled chromophore doped polymers. Experimental evidence was obtained by monitoring the second-harmonic generation intensity, UV-Vis absorption spectrum, and FTIR spectrum. The photo-isomerization reaction process was monitored by optical pump induced absorption anisotropy measurement. Comparisons with the behaviour of a azobenzene dye are also made

  17. Modulating the Physical and Electronic Properties over Positional Isomerism: The Dispirofluorene-Dihydroindacenodithiophene (DSF-IDT) Family.

    Science.gov (United States)

    Peltier, Jean-David; Heinrich, Benoît; Donnio, Bertrand; Jeannin, Olivier; Rault-Berthelot, Joëlle; Poriel, Cyril

    2017-12-06

    We report the first studies on the intrinsic properties of a meta-substituted dihydroindacenodithienyl fragment and more generally the strong impact of positional isomerism on dihydroindacenodithiophene derivatives. The influence of the para and meta linkages has notably been highlighted not only for the electronic properties in solution (electrochemical properties, anodic polymerization, HOMO/LUMO energy levels, optical transitions, fluorescence spectra) but also on the physical properties in the solid state (molecular organization, crystallinity, and phase transitions). The positional isomerism hence appears to be a very efficient tool to drastically tune the properties of dihydroindacenodithiophene derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Isomeric cross-section ratios of some (n,2n) reactions at 14. 7 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Garg, K C; Khurana, C S [Punjabi Univ., Patiala (India). Nuclear Science Labs.

    1979-08-01

    Isomeric cross-section ratios of (n,2n) reactions at 14.7 MeV leading to the millisecond isomeric levels have been calculated theoretically using the statistical theory of nuclear reactions and the spin distribution form due to Bethe and Bloch. The theoretical ratios have been compared with the experimentally measured values in order to evaluate the spin cut-off parameter sigma. This parameter has been used to calculate the effective moment of inertia of the nucleus to draw useful conclusions from the results of present calculations.

  19. First observation of high spin states and isomeric decay in 210Fr

    International Nuclear Information System (INIS)

    Kanjilal, D.; Saha, S.; Bhattacharya, S.; Goswami, A.; Kshetri, R.; Raut, R.; Muralithar, S.; Singh, R. P.; Mukherjee, G.; Mukherjee, B.

    2011-01-01

    The first observation of the prompt and the delayed γ transitions involving the high spin states in 210 Fr is reported. The decay of the high spin states and the isomeric levels of 210 Fr, identified for the first time from the known sequence of low-lying transitions found earlier in the α decay of 214 Ac, were studied. High spin states of the doubly-odd 210 Fr, which were produced by the fusion evaporation reaction 197 Au ( 16 O, xn) 213-x Fr, were populated and the subsequent emitted γ rays were detected through the high-sensitivity germanium clover detector array INGA. The level scheme up to yrast levels of 5.3 MeV excitation energy and ∼20(ℎ/2π) angular momentum could be established for the first time through γγ, γγΔT coincidence, and DCO ratio measurements. A new low-lying isomeric transition at E γ = 203(2) keV was observed. The half-life was measured to be T 1/2 = 41(2) ns. The measured half-life was compared with the corresponding single-particle estimate, based on the level scheme obtained from the experiment.

  20. 1,2-Fluorine Radical Rearrangements: Isomerization Events in Perfluorinated Radicals.

    Science.gov (United States)

    Van Hoomissen, Daniel J; Vyas, Shubham

    2017-11-16

    Devising effective degradation technologies for perfluoroalkyl substances (PFASs) is an active area of research, where the molecular mechanisms involving both oxidative and reductive pathways are still elusive. One commonly neglected pathway in PFAS degradation is fluorine atom migration in perfluoroalkyl radicals, which was largely assumed to be implausible because of the high C-F bond strength. Using density functional theory calculations, it was demonstrated that 1,2-F atom migrations are thermodynamically favored when the fluorine atom migrated from a less branched carbon center to a more branched carbon center. Activation barriers for these rearrangements were within 19-29 kcal/mol, which are possible to easily overcome at elevated temperatures or in photochemically activated species in the gas or aqueous phase. It was also found that the activation barriers for the 1,2-F atom migration are lowered as much as by 10 kcal/mol when common oxidative degradation products such as HF assisted the rearrangements or if the resulting radical center was stabilized by vicinal π-bonds. Natural bond orbital analyses showed that fluorine moves as a radical in a noncharge-separated state. These findings add an important reaction to the existing knowledge of mechanisms for PFAS degradation and highlights the fact that 1,2-F atom shifts may be a small channel for isomerization of these compounds, but upon availability of mineralization products, this isomerization process could become more prominent.

  1. An Insight into Flotation Chemistry of Pyrite with Isomeric Xanthates: A Combined Experimental and Computational Study

    Directory of Open Access Journals (Sweden)

    Guihong Han

    2018-04-01

    Full Text Available The flotation chemistry between pyrite and isomeric xanthates (butyl xanthate and isobutyl xanthate was investigated by means of adsorption experiments, surface tension tests, and molecular dynamic simulations in this work. The flotation chemical results were confirmed and further interpreted by quantum chemical calculations. The experiment results demonstrated that the isobutyl xanthate exhibited superior adsorption capacity and surface activity than those of butyl xanthate in flotation chemistry. In addition, molecular dynamic simulations were simultaneously performed in constant number, constant volume and temperature (NVT, and constant number, constant volume, and pressure (NPT ensemble, indicating that the NPT ensemble was more suitable to the flotation system and the isobutyl xanthate was easier to be adsorbed on pyrite surface compared with butyl xanthate during an appropriate range of concentrations. Furthermore, the quantum chemical calculations elucidated that the isobutyl xanthate presented higher reactivity than that of the corresponding butyl xanthate based on the frontier molecular orbital theory of chemical reactivity, which was consistent with experimental and simulation results obtained. This work can provide theoretical guidance for an in-depth study of the flotation chemistry of pyrite with isomeric xanthates.

  2. In vitro metabolism of nitric oxide-donating aspirin: the effect of positional isomerism.

    Science.gov (United States)

    Gao, Jianjun; Kashfi, Khosrow; Rigas, Basil

    2005-03-01

    NO-donating aspirin (NO-ASA) is a potentially important chemopreventive agent against cancer. Since positional isomerism affects strongly its potency in inhibiting colon cancer cell growth, we studied the metabolic transformations of its ortho-, meta-, and para-isomers in rat liver and colon cytosolic, microsomal, and mitochondrial fractions as well as in intact HT-29 human colon cancer cells. NO-ASA and metabolites were determined by high-performance liquid chromatography and products identified by mass spectroscopy, as required. For all three isomers, the acetyl group on the ASA moiety was hydrolyzed rapidly. This was followed by hydrolysis of the ester bond linking the salicylate anion to the spacer. The ortho- and para-isomers produced salicylic acid and a putative intermediate consisting of the remainder of the molecule, which via a rapid step generated nitrate, (hydroxymethyl)phenol, and a conjugate of spacer with glutathione. The meta-isomer, in contrast, generated salicylic acid and (nitroxymethyl)phenol, the latter leading to (hydroxymethyl)phenol and the glutathione-spacer conjugate. This metabolic pathway takes place in its entirety only in the cytosolic fraction of the tissues tested and in intact human colon cancer cells, perhaps reflecting exposure to the cytosolic glutathione S-transferase, which catalyzes the formation of the spacer-glutathione conjugate. Thus, the three positional isomers of NO-ASA differ in their metabolism and these differences correlate with their differential effects on cancer cell growth, underscoring the importance of positional isomerism in modulating drug effects.

  3. Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

    Science.gov (United States)

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-12-01

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) electronic state has been constructed by fitting ˜37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm-1. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm-1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

  4. Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

    International Nuclear Information System (INIS)

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-01-01

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S 0 ) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm −1 . The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm −1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction

  5. Schiff base switch II precedes the retinal thermal isomerization in the photocycle of bacteriorhodopsin.

    Directory of Open Access Journals (Sweden)

    Ting Wang

    Full Text Available In bacteriorhodopsin, the order of molecular events that control the cytoplasmic or extracellular accessibility of the Schiff bases (SB are not well understood. We use molecular dynamics simulations to study a process involved in the second accessibility switch of SB that occurs after its reprotonation in the N intermediate of the photocycle. We find that once protonated, the SB C15 = NZ bond switches from a cytoplasmic facing (13-cis, 15-anti configuration to an extracellular facing (13-cis, 15-syn configuration on the pico to nanosecond timescale. Significantly, rotation about the retinal's C13 = C14 double bond is not observed. The dynamics of the isomeric state transitions of the protonated SB are strongly influenced by the surrounding charges and dielectric effects of other buried ions, particularly D96 and D212. Our simulations indicate that the thermal isomerization of retinal from 13-cis back to all-trans likely occurs independently from and after the SB C15 = NZ rotation in the N-to-O transition.

  6. Material Balance And Reaction Kinetics Modeling For Penex Isomerization Process In Daura Refinery

    Directory of Open Access Journals (Sweden)

    Hamadi Adel Sharif

    2017-01-01

    Full Text Available Penex Deisohexanizer isomerization of light straight run naphtha is a significant process for petroleum refining and proved to be effective technology to produce gasoline components with a high octane number. Modeling of the chemical kinetic reactions is an important tool because it is a better tool for optimization of the experimental data into parameters used for industrial reactors. The present study deals on the isomerization process in Daura refinery. Material balance calculations were done mathematically on the unit for the kinetics prediction purpose. A kinetic mathematical model was derived for the prediction rate constants K1 and K2 and activation energy Ea at operating temperatures range 120-180°C. According to the model, the results show that with increasing of temperature leads to increased K1 directly, where the K2 values proportional inversely. The activation energy results show that Ea1(nC6

  7. Silver complexation and tandem mass spectrometry for differentiation of isomeric flavonoid diglycosides.

    Science.gov (United States)

    Zhang, Junmei; Brodbelt, Jennifer S

    2005-03-15

    For detection and differentiation of isomeric flavonoids, electrospray ionization mass spectrometry is used to generate silver complexes of the type (Ag + flavonoid)+. Collisionally activated dissociation (CAD) of the resulting 1:1 silver/flavonoid complexes allows isomer differentiation of flavonoids. Eighteen flavonoid diglycosides constituting seven isomeric series are distinguishable from each other based on the CAD patterns of their silver complexes. Characteristic dissociation pathways allow identification of the site of glycosylation, the type of disaccharide (rutinose versus neohesperidose), and the type of aglycon (flavonol versus flavone versus flavanone). This silver complexation method is more universal than previous metal complexation methods, as intense silver complexes are observed even for flavonoids that lack the typical metal chelation sites. To demonstrate the feasibility of using silver complexation and tandem mass spectrometry to characterize flavonoids in complex mixtures, flavonoids extracted from grapefruit juice are separated by high-performance liquid chromatography and analyzed via a postcolumn complexation ESI-MS/MS strategy. Diagnostic fragmentation pathways of the silver complexes of the individual eluting flavonoids allow successful identification of the six flavonoids in the extract.

  8. Isotopic study on mechanism for skeletal isomerization of n-butane over solid acids

    International Nuclear Information System (INIS)

    Suzuki, Tetsuo; Okuhara, Toshio

    2000-01-01

    Reaction mechanism for skeletal isomerization of n-butane over typical strong solid acids were investigated by using 1,4- 13 C 2 -n-butane. We used FI MASS for the analysis of 13 C distribution to get the parent pattern. 13 C-distribution of isobutane formed at 423 K over SO 3 2- /ZrO 2 (SZ) and Cs 2.5 H 0.5 PW 12 O 40 (Cs2.5) were close to binomial distributions, indicating that the isomerization proceeded mainly via a bimolecular mechanism on these catalysts. On the other hand, at 523 K over Cs2.5, the isotopic distribution pattern in isobutane was quite different from the binomial one; the fraction of 13 C 2 -isobutane was much greater than the binomial distribution. This result demonstrates that an intramolecular (monomolecular) rearrangement became significant at 523 K over Cs2.5. The contribution of monomolecular pathway was higher on Cs2.5 than on SZ. We presumed that the contribution of mechanism is related to the acidic property and the dehydrogenation ability of the catalyst. (S.Y.)

  9. Isomeric signatures in the fragmentation of pyridazine and pyrimidine induced by fast ion impact

    Energy Technology Data Exchange (ETDEWEB)

    Wolff, Wania, E-mail: wania@if.ufrj.br; Luna, Hugo; Montenegro, Eduardo C. [Instituto de Física, Universidade Federal do Rio de Janeiro, 21941-972 Rio de Janeiro, RJ (Brazil)

    2015-07-28

    We present fast proton impact induced fragmentations of pyrimidine and pyridazine as an experimental resource to investigate isomeric signatures. Major isomeric imprints are identified for few fragment ions and differences of more than an order of magnitude for the cross sections of fragments of the same mass were measured. The observation of the molecular structure of these isomers gives no apparent indication for the reasons for such substantial differences. It is verified that the simple displacement of the position of one nitrogen atom strongly inhibits or favors the production of some ionic fragment species. The dependency of the fragmentation cross sections on the proton impact energy, investigated by means of time of flight mass spectroscopy and of a model calculation based in first order perturbation theory, allows us to disentangle the complex collision dynamics of the ionic fragments. The proton-induced fragmentation discriminates rather directly the association between a molecular orbital ionization and the fragment-ions creation and abundance, as well as how the redistribution of the energy imparted to the molecules takes place, triggering not only single but also double vacancy and leads to specific fragmentation pathways.

  10. Thermodynamic calculation of simultaneous reactions of n-butane isomerization and isobutane alkylation with ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Batyrshin, N.N.; Beresneva, L.D.; Sidorov, V.A.

    1981-08-01

    Industrial production of ethylene alkylate has gained further development in connection with worldwide ecological problems and the planned changeover of automobile transport to unleaded gasolines, but the scale of production is still substantially less than that of sulfuric acid or hydrogen fluoride alkylates. This is due both to the instability of market prices for ethylene and the shortage of isobutane - a raw material for these large-tonnage production processes and for the synthetic rubber industry. The latter difficulty can be overcome by combining processes of isomerization of n-butane and alkylation of the resultant isobutane with ethylene in a single reaction unit. The possibility of combining these reactions using AlCl/sub 3/-based catalysts has been pointed out previously but in the literature there are no theoretical developments of technology or thermodynamic substantiation of a combined process. We have made a thermodynamic calculation of the consecutive (series-parallel) reactions of isomerization and alkylation with the goal of determining suitable technological conditions for carrying them out simultaneously and establishing the expected equilibrium yields of target products and the compositions of the reaction mixture.

  11. Medication possession ratio predicts antiretroviral regimens persistence in Peru.

    Science.gov (United States)

    Salinas, Jorge L; Alave, Jorge L; Westfall, Andrew O; Paz, Jorge; Moran, Fiorella; Carbajal-Gonzalez, Danny; Callacondo, David; Avalos, Odalie; Rodriguez, Martin; Gotuzzo, Eduardo; Echevarria, Juan; Willig, James H

    2013-01-01

    In developing nations, the use of operational parameters (OPs) in the prediction of clinical care represents a missed opportunity to enhance the care process. We modeled the impact of multiple measurements of antiretroviral treatment (ART) adherence on antiretroviral treatment outcomes in Peru. Retrospective cohort study including ART naïve, non-pregnant, adults initiating therapy at Hospital Nacional Cayetano Heredia, Lima-Peru (2006-2010). Three OPs were defined: 1) Medication possession ratio (MPR): days with antiretrovirals dispensed/days on first-line therapy; 2) Laboratory monitory constancy (LMC): proportion of 6 months intervals with ≥1 viral load or CD4 reported; 3) Clinic visit constancy (CVC): proportion of 6 months intervals with ≥1 clinic visit. Three multi-variable Cox proportional hazard (PH) models (one per OP) were fit for (1) time of first-line ART persistence and (2) time to second-line virologic failure. All models were adjusted for socio-demographic, clinical and laboratory variables. 856 patients were included in first-line persistence analyses, median age was 35.6 years [29.4-42.9] and most were male (624; 73%). In multivariable PH models, MPR (per 10% increase HR=0.66; 95%CI=0.61-0.71) and LMC (per 10% increase 0.83; 0.71-0.96) were associated with prolonged time on first-line therapies. Among 79 individuals included in time to second-line virologic failure analyses, MPR was the only OP independently associated with prolonged time to second-line virologic failure (per 10% increase 0.88; 0.77-0.99). The capture and utilization of program level parameters such as MPR can provide valuable insight into patient-level treatment outcomes.

  12. An upper and lower bound of the Medication Possession Ratio

    Directory of Open Access Journals (Sweden)

    Sperber CM

    2017-08-01

    Full Text Available Christian M Sperber, Suren R Samarasinghe, Grace P Lomax Patient Connect Limited, Guildford, UK Background: The Medication Possession Ratio (MPR is a ubiquitous and central measurement for adherence in the health care industry. However, attempts to standardize its calculation have failed, possibly due to the opacity of a single, static MPR, incapability of directly lending itself to a variety of studies, and challenges of comparing the value across studies. This work shows that the MPR strictly depends on the length of the time interval over which it is measured as well as on the dominant dispense quantity for short time intervals. Furthermore, removing a proportion of the patient cohort based on the number of acquisitions may also have a severe impact on the MPR. Therefore, it is suggested that the MPR is represented as a trend over a range of time intervals. To this end, an upper and lower bound of the MPR trend is developed with an upper bound acknowledging patients who change their treatment and the lower bound acknowledging patients who discontinue their treatment.Purpose: Introducing a representation of the MPR value as a trend rather than a static number by developing a quantitative description of an upper and lower bound of the MPR trend, while shedding light on the impacts on prefiltering the patient cohort.Patients and methods: Anonymized patient-level data was utilized as an example for a suggested calculation of an upper and lower bound of the MPR.Results: Representation of the MPR for a predefined time interval precludes a reliable MPR assessment. A quantitative approach is suggested to generate an upper and lower trend of the MPR while emphasizing the impact on removing patients with a limited number of acquisitions.Conclusion: An upper and lower trend makes the MPR more transparent and allows a better comparison across different studies. Removing patients with a limited number of acquisitions should be avoided. Keywords: MPR

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

    International Nuclear Information System (INIS)

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

    1981-01-01

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

  14. Synthesis of Heterocycles through a Ruthenium‐Catalyzed Tandem Ring‐Closing Metathesis/Isomerization/N‐Acyliminium Cyclization Sequence

    DEFF Research Database (Denmark)

    Ascic, Erhad; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2011-01-01

    Tandem bicycle: In the title reaction double bonds created during ring-closing metathesis isomerize to generate reactive iminium intermediates that undergo intramolecular cyclization reactions with tethered heteroatom and carbon nucleophiles. In this way, a series of biologically interesting hete...... heterocyclic compounds can be made, including a known precursor for the total synthesis of the antiparasitic natural product harmicine....

  15. Ruthenium Stilbenyl and Diruthenium Distyrylethene Complexes: Aspects of Electron Delocalization and Electrocatalyzed Isomerization of the Z-Isomer

    Czech Academy of Sciences Publication Activity Database

    Linseis, M.; Záliš, Stanislav; Zabel, M.; Winter, R. F.

    2012-01-01

    Roč. 134, č. 40 (2012), s. 16671-16692 ISSN 0002-7863 R&D Projects: GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : CIS-TRANS-ISOMERIZATION * MIXED-VALENCE COMPOUNDS * VIBRATIONAL TIME -SCALE Subject RIV: CG - Electrochemistry Impact factor: 10.677, year: 2012

  16. Valence isomerization of 2-phospha-4-silabicyclo[1.1.0]butane: a high-level ab initio study

    NARCIS (Netherlands)

    Slootweg, J.C.; Ehlers, A.W.; Lammertsma, K.

    2006-01-01

    The rearrangements for 2-phospha-4-silabicyclo[1.1.0]butane, analogous to the valence isomerization of the hydrocarbons bicyclobutane, 1,3-butadiene, and cyclobutene, were studied at the (U)QCISD(T)/ 6-311+G**//(U)QCISD/6-31G* level of theory. The monocyclic 1,2-dihydro-1,2-phosphasiletes are shown

  17. Measurements of 14-MeV neutron cross-sections for the production of isomeric states in hafnium isotopes

    International Nuclear Information System (INIS)

    Patrick, B.H.; Sowerby, M.G.; Wilkins, C.G.; Russen, L.C.

    1990-01-01

    The cross sections for the production of isomeric states in the reactions 179 Hf(n,2n) 178m2 Hf, 180 Hf(n,2n) 179m2 Hf, 179 Hf(n,n') 179m2 Hf with 14 MeV neutrons have been measured and compared with the theoretical ones. 4 refs, 3 figs, 4 tabs

  18. Anion-assisted trans-cis isomerization of palladium(II) phosphine complexes containing acetanilide functionalities through hydrogen bonding interactions.

    Science.gov (United States)

    Lu, Xiao-Xia; Tang, Hau-San; Ko, Chi-Chiu; Wong, Jenny Ka-Yan; Zhu, Nianyong; Yam, Vivian Wing-Wah

    2005-03-28

    The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies.

  19. Investigation of the interaction between isomeric derivatives and human serum albumin by fluorescence spectroscopy and molecular modeling

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ruiyong, E-mail: wangry@zzu.edu.cn; Dou, Huanjing; Yin, Yujing; Xie, Yuanzhe; Sun, Li; Liu, Chunmei; Dong, Jingjing; Huang, Gang; Zhu, Yanyan; Song, Chuanjun, E-mail: chjsong@zzu.edu.cn; Chang, Junbiao, E-mail: changjunbiao@zzu.edu.cn

    2014-10-15

    In this paper, we have synthesized 9H-pyrrolo[1,2-a]indol-9-ones and the isomeric indeno[2,1-b]pyrrol-8-ones. The interactions of human serum albumin with series of isomeric derivatives have been studied by spectrophotometric methods. Results show the intrinsic fluorescence is quenched by the derivatives with a static quenching procedure. The thermodynamics parameters indicate that van der Waals forces and hydrogen bonds play a major role in the interactions. The results of synchronous fluorescence spectra demonstrate that the microenvironments of Trp residue of human serum albumin are disturbed by most derivatives. Thermodynamic results showed that the 9H-pyrrolo[1,2-a]indol-9-ones are stronger quenchers and bind to human serum albumin with the higher affinity than isomeric indeno[2,1-b]pyrrol-8-ones. The influence of molecular structure on the binding aspects has been investigated. - Highlights: • The interactions between isomeric derivatives and HSA have been investigated. • Results reveal that 9H-pyrrolo[1,2-a]indol-9-ones are stronger quenchers for HSA. • Hydrogen bonds and van der Waals forces play major role in the binding process. • The influence of molecular structure on the binding aspects has been investigated. • The binding study was also modeled by molecular docking.

  20. Investigation of the interaction between isomeric derivatives and human serum albumin by fluorescence spectroscopy and molecular modeling

    International Nuclear Information System (INIS)

    Wang, Ruiyong; Dou, Huanjing; Yin, Yujing; Xie, Yuanzhe; Sun, Li; Liu, Chunmei; Dong, Jingjing; Huang, Gang; Zhu, Yanyan; Song, Chuanjun; Chang, Junbiao

    2014-01-01

    In this paper, we have synthesized 9H-pyrrolo[1,2-a]indol-9-ones and the isomeric indeno[2,1-b]pyrrol-8-ones. The interactions of human serum albumin with series of isomeric derivatives have been studied by spectrophotometric methods. Results show the intrinsic fluorescence is quenched by the derivatives with a static quenching procedure. The thermodynamics parameters indicate that van der Waals forces and hydrogen bonds play a major role in the interactions. The results of synchronous fluorescence spectra demonstrate that the microenvironments of Trp residue of human serum albumin are disturbed by most derivatives. Thermodynamic results showed that the 9H-pyrrolo[1,2-a]indol-9-ones are stronger quenchers and bind to human serum albumin with the higher affinity than isomeric indeno[2,1-b]pyrrol-8-ones. The influence of molecular structure on the binding aspects has been investigated. - Highlights: • The interactions between isomeric derivatives and HSA have been investigated. • Results reveal that 9H-pyrrolo[1,2-a]indol-9-ones are stronger quenchers for HSA. • Hydrogen bonds and van der Waals forces play major role in the binding process. • The influence of molecular structure on the binding aspects has been investigated. • The binding study was also modeled by molecular docking

  1. Nitrite-reductase and peroxynitrite isomerization activities of Methanosarcina acetivorans protoglobin.

    Directory of Open Access Journals (Sweden)

    Paolo Ascenzi

    Full Text Available Within the globin superfamily, protoglobins (Pgb belong phylogenetically to the same cluster of two-domain globin-coupled sensors and single-domain sensor globins. Multiple functional roles have been postulated for Methanosarcina acetivorans Pgb (Ma-Pgb, since the detoxification of reactive nitrogen and oxygen species might co-exist with enzymatic activity(ies to facilitate the conversion of CO to methane. Here, the nitrite-reductase and peroxynitrite isomerization activities of the CysE20Ser mutant of Ma-Pgb (Ma-Pgb* are reported and analyzed in parallel with those of related heme-proteins. Kinetics of nitrite-reductase activity of ferrous Ma-Pgb* (Ma-Pgb*-Fe(II is biphasic and values of the second-order rate constant for the reduction of NO2- to NO and the concomitant formation of nitrosylated Ma-Pgb*-Fe(II (Ma-Pgb*-Fe(II-NO are k(app1= 9.6 ± 0.2 M(-1 s(-1 and k(app2 = 1.2 ± 0.1 M(-1 s(-1 (at pH 7.4 and 20 °C. The k(app1 and k(app2 values increase by about one order of magnitude for each pH unit decrease, between pH 8.3 and 6.2, indicating that the reaction requires one proton. On the other hand, kinetics of peroxynitrite isomerization catalyzed by ferric Ma-Pgb* (Ma-Pgb*-Fe(III is monophasic and values of the second order rate constant for peroxynitrite isomerization by Ma-Pgb*-Fe(III and of the first order rate constant for the spontaneous conversion of peroxynitrite to nitrate are h(app = 3.8 × 10(4 M(-1 s(-1 and h0 = 2.8 × 10(-1 s(-1 (at pH 7.4 and 20 °C. The pH-dependence of hon and h0 values reflects the acid-base equilibrium of peroxynitrite (pKa = 6.7 and 6.9, respectively; at 20 °C, indicating that HOONO is the species that reacts preferentially with the heme-Fe(III atom. These results highlight the potential role of Pgbs in the biosynthesis and scavenging of reactive nitrogen and oxygen species.

  2. Are symptoms of spirit possessed patients covered by the DSM-IV or DSM-5 criteria for possession trance disorder? A mixed-method explorative study in Uganda

    NARCIS (Netherlands)

    van Duijl, M.; Kleyn, W.; de Jong, J.

    2013-01-01

    Introduction and aims As in many cultures, spirit possession is a common idiom of distress in Uganda. The DSM-IV contains experimental research criteria for dissociative and possession trance disorder (DTD and PTD), which are under review for the DSM-5. In the current proposed categories of the

  3. The Secret Prover : Proving Possession of Arbitrary Files While not Giving Them Away

    NARCIS (Netherlands)

    Teepe, Wouter

    2005-01-01

    The Secret Prover is a Java application which allows a user (A) to prove to another user (B), that A possesses a file. If B also possesses this file B will get convinced, and if B does not possess this file B will gain no information on (the contents of) this file. This is the first implementation

  4. Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents

    KAUST Repository

    Christl, Josefine T.

    2014-10-14

    The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.

  5. Characterization of Isomeric Glycans by Reversed Phase Liquid Chromatography-Electronic Excitation Dissociation Tandem Mass Spectrometry

    Science.gov (United States)

    Tang, Yang; Wei, Juan; Costello, Catherine E.; Lin, Cheng

    2018-04-01

    The occurrence of numerous structural isomers in glycans from biological sources presents a severe challenge for structural glycomics. The subtle differences among isomeric structures demand analytical methods that can provide structural details while working efficiently with on-line glycan separation methods. Although liquid chromatography-tandem mass spectrometry (LC-MS/MS) is a powerful tool for mixture analysis, the commonly utilized collision-induced dissociation (CID) method often does not generate a sufficient number of fragments at the MS2 level for comprehensive structural characterization. Here, we studied the electronic excitation dissociation (EED) behaviors of metal-adducted, permethylated glycans, and identified key spectral features that could facilitate both topology and linkage determinations. We developed an EED-based, nanoscale, reversed phase (RP)LC-MS/MS platform, and demonstrated its ability to achieve complete structural elucidation of up to five structural isomers in a single LC-MS/MS analysis. [Figure not available: see fulltext.

  6. Antifungal activity and isomerization of octadecyl p-coumarates from Ipomoea carnea subsp. fistulosa.

    Science.gov (United States)

    Nidiry, Eugene Sebastian J; Ganeshan, Girija; Lokesha, Ankanahalli N

    2011-12-01

    Bioassay monitored HPLC assisted isolation and purification of the chief antifungal fraction of the leaves of Ipomoea carnea subsp. fistulosa (Convulvulaceae) were achieved using Colletotrichum gloeosporioides and Cladosporium cucumerinum as test organisms. The activity of the purified fraction was further confirmed by the dose dependent inhibition of the spore germination of Alternaria alternata and A. porri. The active fraction was identified as a mixture of (E)-octadecyl p-coumarate and (Z)-octadecyl p-coumarate. The two isomers were detected on an HPLC column with substantially different retention times, but once eluted from the column, one form was partly converted to the other in daylight. Conclusive evidence for the structures and their isomerization were obtained from the HPLC behavior, IR, UV, HRESIMS, CIMS and and NMR spectral data. Important 1H NMR and 13C NMR signals could be separately assigned for the isomers using 2D NMR techniques.

  7. Analysis of carboxylate coordination function of the isomeric lanthanide pyridinedicarboxylates by means of vibration spectroscopy

    International Nuclear Information System (INIS)

    Puntus, L.; Zolin, V.; Kudryashova, V.

    2004-01-01

    The investigation of IR spectra of salts of six isomers of pyridinedicarboxylic acid (PDA): 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-pyridinedicarboxylic acids, have demonstrated that properties of these salts are dependent on the bonding manner of carboxylate groups and on coordination of heterocyclic nitrogen atom. The most prominent differences in properties and spectra of 2,6- and 3,4-PDA salts are conditioned correspondingly by monodentate and bidentate coordination functions of the carboxylate groups in these compounds. The correlation of the breathing vibration frequency, reflecting the rigidity of the heterocyclic ring, with position of the carboxylate substituents, conditioning intramolecular charge transfer (CT), was postulated and proved by shifts of the breathing vibration frequency dependent on the structure of isomeric ligand

  8. Isomerization of butene-1 on rare earth oxides. [Rare earths: La, Nd, Dy

    Energy Technology Data Exchange (ETDEWEB)

    Khodakov, Yu S; Nesterov, V K; Minachev, Kh M [AN SSSR, Moscow. Inst. Organicheskoj Khimii

    1975-09-01

    A study has been made into the isomerization of butene-1 on oxides of rare-earth elements. The dependence of the reaction rate at 20/sup 0/C on the baking temperature of La and Nd oxides have the maximum at 700/sup 0/C. A decrease in the activity of these oxides after bakinq at 800/sup 0/C is observed, as well as during experiments at -30 deq C. In the case of Dy/sub 2/O/sub 3/, the activity at 20/sup 0/C increases gradually with Tsub(bak)=500 to 800/sup 0/C Zeolite 0.57LaNaY exhibits maximum activity at Tsub(bak)=500/sup 0/C Similar data as to the effect of the baking temperature on the catalyst activity were obtained earlier for hydrogenation of ethylene. According to their maximum activity, oxides of rare-earth elements, in the isomerization as well as hydrogenation reactions, can be arranged as follows: La/sub 2/O/sub 3/>Nd/sub 2/O/sub 3/

  9. High-Pressure Limit Rate Rules for α-H Isomerization of Hydroperoxyalkylperoxy Radicals

    KAUST Repository

    Mohamed, Samah Y

    2018-03-09

    Hydroperoxyalkylperoxy (OOQOOH) radical isomerization is an important low-temperature chain branching reaction within the mechanism of hydrocarbon oxidation. This isomerization may proceed via the migration of the α-hydrogen to the hydroperoxide group. In this work, a combination of high level composite methods - CBS-QB3, G3 and G4 - is used to determine the high-pressure-limit rate parameters for the title reaction. Rate rules for H-migration reactions proceeding through 5-, 6-, 7- and 8-membered ring transitions states are determined. Migrations from primary, secondary and tertiary carbon sites to the peroxy group are considered. Chirality is also investigated by considering two diastereomers for reactants and transition states with two chiral centers. This is important since chirality may influence the energy barrier of the reaction as well as the rotational energy barriers of hindered rotors in chemical species and transition states. The effect of chirality and hydrogen bonding interactions in the investigated energies and rate constants is studied. The results show that while the energy difference between two diastereomers ranges from 0.1 - 3.2 kcal, chirality hardly affects the kinetics, except at low temperatures (atmospheric conditions) or when two chiral centers are present in the reactant. Regarding the effects of the peroxy group position and the H-migration ring size, it is found that in most cases, the 1,5 and 1,6 H-migration reactions have similar rates at low temperatures (below ~830K) since the 1,6 H-migration proceeds via a cyclohexane-like transition state similar to that of the 1,5 H-migration.

  10. Interaction of slow neutrons with the second isomeric level Kπ=16+ of the 178Hf isotope

    International Nuclear Information System (INIS)

    Pangault, Laurence

    1999-01-01

    In this work, we study the interaction of low energy neutrons (E≤ 10 eV) with the second isomeric level of 178 Hf (l π =K π =16 + , T 1/2 =31 y) in (n,γ) reactions which proceed through the formation of a compound nucleus. The radiative decay of high K states in 179 Hf is investigated using an isomeric I π =16 + 178 Hf target, 40 ng in weight. The first experiment, performed at the high flux reactor in the Laue Langevin Institute in Grenoble, consisted in γ-ray spectroscopy measurements. For this purpose, an experimental set-up has been built. lt consists of four large Ge detectors shielded against background using a specific F 6 Li collimations ensemble. The second experiments performed at the Fakel (Kurchatov lnstitute, Moscow) and Gelina (IRMM Geel, Belgium) linear accelerators consisted in the investigation of neutron resonances in the 178 Hf m2 (n,γ) reaction using time of flight technique and their γ-decay paths. A high efficiency spectrometer has been built and used for the measurements at bath sites. Two resonances located at 1.82 eV and 0.75 eV have been observed and unambiguously assigned to the (n+ 178 Hf m2 ) compound system. The γ-decay properties of these resonances are very different. Furthermore, the γ-decay path followed by the 0.75 eV resonance is at odd with that expected form statistical model predictions. (author) [fr

  11. LEGAL SIGNIFICANCE AND PROTECTION OF POSSESSION IN THE REPUBLIC OF MACEDONIA

    Directory of Open Access Journals (Sweden)

    Vojo Belovski

    2015-04-01

    Full Text Available In this paper it will be discussed the legal significance and protection of possession in the Republic of Macedonia. Below it will be listed the kinds of possession, and finally the rules for possession termination will be explained. The possession is an indicator that the person who rules one item is also a right holder of that item. The possession itself occurs in two types specially authorized by a law and pure factual power behind which stands no right. The possession enjoys legal protection. Below in the paper it is processed the judicial protection of the possession which is given based on complaint for disturbance of possession and action to recover the possession. The important thing at the judicial protection is that the rulers’ protection is given to the last actual possession of the item, but it is not disputed the right of possession. Further in this paper it is included the protection of indirect possession where a complaint can be made by the indirect holder of the item, the judicial protection of possessory, possession protection of the heirs and permitted self – help for unauthorized harassment and revoking of the possession. With respect to the termination of the actual power of the item, listed and processed are the ways when the item failed, when the item was lost, when it is obvious that it won’t be returned, when the ruler had freely left it and when the item is not taken from him and the ruler hasn’t realized the right to possession.

  12. From distress to disease: a critique of the medicalisation of possession in DSM-5.

    Science.gov (United States)

    Padmanabhan, Divya

    2017-12-01

    This paper critiques the category of possession-form dissociative identity disorder as defined in the Diagnostic and Statistical Manual of Mental Disorders 5 (DSM-5) published in 2013 by the American Psychiatric Association (APA). The DSM as an index of psychiatry pathologises possession by categorising it as a form of dissociative identity disorder. Drawing upon ethnographic fieldwork, this paper argues that such a pathologisation medicalises possession, which is understood as a non-pathological condition in other contexts such as by those individuals who manifest possession at a temple in Kerala, South India. Through medicalising and further by creating distinctions between acceptable and pathological possession, the DSM converts a form of distress into a disease. This has both conceptual and pragmatic implications. The temple therefore becomes reduced to a culturally acceptable site for the manifestation of a mental illness in a form that is culturally available and possession is explained solely through a biomedical framework, denying alternative conceptualisations and theories which inform possession. By focussing on the DSM-5 classification of possession and the limitations of such a classification, this paper seeks to posit an alternative conceptualisation of possession by engaging with three primary areas which are significant in the DSM categorisation of possession: the DSM's conceptualisation of self in the singular, the distinction between pathological and non-pathological forms of possession, and the limitations of the DSM's equation of the condition of possession with the manifestation of possession. Finally, the paper briefly highlights alternative conceptualisations of possession, which emerged from the perspective of those seeking to heal possession at the Chottanikkara temple.

  13. Cardiopulmonary Exercise Testing in Fontan Patients With and Without Isomerism (Heterotaxy) as Compared to Patients With Primary Ciliary Dyskinesia and Subjects With Structurally Normal Hearts

    DEFF Research Database (Denmark)

    Loomba, Rohit S; Danduran, Michael; Nielsen, Kim G

    2017-01-01

    with and without isomerism. We have now compared these finding with those from patients with primary ciliary dyskinesia, as many patients with isomerism have ciliary dyskinesia. We identified patients having the Fontan circulation with and without isomerism who had undergone cardiopulmonary exercise testing......, comparing the findings from healthy individuals undergoing exercise, and a comparable number of individuals with primary ciliary dyskinesia but no congenital heart disease. We were able to include a total of 68 patients in our study, with 17 in each of the four groups. Cardiopulmonary exercise testing...

  14. Compartmental and noncompartmental modeling of ¹³C-lycopene absorption, isomerization, and distribution kinetics in healthy adults.

    Science.gov (United States)

    Moran, Nancy E; Cichon, Morgan J; Riedl, Kenneth M; Grainger, Elizabeth M; Schwartz, Steven J; Novotny, Janet A; Erdman, John W; Clinton, Steven K

    2015-12-01

    Lycopene, which is a red carotenoid in tomatoes, has been hypothesized to mediate disease-preventive effects associated with tomato consumption. Lycopene is consumed primarily as the all-trans geometric isomer in foods, whereas human plasma and tissues show greater proportions of cis isomers. With the use of compartmental modeling and stable isotope technology, we determined whether endogenous all-trans-to-cis-lycopene isomerization or isomeric-bioavailability differences underlie the greater proportion of lycopene cis isomers in human tissues than in tomato foods. Healthy men (n = 4) and women (n = 4) consumed (13)C-lycopene (10.2 mg; 82% all-trans and 18% cis), and plasma was collected over 28 d. Unlabeled and (13)C-labeled total lycopene and lycopene-isomer plasma concentrations, which were measured with the use of high-performance liquid chromatography-mass spectrometry, were fit to a 7-compartment model. Subjects absorbed a mean ± SEM of 23% ± 6% of the lycopene. The proportion of plasma cis-(13)C-lycopene isomers increased over time, and all-trans had a shorter half-life than that of cis isomers (5.3 ± 0.3 and 8.8 ± 0.6 d, respectively; P lycopene bioavailability and endogenous trans-to-cis-lycopene isomerization was predictive of plasma (13)C and unlabeled cis- and all-trans-lycopene concentrations. Although the bioavailability of cis (24.5% ± 6%) and all-trans (23.2% ± 8%) isomers did not differ, endogenous isomerization (0.97 ± 0.25 μmol/d in the fast-turnover tissue lycopene pool) drove tissue and plasma isomeric profiles. (13)C-Lycopene combined with physiologic compartmental modeling provides a strategy for following complex in vivo metabolic processes in humans and reveals that postabsorptive trans-to-cis-lycopene isomerization, and not the differential bioavailability of isomers, drives tissue and plasma enrichment of cis-lycopene. This trial was registered at clinicaltrials.gov as NCT01692340. © 2015 American Society for Nutrition.

  15. Compartmental and noncompartmental modeling of 13C-lycopene absorption, isomerization, and distribution kinetics in healthy adults123

    Science.gov (United States)

    Moran, Nancy E; Cichon, Morgan J; Riedl, Kenneth M; Grainger, Elizabeth M; Schwartz, Steven J; Novotny, Janet A; Erdman, John W; Clinton, Steven K

    2015-01-01

    Background: Lycopene, which is a red carotenoid in tomatoes, has been hypothesized to mediate disease-preventive effects associated with tomato consumption. Lycopene is consumed primarily as the all-trans geometric isomer in foods, whereas human plasma and tissues show greater proportions of cis isomers. Objective: With the use of compartmental modeling and stable isotope technology, we determined whether endogenous all-trans-to-cis-lycopene isomerization or isomeric-bioavailability differences underlie the greater proportion of lycopene cis isomers in human tissues than in tomato foods. Design: Healthy men (n = 4) and women (n = 4) consumed 13C-lycopene (10.2 mg; 82% all-trans and 18% cis), and plasma was collected over 28 d. Unlabeled and 13C-labeled total lycopene and lycopene-isomer plasma concentrations, which were measured with the use of high-performance liquid chromatography–mass spectrometry, were fit to a 7-compartment model. Results: Subjects absorbed a mean ± SEM of 23% ± 6% of the lycopene. The proportion of plasma cis-13C-lycopene isomers increased over time, and all-trans had a shorter half-life than that of cis isomers (5.3 ± 0.3 and 8.8 ± 0.6 d, respectively; P lycopene bioavailability and endogenous trans-to-cis-lycopene isomerization was predictive of plasma 13C and unlabeled cis- and all-trans-lycopene concentrations. Although the bioavailability of cis (24.5% ± 6%) and all-trans (23.2% ± 8%) isomers did not differ, endogenous isomerization (0.97 ± 0.25 μmol/d in the fast-turnover tissue lycopene pool) drove tissue and plasma isomeric profiles. Conclusion: 13C-Lycopene combined with physiologic compartmental modeling provides a strategy for following complex in vivo metabolic processes in humans and reveals that postabsorptive trans-to-cis-lycopene isomerization, and not the differential bioavailability of isomers, drives tissue and plasma enrichment of cis-lycopene. This trial was registered at clinicaltrials.gov as NCT01692340. PMID

  16. Effect of playing tactics on achieving score-box possessions in a random series of team possessions from Norwegian professional soccer matches.

    Science.gov (United States)

    Tenga, Albin; Holme, Ingar; Ronglan, Lars Tore; Bahr, Roald

    2010-02-01

    Methods of analysis that include an assessment of opponent interactions are thought to provide a more valid means of team match performance. The purpose of this study was to examine the effect of playing tactics on achieving score-box possession by assessing opponent interactions in Norwegian elite soccer matches. We analysed a random series of 1703 team possessions from 163 of 182 (90%) matches played in the professional men's league during the 2004 season. Multidimensional qualitative data obtained from ten ordered categorical variables were used. Offensive tactics were more effective in producing score-box possessions when playing against an imbalanced defence (28.5%) than against a balanced defence (6.5%) (P tactics on producing score-box possessions, and improves the validity of team match-performance analysis in soccer.

  17. Traumatic Experience and Somatoform Dissociation Among Spirit Possession Practitioners in the Dominican Republic.

    Science.gov (United States)

    Schaffler, Yvonne; Cardeña, Etzel; Reijman, Sophie; Haluza, Daniela

    2016-03-01

    Recent studies in African contexts have revealed a strong association between spirit possession and severe trauma, with inclusion into a possession cult serving at times a therapeutic function. Research on spirit possession in the Dominican Republic has so far not included quantitative studies of trauma and dissociation. This study evaluated demographic variables, somatoform dissociative symptoms, and potentially traumatizing events in the Dominican Republic with a group of Vodou practitioners that either do or do not experience spirit possession. Inter-group comparisons revealed that in contrast to non-possessed participants (n = 38), those experiencing spirit possession (n = 47) reported greater somatoform dissociation, more problems with sleep, and previous exposure to mortal danger such as assaults, accidents, or diseases. The two groups did not differ significantly in other types of trauma. The best predictor variable for group classification was somatoform dissociation, although those items could also reflect the experience of followers during a possession episode. A factor analysis across variables resulted in three factors: having to take responsibility early on in life and taking on a professional spiritual role; traumatic events and pain; and distress/dissociation. In comparison with the non-possessed individuals, the possessed ones did not seem to overall have a remarkably more severe story of trauma and seemed to derive economic gains from possession practice.

  18. Is HO3 minimum cis or trans? An analytic full-dimensional ab initio isomerization path.

    Science.gov (United States)

    Varandas, A J C

    2011-05-28

    The minimum energy path for isomerization of HO(3) has been explored in detail using accurate high-level ab initio methods and techniques for extrapolation to the complete basis set limit. In agreement with other reports, the best estimates from both valence-only and all-electron single-reference methods here utilized predict the minimum of the cis-HO(3) isomer to be deeper than the trans-HO(3) one. They also show that the energy varies by less than 1 kcal mol(-1) or so over the full isomerization path. A similar result is found from valence-only multireference configuration interaction calculations with the size-extensive Davidson correction and a correlation consistent triple-zeta basis, which predict the energy difference between the two isomers to be of only Δ = -0.1 kcal mol(-1). However, single-point multireference calculations carried out at the optimum triple-zeta geometry with basis sets of the correlation consistent family but cardinal numbers up to X = 6 lead upon a dual-level extrapolation to the complete basis set limit of Δ = (0.12 ± 0.05) kcal mol(-1). In turn, extrapolations with the all-electron single-reference coupled-cluster method including the perturbative triples correction yield values of Δ = -0.19 and -0.03 kcal mol(-1) when done from triple-quadruple and quadruple-quintuple zeta pairs with two basis sets of increasing quality, namely cc-cpVXZ and aug-cc-pVXZ. Yet, if added a value of 0.25 kcal mol(-1) that accounts for the effect of triple and perturbative quadruple excitations with the VTZ basis set, one obtains a coupled cluster estimate of Δ = (0.14 ± 0.08) kcal mol(-1). It is then shown for the first time from systematic ab initio calculations that the trans-HO(3) isomer is more stable than the cis one, in agreement with the available experimental evidence. Inclusion of the best reported zero-point energy difference (0.382 kcal mol(-1)) from multireference configuration interaction calculations enhances further the relative

  19. Production cross sections and isomeric ratios for sup(110m)In/sup(110g)In formed in Cd (d,xn) reactions

    International Nuclear Information System (INIS)

    Herreros Usher, Oscar; Maceiras de Jefimowicz, Elena; De la Vega Vedoya, Mario; Jorge Nassiff, Sonia

    1980-01-01

    Excitation functions and isomeric cross sections ratios have been measured for the 110 Cd (d,2n) and 111 Cd (d,3n) reactions in which the isomeric pair sup(110m)In/sup(110g)In is produced. Activation method was employed and the irradiations were performed at the synchrocyclotron of the Comision Nacional de Energia Atomica, Argentina, with an incident energy of 27.MeV. (author) [es

  20. Thermal solid-state Z/E isomerization of 2-alkylidene-4-oxothiazolidines: effects of non-covalent interactions

    Directory of Open Access Journals (Sweden)

    ZDRAVKO DŽAMBASKI

    2011-03-01

    Full Text Available Configurational isomerization of stereo-defined 5-substituted and unsubstituted 2-alkylidene-4-oxothiazolidines (1 in the solid state, giving the Z/E mixtures in various ratios, was investigated by 1H-NMR spectroscopy, X-ray powder crystallography and differential scanning calorimetry (DSC. The Z/E composition can be rationalized in terms of non-covalent interactions, involving intermolecular and intramolecular hydrogen bonding and directional non-bonded 1,5-type S×××O interactions. X-Ray powder crystallography, using selected crystalline (Z-4-oxothiazolidine substrates, revealed transformation to the amorphous state during the irreversible Z®E process. A correlation between previous results on the Z/E isomerization in solution and now in the solid state was established.

  1. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    Science.gov (United States)

    Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

    2016-07-01

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N2, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  2. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    International Nuclear Information System (INIS)

    Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

    2016-01-01

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N 2 , Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  3. Investigating the large deformation of the 5 /2+ isomeric state in 73Zn: An indicator for triaxiality

    Science.gov (United States)

    Yang, X. F.; Tsunoda, Y.; 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.; Krämer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Otsuka, T.; Papuga, J.; Sánchez, R.; Wraith, C.; Xie, L.; Yordanov, D. T.

    2018-04-01

    Recently reported nuclear spins and moments of neutron-rich Zn isotopes measured at ISOLDE-CERN [C. Wraith et al., Phys. Lett. B 771, 385 (2017), 10.1016/j.physletb.2017.05.085] show an uncommon behavior of the isomeric state in 73Zn. Additional details relating to the measurement and analysis of the Znm73 hyperfine structure are addressed here to further support its spin-parity assignment 5 /2+ and to estimate its half-life. A systematic investigation of this 5 /2+ isomer indicates that significant collectivity appears due to proton/neutron E 2 excitations across the proton Z = 28 and neutron N = 50 shell gaps. This is confirmed by the good agreement of the observed quadrupole moments with large scale Monte Carlo shell model calculations. In addition, potential energy surface calculations in combination with T plots reveal a triaxial shape for this isomeric state.

  4. Retrieving molecular structural information and tracking HNC/HCN isomerization process with high harmonic generation by ultrashort laser pulses

    International Nuclear Information System (INIS)

    Nguyen Ngoc Ty; Le Van Hoang; Vu Ngoc Tuoc; Le Anh Thu

    2010-01-01

    We investigate the possibility of applying the iterative method, suggested in our previous work, for HCN molecule and its HNC isomer. We found that the high-order harmonic generation (HHG) spectra are quite insensitive to the change of H-C (or H-N) bond length so that only the inter-nuclear C-N distance can be retrieved from the high-order harmonic spectra using ultrashort intense lasers. Furthermore, by analyzing the HHG spectra emitted by HCN during the chemical reaction path of isomerization we identify the intensity peaks nearby the stable, metastable and transition states. this finding can be useful for tracking the HNC/HNC isomerization process. (author)

  5. Evidence for tunneling in base-catalyzed isomerization of glyceraldehyde to dihydroxyacetone by hydride shift under formose conditions.

    Science.gov (United States)

    Cheng, Liang; Doubleday, Charles; Breslow, Ronald

    2015-04-07

    Hydrogen atom transfer reactions between the aldose and ketose are key mechanistic features in formose chemistry by which formaldehyde is converted to higher sugars under credible prebiotic conditions. For one of these transformations, we have investigated whether hydrogen tunneling makes a significant contribution to the mechanism by examining the deuterium kinetic isotope effect associated with the hydrogen transfer during the isomerization of glyceraldehyde to the corresponding dihydroxyacetone. To do this, we developed a quantitative HPLC assay that allowed us to measure the apparent large intrinsic kinetic isotope effect. From the Arrhenius plot of the kinetic isotope effect, the ratio of the preexponential factors AH/AD was 0.28 and the difference in activation energies Ea(D) - Ea(H) was 9.1 kJ·mol(-1). All these results imply a significant quantum-mechanical tunneling component in the isomerization mechanism. This is supported by multidimensional tunneling calculations using POLYRATE with small curvature tunneling.

  6. Results of a Direct Search Using Synchrotron Radiation for the Low-Energy (229)Th Nuclear Isomeric Transition.

    Science.gov (United States)

    Jeet, Justin; Schneider, Christian; Sullivan, Scott T; Rellergert, Wade G; Mirzadeh, Saed; Cassanho, A; Jenssen, H P; Tkalya, Eugene V; Hudson, Eric R

    2015-06-26

    We report the results of a direct search for the (229)Th (I(π)=3/2(+)←5/2(+)) nuclear isomeric transition, performed by exposing (229)Th-doped LiSrAlF(6) crystals to tunable vacuum-ultraviolet synchrotron radiation and observing any resulting fluorescence. We also use existing nuclear physics data to establish a range of possible transition strengths for the isomeric transition. We find no evidence for the thorium nuclear transition between 7.3 eV and 8.8 eV with transition lifetime (1-2) s≲τ≲(2000-5600)  s. This measurement excludes roughly half of the favored transition search area and can be used to direct future searches.

  7. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    Energy Technology Data Exchange (ETDEWEB)

    Justino, Licínia L. G., E-mail: liciniaj@ci.uc.pt; Reva, Igor; Fausto, Rui [CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal)

    2016-07-07

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N{sub 2}, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  8. DFT study on the isomerization and tautomerism in vitamins B3 (niacin), B5 (pantothenic acid) and B7 (biotin)

    Science.gov (United States)

    Valadbeigi, Younes; Farrokhpour, Hossein; Tabrizchi, Mahmoud

    2014-05-01

    Isomerization and tautomerism of the three water soluble vitamins including B3, B5 and B7 were studied applying density functional theory using B3LYP method in gas and aqueous phases. Activation energies (Ea), Gibbs free energies of activation (ΔG#), and imaginary frequencies of the transition state structures were calculated for all the isomerization and tautomerism reactions. Activation energies of the neutral → zwitterion (amine-enamine) tautomerism in vitamin B3 were 310-360 kJ/mol where these values for the keto-enol tautomerism were 100-130 kJ/mol. It was found that water molecule catalyzes the tautomerism and decreases the activation energies about 90-160 kJ/mol.

  9. Activation cross section and isomeric cross section ratios for the (n ,2 n ) reaction on 153Eu

    Science.gov (United States)

    Luo, Junhua; Jiang, Li; Li, Suyuan

    2017-10-01

    The 153Eu(n ,2 n ) m1,m2,g152Eu cross section was measured by means of the activation technique at three neutron energies in the range 13-15 MeV. The quasimonoenergetic neutron beam was formed via the 3H(d ,n ) 4He reaction, in the Pd-300 Neutron Generator at the Chinese Academy of Engineering Physics (CAEP). The activities induced in the reaction products were measured using high-resolution γ-ray spectroscopy. The cross section of the population of the second high-spin (8-) isomeric state was measured along with the reaction cross section populating both the ground (3-) and the first isomeric state (0-). Cross sections were also evaluated theoretically using the numerical code TALYS-1.8, with different level density options at neutron energies varying from the reaction threshold to 20 MeV. Results are discussed and compared with the corresponding literature.

  10. New families of conservative systems on $S^2$ possessing an integral of fourth degree in momenta

    OpenAIRE

    Selivanova, Elena N.

    1997-01-01

    There is a well-known example of integrable conservative system on $S^2$, the case of Kovalevskaya in the dynamics of a rigid body, possessing an integral of fourth degree in momenta. Goryachev proposed a one-parameter family of examples of conservative systems on $S^2$ possessing an integral of fourth degree in momenta which includes the case of Kovalevskaya. In this paper we proposed new examples of conservative systems on $S^2$ possessing an integral of fourth degree in momenta.

  11. Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor.

    Science.gov (United States)

    Porterfield, Jessica P; Nguyen, Thanh Lam; Baraban, Joshua H; Buckingham, Grant T; Troy, Tyler P; Kostko, Oleg; Ahmed, Musahid; Stanton, John F; Daily, John W; Ellison, G Barney

    2015-12-24

    The thermal decomposition of cyclohexanone (C6H10═O) has been studied in a set of flash-pyrolysis microreactors. Decomposition of the ketone was observed when dilute samples of C6H10═O were heated to 1200 K in a continuous flow microreactor. Pyrolysis products were detected and identified by tunable VUV photoionization mass spectroscopy and by photoionization appearance thresholds. Complementary product identification was provided by matrix infrared absorption spectroscopy. Pyrolysis pressures were roughly 100 Torr, and contact times with the microreactors were roughly 100 μs. Thermal cracking of cyclohexanone appeared to result from a variety of competing pathways, all of which open roughly simultaneously. Isomerization of cyclohexanone to the enol, cyclohexen-1-ol (C6H9OH), is followed by retro-Diels-Alder cleavage to CH2═CH2 and CH2═C(OH)-CH═CH2. Further isomerization of CH2═C(OH)-CH═CH2 to methyl vinyl ketone (CH3CO-CH═CH2, MVK) was also observed. Photoionization spectra identified both enols, C6H9OH and CH2═C(OH)-CH═CH2, and the ionization threshold of C6H9OH was measured to be 8.2 ± 0.1 eV. Coupled cluster electronic structure calculations were used to establish the energetics of MVK. The heats of formation of MVK and its enol were calculated to be ΔfH298(cis-CH3CO-CH═CH2) = -26.1 ± 0.5 kcal mol(-1) and ΔfH298(s-cis-1-CH2═C(OH)-CH═CH2) = -13.7 ± 0.5 kcal mol(-1). The reaction enthalpy ΔrxnH298(C6H10═O → CH2═CH2 + s-cis-1-CH2═C(OH)-CH═CH2) is 53 ± 1 kcal mol(-1) and ΔrxnH298(C6H10═O → CH2═CH2 + cis-CH3CO-CH═CH2) is 41 ± 1 kcal mol(-1). At 1200 K, the products of cyclohexanone pyrolysis were found to be C6H9OH, CH2═C(OH)-CH═CH2, MVK, CH2CHCH2, CO, CH2═C═O, CH3, CH2═C═CH2, CH2═CH-CH═CH2, CH2═CHCH2CH3, CH2═CH2, and HC≡CH.

  12. Thiyl radical-induced cis-trans-isomerization of arachidonic acid inhibits prostaglandin metabolism

    International Nuclear Information System (INIS)

    Kratzsch, S.; Droessler, K.; Sprinz, H.; Brede, O.

    2002-01-01

    Complete text of publication follows. Thiyl radicals radiolytically generated from thiophenol in methanolic solution are known to isomerise double bonds of poly-unsaturated fatty acids (PUFA). γ-irradiating of such a system containing all-cis 5,8,11,14 eicosatetraenoic acid (arachidonic acid, AA) with low doses (0.1-0.8 kGy) results in a mixture of 8 to 32% mono-trans-isomers. Here we report about the influence of mono-trans-AA on the primary steps of AA-metabolism and prostaglandin synthesis, catalysed by cyclooxygenase (COX). In the cell-free model system the reaction of COX-1 with AA was analysed by controlling the oxygen level during the enzymatic reaction. As an example, a mixture of a low quantity of mono-trans-isomerized AA (10%) and 90% all-cis-isomer exhibits a marked reduced oxygen consumption by 45%. As further proofs - the yield of reactive oxygen species (ROS) generated by the COX-coupled peroxidase reaction was detected, - and the COX-1 activity in presence of different amounts of trans-AA was characterized using a photometric assay based on the oxidation of TMPD. All these methods indicated semiquantitatively a reduced activity of COX-1, depending on the trans-isomer yield. Therefore, an inhibition of COX-1 activity by only one trans-double-bond in AA could be concluded. Furthermore, in vitro cell-line experiments were performed analysing the influence of mono-trans-isomerized AA on the activity of the cell-own COX-2. Hence, VD 3 -differentiated and LPS-stimulated monocyte-like cells were incubated with mono-trans-AA and ROS-production was detected by the chemiluminescence measurements mentioned above. Compared to the reaction with all-cis-AA we found a considerable lowered formation of ROS. Likewise, we obtained a reduced PGE 2 -expression between 15 and 40% for cells treated with 8 to 29% trans-AA. The model as well as in vivo experiments demonstrate an inhibition effect of mono-trans-AA and give rise for postulating an enzyme blocking mechanism

  13. Biosynthesis of monoterpenes: Stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes

    International Nuclear Information System (INIS)

    Croteau, R.; Gershenzon, J.; Wheeler, C.J.; Satterwhite, D.M.

    1990-01-01

    The conversion of geranyl pyrophosphate to (+)-bornyl pyrophosphate and (+)-camphene is considered to proceed by the initial isomerization of the substrate to (-)-(3R)-linalyl pyrophosphate and the subsequent cyclization of this bound intermediate. In the case of (-)-bornyl pyrophosphate and (-)-camphene, isomerization of the substrate to the (+)-(3S)-linalyl intermediate precedes cyclization. The geranyl and linalyl precursors were shown to be mutually competitive substrates (inhibitors) of the relevant cyclization enzymes isolated from Salvia officinalis (sage) and Tanacetum vulgare (tansy) by the mixed substrate analysis method, demonstrating that isomerization and cyclization take place at the same active site. Incubation of partially purified enzyme preparations with (3R)-[1Z-3H]linalyl pyrophosphate plus [1-14C]geranyl pyrophosphate gave rise to double-labeled (+)-bornyl pyrophosphate and (+)-camphene, whereas incubation of enzyme preparations catalyzing the antipodal cyclizations with (3S)-[1Z-3H]-linalyl pyrophosphate plus [1-14C]geranyl pyrophosphate yielded double-labeled (-)-bornyl pyrophosphate and (-)-camphene. Each product was then transformed to the corresponding (+)- or (-)-camphor without change in the 3H:14C isotope ratio, and the location of the tritium label was deduced in each case by stereoselective, base-catalyzed exchange of the exo-alpha-hydrogen of the derived ketone. The finding that the 1Z-3H of the linalyl precursor was positioned at the endo-alpha-hydrogen of the corresponding camphor in all cases, coupled to the previously demonstrated retention of configuration at C1 of the geranyl substrate in these transformations, confirmed the syn-isomerization of geranyl pyrophosphate to linalyl pyrophosphate and the cyclization of the latter via the anti,endo- conformer

  14. Comparison of Separation of Seed Oil Triglycerides Containing Isomeric Conjugated Octadecatrienoic Acid Moieties by Reversed-Phase HPLC

    OpenAIRE

    Anh Van Nguyen; Victor Deineka; Lumila Deineka; Anh Vu Thi Ngoc

    2017-01-01

    Relative retention analysis and increment approach were applied for the comparison of triglycerides (TGs) retention of a broad set of plant seed oils with isomeric conjugated octadecatrienoic acids (CLnA) by reversed-phase HPLC for “propanol-2-acetonitrile” mobile phases and Kromasil 100-5C18 stationary phase with diode array detection (DAD) and mass spectrometric (MS) detection. The subjects of investigation were TGs of seed oils: Calendula officinalis, Catalpa ovata, Jacaranda mimosifolia, ...

  15. Stability constants of mixed ligand complexes of dioxouranium(II) and thorium(IV) with complexones and isomeric alanines

    International Nuclear Information System (INIS)

    Singh, R.K.; Saxena, M.C.

    1992-01-01

    The present work reports on the stability sequence between UO 2 II and Th IV ions for their mixed ligands complexes with the two isomeric alanines, α-alanine (α-ala) and β-alanine (β-ala) containing a complexone as primary ligand. The complexones used are iminodiacetate (IMDA), nitrilotricetate (NTA), 2-hydroxyethylenediaminetriacetate (HEDTA), ethylenediaminetetraacetate (EDTA), 1,2-diaminocyclohexanetraacetate (CDTA) and diethylenetriminepentaacetate (DTPA). (author). 9 refs., 1 tab

  16. Hydro-isomerization of n-hexane on bi-functional catalyst: Effect of total and hydrogen partial pressures

    Science.gov (United States)

    Thoa, Dao Thi Kim; Loc, Luu Cam

    2017-09-01

    The effect of both total pressure and hydrogen partial pressure during n-hexane hydro-isomerization over platinum impregnated on HZSM-5 was studied. n-Hexane hydro-isomerization was conducted at atmospheric pressure and 0.7 MPa to observe the influence of total pressure. In order to see the effect of hydrogen partial pressure, the reaction was taken place at different partial pressure of hydrogen varied from 307 hPa to 718 hPa by dilution with nitrogen to keep the total pressure at 0.1 MPa. Physico-chemical characteristics of catalyst were determined by the methods of nitrogen physi-sorption BET, SEM, XRD, TEM, NH3-TPD, TPR, and Hydrogen Pulse Chemi-sorption. Activity of catalyst in the hydro-isomerization of n-hexane was studied in a micro-flow reactor in the temperature range of 225-325 °C; the molar ratio H2/ hydrocarbon: 5.92, concentration of n-hexane: 9.2 mol.%, GHSV 2698 h-1. The obtained catalyst expressed high acid density, good reducing property, high metal dispersion, and good balance between metallic and acidic sites. It is excellent contact for n-hexane hydro-isomerization. At 250 °C, n-hexane conversion and selectivity were as high as 59-76 % and 85-99 %, respectively. It was found that catalytic activity was promoted either by total pressure or hydrogen partial pressure. At total pressure of 0.7 MPa while hydrogen partial pressure of 718 hPa, catalyst produced 63 RON liquid product containing friendly environmental iso-paraffins which is superior blending stock for green gasoline. Hydrogen did not only preserve catalyst actives by depressing hydrocracking and removing coke precursors but also facilitated hydride transfer step in the bi-functional bi-molecular mechanism.

  17. The introduction of hydrogen bond and hydrophobicity effects into the rotational isomeric states model for conformational analysis of unfolded peptides

    Science.gov (United States)

    Engin, Ozge; Sayar, Mehmet; Erman, Burak

    2009-03-01

    Relative contributions of local and non-local interactions to the unfolded conformations of peptides are examined by using the rotational isomeric states model which is a Markov model based on pairwise interactions of torsion angles. The isomeric states of a residue are well described by the Ramachandran map of backbone torsion angles. The statistical weight matrices for the states are determined by molecular dynamics simulations applied to monopeptides and dipeptides. Conformational properties of tripeptides formed from combinations of alanine, valine, tyrosine and tryptophan are investigated based on the Markov model. Comparison with molecular dynamics simulation results on these tripeptides identifies the sequence-distant long-range interactions that are missing in the Markov model. These are essentially the hydrogen bond and hydrophobic interactions that are obtained between the first and the third residue of a tripeptide. A systematic correction is proposed for incorporating these long-range interactions into the rotational isomeric states model. Preliminary results suggest that the Markov assumption can be improved significantly by renormalizing the statistical weight matrices to include the effects of the long-range correlations.

  18. Light-induced linkage isomerization of photochromic [Ru(bpy){sub 2}(R-OSO)]{sup +} compounds

    Energy Technology Data Exchange (ETDEWEB)

    Springfeld, Kristin; Dieckmann, Volker; Eicke, Sebastian; Imlau, Mirco [Department of Physics, University of Osnabrueck (Germany); Rack, Jeffrey J. [Department of Chemistry and Biochemistry, Ohio University, Athens, Ohio (United States)

    2010-07-01

    Ruthenium sulfoxides exhibit light-induced linkage isomerization of the SO-bond with remarkable photosensitivity S=(0.25{+-}0.03) Ws cm{sup -1} and extended lifetimes of the related metastable states in the order of 10{sup 4} s. The isomerization is accompanied with tremendous changes of the optical extinction up to 9350 cm{sup -1} mol{sup -1} thus enabling the study of linkage isomerization by means of time-resolved optical spectroscopy. Here, the influence of ligand substitution is studied via inspection of the photosensitivity and the generation and relaxation dynamics of the photochromic response as a function of temperature (pump at {lambda}=405 nm, probe at {lambda}=532 nm). The spectra of the modified compounds, where ligands R=Bn, BnCl, and BnMe were attached to OSO, were compared with the reference system [Ru(bpy){sub 2}(OSO)]{sup +}. It turns out, that the new ligands affect the absorption features and the photosensitivity of the system only slightly. In contrast, a strong influence of the thermal relaxation of the metastable states is uncovered. Remarkably, the influence on the frequency factors is much more pronounced than on the activation energies achieved by Arrhenius' law.

  19. The introduction of hydrogen bond and hydrophobicity effects into the rotational isomeric states model for conformational analysis of unfolded peptides

    International Nuclear Information System (INIS)

    Engin, Ozge; Sayar, Mehmet; Erman, Burak

    2009-01-01

    Relative contributions of local and non-local interactions to the unfolded conformations of peptides are examined by using the rotational isomeric states model which is a Markov model based on pairwise interactions of torsion angles. The isomeric states of a residue are well described by the Ramachandran map of backbone torsion angles. The statistical weight matrices for the states are determined by molecular dynamics simulations applied to monopeptides and dipeptides. Conformational properties of tripeptides formed from combinations of alanine, valine, tyrosine and tryptophan are investigated based on the Markov model. Comparison with molecular dynamics simulation results on these tripeptides identifies the sequence-distant long-range interactions that are missing in the Markov model. These are essentially the hydrogen bond and hydrophobic interactions that are obtained between the first and the third residue of a tripeptide. A systematic correction is proposed for incorporating these long-range interactions into the rotational isomeric states model. Preliminary results suggest that the Markov assumption can be improved significantly by renormalizing the statistical weight matrices to include the effects of the long-range correlations

  20. Specific racemization and isomerization of the aspartyl residue of αA-crystallin due to UV-B irradiation

    International Nuclear Information System (INIS)

    Fujii, Noriko; Momose, Yuko; Ishibasi, Yoshihiro; Uemura, Toshimasa; Takita, Masatoshi; Takehana, Makoto

    1997-01-01

    We have reported that the aspartyl (Asp)-151 residue in αA-crystallin in human eye lens was inverted to the D-isomer and isomerized to β-Asp residue with age. We report here that ultraviolet (UV)-B irradiation induces the racemization and isomerization of the Asp-151 residue of αA-crystallin from lenses of 6-week-old rats to form D-isomer and β-Asp residue. Simultaneous racemization and isomerization of the specific Asp residue indicate that the reaction proceeds via formation of a succinimide intermediate. This modification was not observed in UV-A irradiated and normal lenses. UV-B irradiation induced the racemization of only the Asp-151 residue and did not affect the other Asp residues in αA-crystallin. On the other hand, the high molecular weight fraction of the lens protein increased upon UV-B irradiation. Modification of the Asp residue would affect the three-dimensional packing array of the lens protein. (author)

  1. Isomeric ratios in photonuclear reactions of molybdenum isotopes induced by bremsstrahlung in the giant dipole resonance region

    International Nuclear Information System (INIS)

    Tran Duc Thiep; Truong Thi An; Phan Viet Cuong; Nguyen The Vinh; Bui Minh Hue; Belov, A.G.; Maslov, O.D.; Mishinsky, G.V.; Zhemenik, V.I.

    2017-01-01

    We have determined the isomeric ratios of isomeric pairs "9"7"m","gNb, "9"5"m","gNb and "9"1"m","gMo produced in "9"8Mo(γ, p)"9"7"m","gNb, "9"6Mo(γ, p)"9"5"m","gNb and "9"2Mo(γ, n)"9"1"m","gMo photonuclear reactions in the giant dipole resonance (GDR) region by the activation method. The results were analyzed, discussed and compared with the similar data from literature to examine the role of excitation energy, neutron configuration, channel effect, and direct and pre-equilibrium processes in (γ, p) photonuclear reactions. In this work the isomeric ratios for "9"7"m","gNb from 14 to 19 MeV, for "1"9"5"m","gNb from 14 to 24 MeV except 20 and 23.5 MeV and for "9"1"m","gMo at 14 and 15 MeV were first measured.

  2. The thermal Z-isomerization-induced change in solubility and physical properties of (all-E)-lycopene.

    Science.gov (United States)

    Murakami, Kazuya; Honda, Masaki; Takemura, Ryota; Fukaya, Tetsuya; Kubota, Mitsuhiro; Wahyudiono; Kanda, Hideki; Goto, Motonobu

    2017-09-16

    The effect of Z-isomerization of (all-E)-lycopene on its solubility in organic solvents and physical properties was investigated. Lycopene samples containing different Z-isomer contents (23.8%, 46.9%, and 75.6% of total lycopene) were prepared from high-purity (all-E)-lycopene by thermal Z-isomerization in dichloromethane (CH 2 Cl 2 ). As the Z-isomer content increased, the relative solubility of lycopene significantly improved. Although (all-E)-lycopene barely dissolved in ethanol (0.6 mg/L), the solubilities of lycopene containing 23.8%, 46.9%, and 75.6% Z-isomers were 484.5, 914.7, and 2401.7 mg/L, respectively. Furthermore, differential scanning calorimetry (DSC), powder X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses clearly indicated that (all-E)-lycopene was present in the crystal state, while Z-isomers of lycopene were present in amorphous states. A number of studies have suggested that Z-isomers of lycopene are better absorbed in the human body than the all-E-isomer. This may be due to the change in solubility and physical properties of lycopene by the Z-isomerization. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. First spatial separation of a heavy ion isomeric beam with a multiple-reflection time-of-flight mass spectrometer

    Science.gov (United States)

    Dickel, T.; Plaß, W. R.; Ayet San Andres, S.; Ebert, J.; Geissel, H.; Haettner, E.; Hornung, C.; Miskun, I.; Pietri, S.; Purushothaman, S.; Reiter, M. P.; Rink, A.-K.; Scheidenberger, C.; Weick, H.; Dendooven, P.; Diwisch, M.; Greiner, F.; Heiße, F.; Knöbel, R.; Lippert, W.; Moore, I. D.; Pohjalainen, I.; Prochazka, A.; Ranjan, M.; Takechi, M.; Winfield, J. S.; Xu, X.

    2015-05-01

    211Po ions in the ground and isomeric states were produced via 238U projectile fragmentation at 1000 MeV/u. The 211Po ions were spatially separated in flight from the primary beam and other reaction products by the fragment separator FRS. The ions were energy-bunched, slowed-down and thermalized in a gas-filled cryogenic stopping cell (CSC). They were then extracted from the CSC and injected into a high-resolution multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS). The excitation energy of the isomer and, for the first time, the isomeric-to-ground state ratio were determined from the measured mass spectrum. In the subsequent experimental step, the isomers were spatially separated from the ions in the ground state by an ion deflector and finally collected with a silicon detector for decay spectroscopy. This pioneering experimental result opens up unique perspectives for isomer-resolved studies. With this versatile experimental method new isomers with half-lives longer than a few milliseconds can be discovered and their decay properties can be measured with highest sensitivity and selectivity. These experiments can be extended to studies with isomeric beams in nuclear reactions.

  4. Possession Zone as a Performance Indicator in Football. The Game of the Best Teams

    Directory of Open Access Journals (Sweden)

    Claudio A. Casal

    2017-07-01

    Full Text Available Possession time in football has been widely discussed in research but few studies have analyzed the importance of the field area in which possession occurs. The objective of this study was to identify the existence of significant differences in the field zone of ball possession between successful and unsuccessful teams and to acknowledge if the match status modulates the possession model. To this end, 2,284 attacks were analyzed corresponding to the matches in the final phase of the UEFA Euro 2016 France, recording possession time and field zone in which possession occurred. Video recordings of matches were analyzed and coded post-event using notational analysis. We have found that successful offensive game patterns are different from unsuccessful ones. Specifically, field zone in which major possession occurs changes significantly between successful and unsuccessful teams (x2 = 15.72, p < 0.05 and through Welch’s T significant differences were detected in possession time between successful and unsuccessful teams (H = 24.289, p < 0.001. The former are characterized by longer possession times, preferably in the middle offensive zone, on the other hand, unsuccessful teams have shorter possession times and preferably on the middle defensive zone. Logistic regression also allowed us to identify that greater possession in the middle offensive zone is a good indicator of success in the offensive game, allowing us to predict a greater chance of victory in the match. Specifically, every time the teams achieve possession in the middle offensive zone, the chance of winning the match will increase 1.72 times and, the probability of winning the match making longer possessions in the middle offensive zone is 44.25%. Applying the Kruskal–Wallis test we have also been able to verify how match status modulates the teams possession time, specifically, when teams are winning they have longer possessions x2 = 92.628, p = 0.011. Results obtained are expected to

  5. Advances in gamma ray resonant scattering and absorption long-lived isomeric nuclear states

    CERN Document Server

    Davydov, Andrey V

    2015-01-01

    This book presents the basics and advanced topics of research of gamma ray physics. It describes measuring of  Fermi surfaces with gamma resonance spectroscopy and the theory of angular distributions of resonantly scattered gamma rays. The dependence of excited-nuclei average lifetime on the shape of the exciting-radiation spectrum and electron binding energies in the spectra of scattered gamma rays is described. Resonant excitation by gamma rays of nuclear isomeric states with long lifetime leads to the emission and absorption lines. In the book, a new gamma spectroscopic method, gravitational gamma spectrometry, is developed. It has a resolution hundred million times higher than the usual Mössbauer spectrometer. Another important topic of this book is resonant scattering of annihilation quanta by nuclei with excited states in connection with positron annihilation. The application of the methods described is to explain the phenomenon of Coulomb fragmentation of gamma-source molecules and resonant scatt...

  6. 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.

  7. Ensemble of Transition State Structures for the Cis-Trans Isomerization of N-Methylacetamide

    Energy Technology Data Exchange (ETDEWEB)

    Mantz, Yves A. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Branduardi, Davide [Italian Inst. of Technology, Genoa (Italy); Bussi, Giovanni [Univ. of Modena and Reggio Emilia and INFM-CNR (Italy); Parrinello, Michele [ETH Zurich, Lugano (Switzerland). Dept. of Chemistry and Applied Biosciences

    2009-09-17

    The cis-trans isomerization of N-methylacetamide (NMA), a model peptidic fragment, is studied theoretically in vacuo and in explicit water solvent at 300 K using the metadynamics technique. The computed cis-trans free energy difference is very similar for NMA(g) and NMA(aq), in agreement with experimental measurements of population ratios and theoretical studies at 0 K. By exploiting the flexibility in the definition of a pair of recently introduced collective variables (Branduardi, D.; Gervasio, F. L.; Parrinello, M. J. Chem. Phys. 2007, 126, 054103), an ensemble of transition state structures is generated at finite temperature for both NMA(g) and NMA(aq), as verified by computing committor distribution functions. Ensemble members of NMA(g) are shown to have correlated values of the backbone dihedral angle and a second dihedral angle involving the amide hydrogen atom. The dynamical character of these structures is preserved in the presence of solvent, whose influence on the committor functions can be modeled using effective friction/noise terms.

  8. A comparative cytotoxicity study of isomeric alkylphthalates to metabolically variant bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Sandy, Edward H. [Key Laboratory of Biogeology and Environmental Geology Laboratory of Chinese Ministry of Education and School of Environmental Studies and Sino-Hungarian Joint Laboratory of Environmental Science and Health, China University of Geosciences, Wuhan 430074 (China); Chemistry Department, Fourah Bay College, University of Sierra Leone, Freetown (Sierra Leone); Yao Jun, E-mail: yaojun@cug.edu.cn [Key Laboratory of Biogeology and Environmental Geology Laboratory of Chinese Ministry of Education and School of Environmental Studies and Sino-Hungarian Joint Laboratory of Environmental Science and Health, China University of Geosciences, Wuhan 430074 (China); Zheng Shixue [State Key Laboratory of Agricultural Microbiology, College of Life Science and Technology, Huazhong Agricultural University, Wuhan 430070 (China); Gogra, Alhaji B.; Chen Huilun [Key Laboratory of Biogeology and Environmental Geology Laboratory of Chinese Ministry of Education and School of Environmental Studies and Sino-Hungarian Joint Laboratory of Environmental Science and Health, China University of Geosciences, Wuhan 430074 (China); Zheng Hui [State Key Laboratory of Agricultural Microbiology, College of Life Science and Technology, Huazhong Agricultural University, Wuhan 430070 (China); Yormah, Thomas B.R. [Chemistry Department, Fourah Bay College, University of Sierra Leone, Freetown (Sierra Leone); Zhang Xin [Yale School of Forestry and Environmental Studies, Yale University, 195 Prospect St., New Haven, CT 06511 (United States); Zaray, Gyula [Department of Chemical Technology and Environmental Chemistry, Eoetvoes University, H-1518 Budapest, P.O. Box 32 (Hungary); Ceccanti, Brunello [Institute of Ecosystem Studies (ISE)-Italian National Research Council (ICT-CNR) (Italy); Choi, Martin M.F., E-mail: mfchoi@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, 224 Waterloo Road, Kowloon Tong (Hong Kong)

    2010-10-15

    This work investigated the toxicity of two isomeric alkylphthalates, i.e., di-n-octyl phthalate (DOP) and di-2-ethylhexyl phthalate (DEHP) to two model bacteria, Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis), which have been previously used to study the toxicity of environmental pollutants. Microcalorimetry was used as the key analytical tool alongside scanning electron microscopy (SEM) and traditional microbiology techniques. The thermokinetic parameters from microcalorimetry showed that the phthalates had a biphasic effect on the metabolic activities of the bacteria; serving as energy sources for the bacteria thereby stimulating their growth at low dosages ({<=}150 {mu}g/mL), but displaying inhibitory effects at higher dosages ({>=}300 {mu}g/mL), indicated by a sharp decrease in growth rate constants at 450 {mu}g/mL. The SEM revealed that the bacterial cells were morphological deformed, with shrunk cells and elongated strands at 600 {mu}g/mL of both phthalates. The elongated strands inferred that the phthalates inhibited the reproductive processes of the bacteria by possibly impeding some stages of cell division. The half inhibitory concentrations of the phthalates showed that DEHP was more toxic than DOP. Additionally, E. coli, a facultative anaerobe, was more susceptible to the toxic effects of phthalates than B. subtilis, an obligate aerobe capable of forming endospores crucial for tolerating extreme environmental conditions.

  9. How to compute isomerization energies of organic molecules with quantum chemical methods.

    Science.gov (United States)

    Grimme, Stefan; Steinmetz, Marc; Korth, Martin

    2007-03-16

    The reaction energies for 34 typical organic isomerizations including oxygen and nitrogen heteroatoms are investigated with modern quantum chemical methods that have the perspective of also being applicable to large systems. The experimental reaction enthalpies are corrected for vibrational and thermal effects, and the thus derived "experimental" reaction energies are compared to corresponding theoretical data. A series of standard AO basis sets in combination with second-order perturbation theory (MP2, SCS-MP2), conventional density functionals (e.g., PBE, TPSS, B3-LYP, MPW1K, BMK), and new perturbative functionals (B2-PLYP, mPW2-PLYP) are tested. In three cases, obvious errors of the experimental values could be detected, and accurate coupled-cluster [CCSD(T)] reference values have been used instead. It is found that only triple-zeta quality AO basis sets provide results close enough to the basis set limit and that sets like the popular 6-31G(d) should be avoided in accurate work. Augmentation of small basis sets with diffuse functions has a notable effect in B3-LYP calculations that is attributed to intramolecular basis set superposition error and covers basic deficiencies of the functional. The new methods based on perturbation theory (SCS-MP2, X2-PLYP) are found to be clearly superior to many other approaches; that is, they provide mean absolute deviations of less than 1.2 kcal mol-1 and only a few (computational thermochemistry methods.

  10. Design Efficient and Ultralong Pure Organic Room-Temperature Phosphorescent Materials by Structural Isomerism.

    Science.gov (United States)

    Xiong, Yu; Zhao, Zheng; Zhao, Wei Jun; Ma, Hui Li; Peng, Qian; He, Zi Kai; Zhang, Xue Peng; Chen, Yun Cong; He, Xue Wen; Lam, Jacky; Tang, Ben Zhong

    2018-05-08

    Pure organic materials with ultralong room temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, without heavy atoms and carbonyl or heteroatomic groups, they generally show inefficient intersystem crossing (ISC) due to the weak spin-orbit coupling (SOC). Many efforts have been made to enhance SOC but examples in realizing both efficient and ultralong RTP have been limited. Here we present a novel design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔEST) and pure ππ* configuration of the lowest triplet state (T1) via structural isomerism to obtain efficient and ultralong RTP materials. The meta-isomer of carbazole-substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1%, whose performance is among the best RTP materials reported so far. Study on the structure-property relationship demonstrates that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔEST and pure ππ* configuration of T1. This rational design will open a new avenue for exploring novel pure organic RTP materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. The decay of 399 KeV isomeric state in 197Pt

    International Nuclear Information System (INIS)

    Soares, J.C.; Melo, A.A.; Gil, F.B.; Dias, H.

    1981-02-01

    The nuclear levels in 197 Pt have been studied from decay of 95.4 min 197 (sup m)Pt. The isomeric state was produced by (n,#betta#) reaction on the enriched 196 Pt. The #betta#-ray spectra have been observed with a hyperpure Ge detector and a large volume Ge(Li) detector. The half lives of the 399 KeV and the 53 KeV states were determined with improved precision. The results are: T1/2 (399 KeV) = 95.41 +- 0.18 min and T1/2(53 KeV) = 16.58 +- 0.17 ns. The g-factor of the 53 Kev 5/2 - state has been measured by the gamma-gamma time differential perturbed angular correlation (TDPAC) method in an external magnetic field of 25,1 kG using the 346 - 53 KeV gamma cascade. The value of g-factor was obtained to be + 0.335 +- 0.010. This result is compared with the known g-factors of the similar states in 195 Pt, and in 197 Hg and 199 Hg and also with the theoretical calculations based on the quasiparticle-phonon coupling scheme. Possibility of using the 346 - 53 KeV gamma cascade in 197 Pt in the future TDPAC studies is discussed. (Author) [pt

  12. Identification of levels above 6{sup -} isomeric state in {sup 66}Cu

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Purnima; Palit, R.; Biswas, S.; Saha, S. [Tata Institute of Fundamental Research, Department of Nuclear and Atomic Physics, Mumbai (India); Choudhury, D. [Horia Hulubei National Institute for Physics and Nuclear Engineering, ELI-NP, Magurele (Romania); Srivastava, P.C. [Indian Institute of Technology Roorkee, Department of Physics, Roorkee (India); Sethi, J. [Tata Institute of Fundamental Research, Department of Nuclear and Atomic Physics, Mumbai (India); University of Maryland, Department of Chemistry and Biochemistry, College Park, MD (United States)

    2017-04-15

    Excited states in odd-odd {sup 66}Cu were investigated in a reaction between a 136 MeV {sup 30}Si beam and a {sup 65}Cu target with the Indian National Gamma Array. Six new transitions have been identified including four transitions feeding the 600 ns 6{sup -} isomeric state from an investigation of prompt-prompt and prompt-delayed coincidence events. The results of the present work have extended the level structure of this nucleus up to I{sup π} = (9{sup -}). In addition, new information on the set of πp{sub 3/2}νg{sub 9/2} multiplets in this nucleus have been added. Shell model calculations were performed within the fpg{sub 9/2} and f{sub 5/2}pg{sub 9/2} model spaces. The results of shell model calculations using the fpg{sub 9/2} model space have been observed to be in better agreement with experimental excitation energies up to the highest spin observed. The results of the present work highlight the necessity of f{sub 7/2} proton holes to describe the positive as well as negative parity states in {sup 66}Cu. (orig.)

  13. High rate gamma spectroscopy system for activation analysis of short-lived isomeric transitions

    Energy Technology Data Exchange (ETDEWEB)

    Westphall, G P [Atominstitut der Oesterreichischen Hochschulen, Vienna

    1976-07-15

    A high rate spectroscopy system specially suited for measurement of short-lived isomeric transitions is described, which, as part of a fast activation analysis facility at the TRIGA Mark II reactor, provides for automatic recording and immediate evaluation of gamma spectra taken from nuclides activated at stationary or pulsed reactor power. The system consists of a commercial de-coupled Ge(Li)-detector of 70 cm/sup 3/ modified for recycling operation for input rates in excess of 500000 c/s /sup 60/Co, a time variant trapezoidal shaping section and a fast constant dead-time ADC coupled to a programmed multichannel analyzer. Novel circuits for efficient pile-up rejection and time variant base line restoration extend the concept of gated integration up to count rates of more than 200000 c/s /sup 60/Co. Time-sequenced recording of spectra is performed by a minicomputer operated as a front-end processor of a larger laboratory computer, where final data processing takes place. New concepts for very simple and cost-effective implementation of multichannel analyzers by means of general purpose small computers are described.

  14. Sugar Profile, Mineral Content, and Rheological and Thermal Properties of an Isomerized Sweet Potato Starch Syrup.

    Science.gov (United States)

    Dominque, Brunson; Gichuhi, Peter N; Rangari, Vijay; Bovell-Benjamin, Adelia C

    2013-01-01

    Currently, corn is used to produce more than 85% of the world's high fructose syrup (HFS). There is a search for alternative HFS substrates because of increased food demand and shrinking economies, especially in the developing world. The sweet potato is a feasible, alternative raw material. This study isomerized a high glucose sweet potato starch syrup (SPSS) and determined its sugar profile, mineral content, and rheological and thermal properties. Rheological and thermal properties were measured using a rheometer and DSC, respectively. Sweet potato starch was hydrolyzed to syrup with a mean fructose content of 7.6 ± 0.4%. The SPSS had significantly higher (P syrups. During 70 days of storage, the SPSS acted as a non-Newtonian, shear-thinning liquid in which the viscosity decreased as shear stress increased. Water loss temperature of the SPSS continually decreased during storage, while pancake and ginger syrups' peak water loss temperature decreased initially and then increased. Further and more detailed studies should be designed to further enhance the fructose content of the syrup and observe its stability beyond 70 days. The SPSS has the potential to be used in human food systems in space and on Earth.

  15. Sugar Profile, Mineral Content, and Rheological and Thermal Properties of an Isomerized Sweet Potato Starch Syrup

    Directory of Open Access Journals (Sweden)

    Brunson Dominque

    2013-01-01

    Full Text Available Currently, corn is used to produce more than 85% of the world’s high fructose syrup (HFS. There is a search for alternative HFS substrates because of increased food demand and shrinking economies, especially in the developing world. The sweet potato is a feasible, alternative raw material. This study isomerized a high glucose sweet potato starch syrup (SPSS and determined its sugar profile, mineral content, and rheological and thermal properties. Rheological and thermal properties were measured using a rheometer and DSC, respectively. Sweet potato starch was hydrolyzed to syrup with a mean fructose content of 7.6±0.4%. The SPSS had significantly higher (P<0.05 mineral content when compared to commercial ginger and pancake syrups. During 70 days of storage, the SPSS acted as a non-Newtonian, shear-thinning liquid in which the viscosity decreased as shear stress increased. Water loss temperature of the SPSS continually decreased during storage, while pancake and ginger syrups’ peak water loss temperature decreased initially and then increased. Further and more detailed studies should be designed to further enhance the fructose content of the syrup and observe its stability beyond 70 days. The SPSS has the potential to be used in human food systems in space and on Earth.

  16. Ligand photo-isomerization triggers conformational changes in iGluR2 ligand binding domain.

    Directory of Open Access Journals (Sweden)

    Tino Wolter

    Full Text Available Neurological glutamate receptors bind a variety of artificial ligands, both agonistic and antagonistic, in addition to glutamate. Studying their small molecule binding properties increases our understanding of the central nervous system and a variety of associated pathologies. The large, oligomeric multidomain membrane protein contains a large and flexible ligand binding domains which undergoes large conformational changes upon binding different ligands. A recent application of glutamate receptors is their activation or inhibition via photo-switchable ligands, making them key systems in the emerging field of optochemical genetics. In this work, we present a theoretical study on the binding mode and complex stability of a novel photo-switchable ligand, ATA-3, which reversibly binds to glutamate receptors ligand binding domains (LBDs. We propose two possible binding modes for this ligand based on flexible ligand docking calculations and show one of them to be analogues to the binding mode of a similar ligand, 2-BnTetAMPA. In long MD simulations, it was observed that transitions between both binding poses involve breaking and reforming the T686-E402 protein hydrogen bond. Simulating the ligand photo-isomerization process shows that the two possible configurations of the ligand azo-group have markedly different complex stabilities and equilibrium binding modes. A strong but slow protein response is observed after ligand configuration changes. This provides a microscopic foundation for the observed difference in ligand activity upon light-switching.

  17. Isomerization and dissociation in competition: the two-component dissociation rates of methyl acetate ions

    Science.gov (United States)

    Mazyar, Oleg A.; Mayer, Paul M.; Baer, Tomas

    1997-11-01

    Threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy has been used to investigate the unimolecular chemistry of metastable methyl acetate ions, CH3COOCH3.+. The rate of molecular ion fragmentation with the loss of CH3O. and CH2OH radicals as a function of ion internal energy was obtained from the coincidence data and used in conjunction with Rice-Ramsperger-Kassel-Markus and ab initio molecular orbital calculations to model the dissociation/isomerization mechanism of the methyl acetate ion (A). The data were found to be consistent with the mechanism involving a hydrogen-bridged complex CH3CO[middle dot][middle dot][middle dot]H[middle dot][middle dot][middle dot]OCH2.+(E) as the direct precursor of the observed fragments CH3CO+ and CH2OH.. The two-component decay rates were modeled with a three-well-two-product potential energy surface including the distonic ion CH3C(OH)OCH2.+(B) and enol isomer CH2C(OH)OCH3.+(C), which are formed from the methyl acetate ion by two consecutive [1,4]-hydrogen shifts. The 0 K heats of formation of isomers B and C as well as transition states TSAB, TSBC, and TSBE (relative to isomer A) were calculated from Rice-Ramsperger-Kassel-Markus (RRKM) theory.

  18. A comparative cytotoxicity study of isomeric alkylphthalates to metabolically variant bacteria

    International Nuclear Information System (INIS)

    Sandy, Edward H.; Yao Jun; Zheng Shixue; Gogra, Alhaji B.; Chen Huilun; Zheng Hui; Yormah, Thomas B.R.; Zhang Xin; Zaray, Gyula; Ceccanti, Brunello; Choi, Martin M.F.

    2010-01-01

    This work investigated the toxicity of two isomeric alkylphthalates, i.e., di-n-octyl phthalate (DOP) and di-2-ethylhexyl phthalate (DEHP) to two model bacteria, Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis), which have been previously used to study the toxicity of environmental pollutants. Microcalorimetry was used as the key analytical tool alongside scanning electron microscopy (SEM) and traditional microbiology techniques. The thermokinetic parameters from microcalorimetry showed that the phthalates had a biphasic effect on the metabolic activities of the bacteria; serving as energy sources for the bacteria thereby stimulating their growth at low dosages (≤150 μg/mL), but displaying inhibitory effects at higher dosages (≥300 μg/mL), indicated by a sharp decrease in growth rate constants at 450 μg/mL. The SEM revealed that the bacterial cells were morphological deformed, with shrunk cells and elongated strands at 600 μg/mL of both phthalates. The elongated strands inferred that the phthalates inhibited the reproductive processes of the bacteria by possibly impeding some stages of cell division. The half inhibitory concentrations of the phthalates showed that DEHP was more toxic than DOP. Additionally, E. coli, a facultative anaerobe, was more susceptible to the toxic effects of phthalates than B. subtilis, an obligate aerobe capable of forming endospores crucial for tolerating extreme environmental conditions.

  19. Synthesis, characterization and ESR study of polyesters containing isomeric naphthylene units by gamma irradiation

    International Nuclear Information System (INIS)

    Choi, B.K.; Hill, D.J.T.; Choi, E.J.; Ahn, H.K.

    1998-01-01

    Full text: Aromatic polyesters containing naphthalene groups have interesting properties because the geometry of the naphthalene group can provide many of the structural features for the polymer chain. In this study we synthesized six polyesters from 4,4 ' - (hexafluoroisopropyl-idene)bis(benzoic acid) and isomeric naphthylene-diols. An ESR study of the radicals formed on gamma radiolysis of the polyesters has been undertaken to investigate their relative radiation sensitivities. The structures of the polyesters were characterized by means of IR spectroscopy. Inherent viscosities were measured in the range of 0.11 - 0.46 dL/g. Thermal properties of polyesters were determined by DSC and TGA thermograms, respectively. All polyesters were irradiated in an AECL Gamma cell with a dose rate of approximately 6.7kGy h -1 to doses in the range of 0 - 15kGy at 77K and 300K, respectively. In order to identify other radicals present at 77K, annealing studies were utilized by taking advantage of the different reactivities of these radicals

  20. LC-MS n Analysis of Isomeric Chondroitin Sulfate Oligosaccharides Using a Chemical Derivatization Strategy

    Science.gov (United States)

    Huang, Rongrong; Pomin, Vitor H.; Sharp, Joshua S.

    2011-09-01

    Improved methods for structural analyses of glycosaminoglycans (GAGs) are required to understand their functional roles in various biological processes. Major challenges in structural characterization of complex GAG oligosaccharides using liquid chromatography-mass spectrometry (LC-MS) include the accurate determination of the patterns of sulfation due to gas-phase losses of the sulfate groups upon collisional activation and inefficient on-line separation of positional sulfation isomers prior to MS/MS analyses. Here, a sequential chemical derivatization procedure including permethylation, desulfation, and acetylation was demonstrated to enable both on-line LC separation of isomeric mixtures of chondroitin sulfate (CS) oligosaccharides and accurate determination of sites of sulfation by MS n . The derivatized oligosaccharides have sulfate groups replaced with acetyl groups, which are sufficiently stable to survive MS n fragmentation and reflect the original sulfation patterns. A standard reversed-phase LC-MS system with a capillary C18 column was used for separation, and MS n experiments using collision-induced dissociation (CID) were performed. Our results indicate that the combination of this derivatization strategy and MS n methodology enables accurate identification of the sulfation isomers of CS hexasaccharides with either saturated or unsaturated nonreducing ends. Moreover, derivatized CS hexasaccharide isomer mixtures become separable by LC-MS method due to different positions of acetyl modifications.

  1. Nanopore Analysis of the 5-Guanidinohydantoin to Iminoallantoin Isomerization in Duplex DNA.

    Science.gov (United States)

    Zeng, Tao; Fleming, Aaron M; Ding, Yun; Ren, Hang; White, Henry S; Burrows, Cynthia J

    2018-04-06

    In DNA, guanine oxidation yields diastereomers of 5-guanidinohydantoin (Gh) as one of the major products. In nucleosides and single-stranded DNA, Gh is in a pH-dependent equilibrium with its constitutional isomer iminoallantoin (Ia). Herein, the isomerization reaction between Gh and Ia was monitored in duplex DNA using a protein nanopore by measuring the ionic current when duplex DNA interacts with the pore under an electrophoretic force. Monitoring current levels in this single-molecule method proved to be superior for analysis of population distributions in an equilibrating mixture of four isomers in duplex DNA as a function of pH. The results identified Gh as a major isomer observed when base paired with A, C, or G at pH 6.4-8.4, and Ia was a minor isomer of the reaction mixture that was only observed when the pH was >7.4 in the duplex DNA context. The present results suggest that Gh will be the dominant isomer in duplex DNA under physiological conditions regardless of the base-pairing partner in the duplex.

  2. A high rate gamma spectroscopy system for activation analysis of short lived isomeric transitions

    Energy Technology Data Exchange (ETDEWEB)

    Westphal, G P [Atominstitut, Vienna (Austria)

    1976-07-01

    A high rate spectroscopy system specially suited for measurement of short-lived isomeric transitions is described, which, as part of a fast activation analysis facility at the TRIGA Mark II reactor, provides for automatic recording and immediate evaluation of gamma spectra taken from nuclides activated at stationary or pulsed reactor power. The system consists of a commercial DC-coupled Ge(Li)-detector of 70 cm{sup 3} modified for recycling operation for input rates in excess of 500,000 c/s Co-60, a time variant trapezoidal shaping section and a fast constant dead-time ADC coupled to a programmed multi-channel analyzer. Novel circuits for efficient pile-up rejection and time variant base line restoration extend the concept of gated integration up to count rates of more than 300,000 c/s Co-60. Time-sequenced recording of spectra is performed by a mini computer operated as a front-end processor of a larger laboratory computer, where final data processing takes place. New concepts for very simple and cost-effective implementation of multi-channel analyzers by means of general purpose small computers are described. (author)

  3. Excitation function and isomeric ratio of Tc-isotopes from the 93Nb(α, xn) reaction

    International Nuclear Information System (INIS)

    Kim, K.; Kim, G.N.; Naik, H.; Zaman, M.; Yang, S.-C.; Song, T.-Y.; Guin, R.; Das, S.K.

    2015-01-01

    The excitation functions of 94–96 Tc isotopes and independent isomeric ratios of 93m, g Tc, 94m, g Tc, and 95m, g Tc from the 93 Nb(α, xn) reaction within the energy range below 40 MeV have been determined by using a stacked-foil activation and an off-line γ-ray spectrometric technique at the Variable Energy Cyclotron Center, Kolkota, India. The excitation function of 94–96 Tc in the 93 Nb(α, xn) reaction was also calculated by using the computer code TALYS 1.6. The present data are found to be in general agreement with the literature data but have similar trend with some deviation from calculated data of the TALYS 1.6 code. The isomeric ratios of 93m, g Tc, 94m, g Tc, and 95m, g Tc in the 93 Nb(α, xn) reactions from the present work and literature data were compared with similar data in the 93 Nb( 3 He, xn) and 96 Mo(p, xn) reactions. In all the three reactions, the isomeric ratios increase with the increasing excitation energy. However, at all excitation energies, the isomeric ratios of 93m, g Tc, 94m, g Tc, and 95m, g Tc in the 93 Nb(α, xn) and 93 Nb( 3 He, xn) reactions are higher than those in the 96 Mo(p, xn) reactions, which indicate the role of input angular momentum besides excitation energy. Above the excitation energy of 35–55 MeV, the isomeric ratios of 95m, g Tc, 94m, g Tc, and 93m, g Tc decrease in all the 93 Nb(α, xn), 93 Nb( 3 He, xn) and 96 Mo(p, xn) reactions. This decreasing trend at higher excitation energy indicates the starting of pre-equilibrium reaction, which depends on the target, projectile, and type of reaction products

  4. 19 CFR 7.2 - Insular possessions of the United States other than Puerto Rico.

    Science.gov (United States)

    2010-04-01

    ... than Puerto Rico. 7.2 Section 7.2 Customs Duties U.S. CUSTOMS AND BORDER PROTECTION, DEPARTMENT OF... NAVAL STATION § 7.2 Insular possessions of the United States other than Puerto Rico. (a) Insular possessions of the United States other than Puerto Rico are also American territory but, because those insular...

  5. 50 CFR 92.6 - Use and possession of migratory birds.

    Science.gov (United States)

    2010-10-01

    ... 50 Wildlife and Fisheries 6 2010-10-01 2010-10-01 false Use and possession of migratory birds. 92... INTERIOR (CONTINUED) MISCELLANEOUS PROVISIONS MIGRATORY BIRD SUBSISTENCE HARVEST IN ALASKA General Provisions § 92.6 Use and possession of migratory birds. You may not sell, offer for sale, purchase, or offer...

  6. 50 CFR 600.1204 - Shark finning; possession at sea and landing of shark fins.

    Science.gov (United States)

    2010-10-01

    ... 50 Wildlife and Fisheries 8 2010-10-01 2010-10-01 false Shark finning; possession at sea and landing of shark fins. 600.1204 Section 600.1204 Wildlife and Fisheries FISHERY CONSERVATION AND... PROVISIONS Shark Finning § 600.1204 Shark finning; possession at sea and landing of shark fins. (a)(1) No...

  7. 10 CFR 70.20a - General license to possess special nuclear material for transport.

    Science.gov (United States)

    2010-01-01

    ... 10 Energy 2 2010-01-01 2010-01-01 false General license to possess special nuclear material for transport. 70.20a Section 70.20a Energy NUCLEAR REGULATORY COMMISSION (CONTINUED) DOMESTIC LICENSING OF... transport. (a) A general license is issued to any person to possess formula quantities of strategic special...

  8. Stability properties of solutions to nonlinear models possessing a sign-undefined metric

    International Nuclear Information System (INIS)

    Barashenkov, I.V.

    1983-01-01

    Multicomponent field systems possessing a sign-undefined internal space metric, in particular models with a noncompact global invariance group are investigated. It is shown that the energy cannot have even a conditional relative minimum. It is demonstrated, nevertheless, that the corresponding nonlinear equations of motion are permitted to possess stable particle-like solutions

  9. Stability properties of solutions to nonlinear models possessing a sign-undefined metric

    International Nuclear Information System (INIS)

    Barashenkov, I.V.

    1983-01-01

    Multicomponent field systems possessing a sign-undefined internal space metric, in particular models with a noncompact global invariance group, are investigated. It is shown that the energy cannot have even a conditional relative minimum. It is demonstrated, nevertheless, that the corresponding nonlinear equations of motion are permitted to possess stable particle-like solutions. (Auth.)

  10. The Regulation of the Possession of Weapons at Gatherings | du Toit

    African Journals Online (AJOL)

    The Act also amends the Regulation of Gatherings Act 205 of 1993 to prohibit the possession of any dangerous weapon at a gathering or demonstration. ... (b) possession of dangerous weapons during the participation in any religious or cultural activities or lawful sport, recreation or entertainment or (c) legitimate collection, ...

  11. The expected value of possession in professional rugby league match-play.

    Science.gov (United States)

    Kempton, Thomas; Kennedy, Nicholas; Coutts, Aaron J

    2016-01-01

    This study estimated the expected point value for starting possessions in different field locations during rugby league match-play and calculated the mean expected points for each subsequent play during the possession. It also examined the origin of tries scored according to the method of gaining possession. Play-by-play data were taken from all 768 regular-season National Rugby League (NRL) matches during 2010-2013. A probabilistic model estimated the expected point outcome based on the net difference in points scored by a team in possession in a given situation. An iterative method was used to approximate the value of each situation based on actual scoring outcomes. Possessions commencing close to the opposition's goal-line had the highest expected point equity, which decreased as the location of the possession moved towards the team's own goal-line. Possessions following an opposition error, penalty or goal-line dropout had the highest likelihood of a try being scored on the set subsequent to their occurrence. In contrast, possessions that follow an opposition completed set or a restart were least likely to result in a try. The expected point values framework from our model has applications for informing playing strategy and assessing individual and team performance in professional rugby league.

  12. Are symptoms of spirit possessed patients covered by the DSM-IV or DSM-5 criteria for possession trance disorder? A mixed-method explorative study in Uganda.

    Science.gov (United States)

    van Duijl, Marjolein; Kleijn, Wim; de Jong, Joop

    2013-09-01

    As in many cultures, spirit possession is a common idiom of distress in Uganda. The DSM-IV contains experimental research criteria for dissociative and possession trance disorder (DTD and PTD), which are under review for the DSM-5. In the current proposed categories of the DSM-5, PTD is subsumed under dissociative identity disorder (DID) and DTD under dissociative disorders not elsewhere classified. Evaluation of these criteria is currently urgently required. This study explores the match between local symptoms of spirit possession in Uganda and experimental research criteria for PTD in the DSM-IV and proposed criteria for DID in the DSM-5. A mixed-method approach was used combining qualitative and quantitative research methods. Local symptoms were explored of 119 spirit possessed patients, using illness narratives and a cultural dissociative symptoms' checklist. Possible meaningful clusters of symptoms were inventoried through multiple correspondence analysis. Finally, local symptoms were compared with experimental criteria for PTD in the DSM-IV and proposed criteria for DID in the DSM-5. Illness narratives revealed different phases of spirit possession, with passive-influence experiences preceding the actual possession states. Multiple correspondence analysis of symptoms revealed two dimensions: 'passive' and 'active' symptoms. Local symptoms, such as changes in consciousness, shaking movements, and talking in a voice attributed to spirits, match with DSM-IV-PTD and DSM-5-DID criteria. Passive-influence experiences, such as feeling influenced or held by powers from outside, strange dreams, and hearing voices, deserve to be more explicitly described in the proposed criteria for DID in the DSM-5. The suggested incorporation of PTD in DID in the DSM-5 and the envisioned separation of DTD and PTD in two distinctive categories have disputable aspects.

  13. "Satan has afflicted me!" Jinn-possession and mental illness in the Qur'an.

    Science.gov (United States)

    Islam, F; Campbell, R A

    2014-02-01

    Mental health stigma in Muslim communities may be partly due to a commonly held belief among some Muslims about the supernatural causes of mental illness (i.e. jinn-possession brought on by one's sinful life). A thematic analysis was carried out on four English translations and the Arabic text of the Qur'an to explore whether the connection between jinn-possession and insanity exists within the Muslim holy book. No connection between spirit-possession and madness or mental illness was found. Pagans taunted and labelled people as jinn-possessed only to ostracize and scapegoat. Linking the labelling of people as jinn-possession to a pagan practice may be used to educate Muslims, so they can reassess their community's stigma towards the mentally ill.

  14. g-factor of the 7/2+ isomeric bandhead in 175 W

    International Nuclear Information System (INIS)

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

    2000-01-01

    Considerable effort is presently devoted to the investigation of the high-K isomers of multi-quasiparticle intrinsic structure systematically found in the deformed nuclei with Z=72-76 of the A ≅ 180 mass region. The configuration assignments for these isomers are based on measured static moments, as well as, on experimental branching ratios in the associated bands, from which (g K - g R )/Q 0 are derived. In the multi-quasiparticle state g-factor calculations, values taken from neighbouring odd-mass nuclei are generally used for the proton and neutron deformed single-particle g-factors. A good knowledge of these quantities is required for reliable high-K state g-factor evaluations. In the present work we report on the g-factor measurement for the low-lying J π = 7/2 + isomer bandhead in 175 W described by the neutron 7/2 + [633] Nilsson orbital. The isomeric state was populated in the 164 Dy( 16 O,5n) 175 W reaction using the 83 MeV pulsed 16 O beam (pulse width 1.5 ns, repetition period 800 ns) delivered by the LNL XTU-Tandem. The target consisted of 0.5 mg/cm 2 metallic 164 Dy on thick Pb backing which stopped the recoiling 175 W nuclei and the 16 O beam. The target was placed in an external magnetic field of 27.2(6) kG whose direction was periodically reversed. The 7/2 + isomeric state with T 1/2 = 216(6) ns and E x =234.9 keV de-excites by a dipole transition of 130.9 keV to the 5/2 - level. The angular distribution of the 130.9 keV gamma-ray has been observed time-differentially by using two planar Ge detectors placed at ± 135 angle with respect to the beam direction. The background corrected time spectra I(t,θ) obtained for the magnetic field direction up and down were used to form the experimental modulation ratio R exp (t)=[I↑(t,θ) - I ↓ (t,θ)]/[I↑(t,θ) + I ↓ (t,θ)]. The modulation pattern revealed Larmor oscillations with an amplitude strongly attenuated in time. The observed damping of the anisotropy has been attributed to quadrupole

  15. Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications

    KAUST Repository

    Monge Palacios, Manuel

    2018-01-29

    We performed a theoretical study on the double hydrogen shift isomerization reaction of a six carbon atom Criegee intermediate (C6-CI), catalyzed by formic acid (HCOOH), to produce vinylhydroperoxide (VHP), C6-CI+HCOOH→VHP+HCOOH. This Criegee intermediate can serve as a surrogate for larger CIs derived from important volatile organic compounds like monoterpenes, whose reactivity is not well understood and are difficult to handle computationally. The reactant HCOOH exerts a pronounced catalytic effect on the studied reaction by lowering the barrier height, but the kinetic enhancement is hindered by the multistructural anharmonicity. First, the rigid ring-structure adopted by the saddle point to facilitate simultaneous transfer of two atoms does not allow formation of as many conformers as those formed by the reactant C6-CI. And second, the flexible carbon chain of C6-CI facilitates the formation of stabilizing intramolecular C–H···O hydrogen bonds; this stabilizing effect is less pronounced in the saddle point structure due to its tightness and steric effects. Thus, the contribution of the reactant C6-CI conformers to the multistructural partition function is larger than that of the saddle point conformers. The resulting low multistructural anharmonicity factor partially cancels out the catalytic effect of the carboxylic acid, yielding in a moderately large rate coefficient, k(298 K) = 4.9·10-13 cm3 molecule-1 s-1. We show that carboxylic acids may promote the conversion of stabilized Criegee intermediates into vinylhydroperoxides in the atmosphere, which generates OH radicals and leads to secondary organic aerosol, thereby affecting the oxidative capacity of the atmosphere and ultimately the climate.

  16. Differentiation of isomeric 2-aryldimethyltetrahydro-5-quinolinones by electron ionization and electrospray ionization mass spectrometry.

    Science.gov (United States)

    Kumar, Ch Dinesh; Chary, V Naresh; Dinesh, A; Reddy, P S; Srinivas, K; Gayatri, G; Sastry, G N; Prabhakar, S

    2011-10-15

    A series of isomeric 2-aryl-6,6-dimethyltetrahydro-5-quinolinones (set I) and 2-aryl-7,7-dimethyltetrahydro-5-quinolinones (set II) were studied under positive ion electron ionization (EI) and electrospray ionization (ESI) techniques. Under EI conditions, the molecular ions were found to be less stable in set I isomers, and they resulted in abundant fragment ions, i.e., [M-CH(3)](+), [M-CO](+.), [M-HCO](+), [M-(CH(3),CO)](+), and [M-(CH(3),CH(2)O)](+), when compared with set II isomers. In addition, the set I isomers showed specific fragment ions corresponding to [M-OH](+) and [M-OCH(3)](+). The retro-Diels-Alder (RDA) product ion was always higher in set II isomers. The ESI mass spectra produced [M + H](+) ions, and their decomposition showed favorable loss of CH(3) radical, CH(4) and C(2)H(6) molecules in set I isomers. The set II isomers, however, showed predominant RDA product ions, and specific loss of H(2)O. The selectivity in EI and ESI was attributed to the instability of set I isomers by the presence of a gem-dimethyl group at the α-position, and it was supported by the data from model compounds without a gem-dimethyl group. Density functional theory (DFT) calculations successfully corroborated the fragmentation pathways for diagnostic ions. This study revealed the effect of a gem-dimethyl group located at the α-position to the carbonyl having aromatic/unsaturated carbon on the other side of the carbonyl group. Copyright © 2011 John Wiley & Sons, Ltd.

  17. Structures of butyl ions formed by electron impact ionization of isomeric butyl halides and alkanes

    International Nuclear Information System (INIS)

    Shold, D.M.; Ausloos, P.

    1978-01-01

    Using a pulsed ion cyclotron resonance (ICR) spectrometer, it is demonstrated that at pressures of about 10 -6 Torr and at observation times ranging from 10 -3 to 0.5 s, isobutane, neopentane, 2,2-dimethylbutane, isobutyl halides, and tert-butyl halides form C 4 H 9 + ions having the tertiary structure. In n-alkanes, 2-methylbutane, 3-methylpentane, n-butyl halides, and sec-butyl halides, both sec-C 4 H 9 + and t-C 4 H 9 + ions are observed, the sec-C 4 H 9 + ions surviving without rearrangement for at least 0.1 s. However, in the case of the halides, a collision-induced isomerization of the sec-C 4 H 9 + to the t-C 4 H 9 + ions occurs. The efficiency of this process increases with the basicity of the alkyl halide. Radiolysis experiments carried out at atmospheric pressures indicate, in agreement with ICR and solution experiments, that at times as short as 10 -10 s the majority of the i-C 4 H 9 + ions from isobutyl bromide rearrange to the t-C 4 H 9 + structure. On the other hand, in the radiolysis of both n-hexane and 3-methylpentane, the abundance of t-C 4 H 9 + relative to sec-C 4 H 9 + is substantially smaller than that observed in the ICR experiments, and decreases with decreasing collision interval. It is suggested that about 90% of the i-C 4 H 9 + can rearrange to t-C 4 H 9 + by simple 1,2-hydride shift without involving secondary or protonated methylcyclopropane structures as intermediates. 4 figures, 2 tables

  18. Pathological spirit possession as a cultural interpretation of trauma-related symptoms.

    Science.gov (United States)

    Hecker, Tobias; Barnewitz, Eva; Stenmark, Hakon; Iversen, Valentina

    2016-07-01

    Spirit possession is a phenomenon frequently occurring in war-torn countries. It has been shown to be an idiom of distress entailing dissociative symptoms. However, its association with trauma exposure and trauma-related disorders remains unclear. This study aimed to explore subjective disease models and the relationship between pathological spirit possession and trauma-related disorders in the Eastern Democratic Republic of the Congo. Seventy-three (formerly) possessed persons (74% female, mean age = 34 years), referred by traditional and spiritual healers, were interviewed about their experiences of pathological spirit possession, trauma exposure, posttraumatic stress disorder (PTSD) symptoms, depressive symptoms, shame and guilt, psychotic symptoms, somatic complaints, and the impairment of psychosocial functioning. The most common disease model for pathological spirit possession was another person having sent the spirit, mostly a family member or a neighbor, out of jealousy or conflict over resources. Significant correlations were found between spirit possession over lifetime and PTSD symptom severity, feelings of shame and guilt, depressive symptoms, somatic complaints, and psychotic symptoms. Spirit possession during the preceding 4 weeks was associated with PTSD symptom severity, impairment of psychosocial functioning, and psychotic symptom severity. The results of this study indicate that pathological spirit possession is a broad explanatory framework for various subjectively unexplainable mental and physical health problems, including but not limited to trauma-related disorders. Understanding pathological spirit possession as a subjective disease model for various mental and physical health problems may help researchers and clinicians to develop culturally sensitive treatment approaches for affected individuals. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

  19. Single-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids

    KAUST Repository

    Goldbach, Verena

    2016-11-09

    Dicarboxylic acids are compounds of high value, but to date long-chain alpha,omega-dicarboxylic acids have been difficult to access in a direct way. Unsaturated fatty acids are ideal starting materials with their molecular structure of long methylene sequences and a carboxylate functionality, in addition to a double bond that offers itself for functionalization. Within this paper, we established a direct access to alpha,omega-dicarboxylic acids by combining isomerization and selective terminal carbonylation of the internal double bond with water as a nucleophile on unsaturated fatty acids. We identified the key elements of this reaction: a homogeneous reaction mixture ensuring sufficient contact between all reactants and a catalyst system allowing for activation of the Pd precursor under aqueous conditions. Experiments under pressure reactor conditions with [(dtbpx)Pd(OTf)(2)] as catalyst precursor revealed the importance of nucleophile and reactant concentrations and the addition of the diprotonated diphosphine ligand (dtbpxH(2))(OTf)(2) to achieve turnover numbers >120. A variety of unsaturated fatty acids, including a triglyceride, were converted to valuable long-chain dicarboxylic acids with high turnover numbers and selectivities for the linear product of >90%. We unraveled the activation pathway of the Pd-II precursor, which proceeds via a reductive elimination step forming a Pd species and oxidative addition of the diprotonated diphosphine ligand, resulting in the formation of the catalytically active Pd hydride species. Theoretical calculations identified the hydrolysis as the rate-determining step. A low nucleophile concentration in the reaction mixture in combination with this high energetic barrier limits the potential of this reaction. In conclusion, water can be utilized as a nucleophile in isomerizing functionalization reactions and gives access to long-chain dicarboxylic acids from a variety of unsaturated substrates. The activity of the catalytic

  20. Isomeric States in the Second and Third Well of the Potential and Long-Lived Superheavy Element

    International Nuclear Information System (INIS)

    Marinov, A.; Gelberg, S.; Kolb, D.

    1999-01-01

    Recently, in a study of the 16 O + 197 Au and 28 Si + 181 Ta reactions near and below the Coulomb barrier, long-lived high spin isomeric states have been found by us in the second and third well of the potential-energy surfaces. Such isomeric states have very unusual physical properties. In addition to their very long lifetimes, much longer than of their corresponding ground states, they have very unusual decay properties. They may decay by 5 to 7 orders of magnitude enhanced alpha particles, in transitions from the second or third well of the potential in the parent nuclei to the respective well in the daughters, or by very retarded alpha particles, in transitions from the second well in the parent nucleus to normal states in the daughter, or from the third well in the parent to the second well in the daughter. They also may decay by long-lived proton activities, in transitions from the second well in the parent nucleus to the normal states in the daughter. Experimental evidences for all these new phenomena will be presented in the conference. The existence of long-lived isomeric states in the second and third well of the potential is very important when the production of superheavy elements is considered. Because of the very much reduced extra-push energy needed for their production, they may be produced much easier than the normal states, in reactions between very heavy nuclei. In particular, the discovery of the long-lived superheavy element with Z = 112 can consistently be understood

  1. Comparison of Separation of Seed Oil Triglycerides Containing Isomeric Conjugated Octadecatrienoic Acid Moieties by Reversed-Phase HPLC

    Directory of Open Access Journals (Sweden)

    Anh Van Nguyen

    2017-12-01

    Full Text Available Relative retention analysis and increment approach were applied for the comparison of triglycerides (TGs retention of a broad set of plant seed oils with isomeric conjugated octadecatrienoic acids (CLnA by reversed-phase HPLC for “propanol-2-acetonitrile” mobile phases and Kromasil 100-5C18 stationary phase with diode array detection (DAD and mass spectrometric (MS detection. The subjects of investigation were TGs of seed oils: Calendula officinalis, Catalpa ovata, Jacaranda mimosifolia, Centranthus ruber, Momordica charantia, Trichosanthes anguina, Punica granatum, Thladiantha dubia, Valeriana officinalis, and Vernicia montana. It was found that a sequence of elution of TGs of the same types is the same without any inversions for full range of mobile phase compositions: punicic (C18:39Z11E13Z < jacaric (C18:38Z10E12Z < catalpic (C18:39E11E13Z < α-eleostearic (C18:39Z11E13E < calendic (C18:38E10E12Z < β-eleostearic (C18:39E11E13E < all-E calendic (C18:38E10E12E acids. TGs and fatty acid compositions were calculated for all oil samples. Regularities of solute retentions as a function of isomeric conjugated octadecatrienoic acid moiety structure are discussed. Thus, it was proven that it is possible to differentiate TGs of complex composition with moieties of all natural CLnA by retention control accomplished by electronic spectra comparison, even though there are only three types of electronic-vibration spectra for seven isomeric CLnA.

  2. 48 CFR 52.236-11 - Use and Possession Prior to Completion.

    Science.gov (United States)

    2010-10-01

    ... possession or use shall not be deemed an acceptance of any work under the contract. (b) While the Government... adjustment shall be made in the contract price or the time of completion, and the contract shall be modified...

  3. Schizophrenia-The spirit possessed 23 year old male from rural ...

    African Journals Online (AJOL)

    A case of a twenty-three year old rural Ghanaian male suffering from schizophrenia and presenting as “possessed by spirits” is reported. Treatment, and outcome by physical means with chlorpromazine; and implications for further research are discussed.

  4. 32 CFR 552.122 - Personnel not authorized to possess or retain personal weapons.

    Science.gov (United States)

    2010-07-01

    ... THE ARMY MILITARY RESERVATIONS AND NATIONAL CEMETERIES REGULATIONS AFFECTING MILITARY RESERVATIONS... person who has been convicted in any court of the possession, use, or sale of marijuana, dangerous or...

  5. Feature interpretability and the positions of 2nd person possessives in Brazilian Portuguese

    Directory of Open Access Journals (Sweden)

    Bruna Karla Pereira

    2016-12-01

    Full Text Available Interpretability and valuation of φ-features (Chomsky, 2001; Pesetsky and Torrego, 2007 have played a central role in the investigation of language universals. With regard to that, in standard Brazilian Portuguese (BP, as well as in other Romance languages, possessives have uninterpretable number features, which are valued via nominal agreement. However, dialects of BP, especially the one spoken in Minas Gerais, have shown that 2nd person possessives, in postnominal position, do not have number agreement with the noun. In order to account for these facts, I will argue that, in this grammar, number features on 2nd person possessives are reanalyzed as being: (i associated with the person (rather than the noun and (ii interpretable. From the first postulation, ‘seu’ is expected to be the possessive for 2nd person singular, and ‘seus’ for 2nd person plural. From the second postulation, no number concord is expected to be triggered on the possessive. In addition, based on Danon (2011 and Norris (2014, I will argue that cardinals divide BP DPs into two domains in that phrases located above NumP are marked with the plural morpheme, while phrases below it are unmarked. In this sense, because prenominal possessives precede cardinals (NumP, they must be marked with the plural morpheme for nominal agreement; whereas postnominal possessives, which follow NumP, must be unmarked. Free from the plural marking associated with nominal agreement, postnominal 2nd person possessives favor the reanalysis of the morpheme ‘-s’ as indicating the number associated with person features.

  6. Probing the Single-Particle Character of Rotational States in F 19 Using a Short-Lived Isomeric Beam

    Science.gov (United States)

    Santiago-Gonzalez, D.; Auranen, K.; Avila, M. L.; Ayangeakaa, A. D.; Back, B. B.; Bottoni, S.; Carpenter, M. P.; Chen, J.; Deibel, C. M.; Hood, A. A.; Hoffman, C. R.; Janssens, R. V. F.; Jiang, C. L.; Kay, B. P.; Kuvin, S. A.; Lauer, A.; Schiffer, J. P.; Sethi, J.; Talwar, R.; Wiedenhöver, I.; Winkelbauer, J.; Zhu, S.

    2018-03-01

    A beam containing a substantial component of both the Jπ=5+ , T1 /2=162 ns isomeric state of F 18 and its 1+, 109.77-min ground state is utilized to study members of the ground-state rotational band in F 19 through the neutron transfer reaction (d ,p ) in inverse kinematics. The resulting spectroscopic strengths confirm the single-particle nature of the 13 /2+ band-terminating state. The agreement between shell-model calculations using an interaction constructed within the s d shell, and our experimental results reinforces the idea of a single-particle-collective duality in the descriptions of the structure of atomic nuclei.

  7. Isomerization of α-pinene in the terpentin oil with TCA/Natural Zeolite using microwave irradiation

    Science.gov (United States)

    Wijayati, N.; Supartono; Kusumastuti, E.

    2018-04-01

    The catalytic potensial of trichloroacetic acid (TCA)//Natural Zeolite in the isomerization of α-pinene in the terpentin oil was investigated. The purpose of this study is to investigate the influence of the power of microvawe on activity and selectivity of catalyst. The main product were champhene, terpinene, limonene, p-cymene, and terpinolene. The highest selectivity was 28.26% with a conversion of 23.25%, whereas the higher conversion was 98.99% with selectivity of 16.90% at room temperature using power of microwave 640 W.

  8. Biofuel by isomerizing metathesis of rapeseed oil esters with (bio)ethylene for use in contemporary diesel engines.

    Science.gov (United States)

    Pfister, Kai F; Baader, Sabrina; Baader, Mathias; Berndt, Silvia; Goossen, Lukas J

    2017-06-01

    Rapeseed oil methyl ester (RME) and (bio)ethylene are converted into biofuel with an evenly rising boiling point curve, which fulfills the strict boiling specifications prescribed by the fuel standard EN 590 for modern (petro)diesel engines. Catalyzed by a Pd/Ru system, RME undergoes isomerizing metathesis in a stream of ethylene gas, leading to a defined olefin, monoester, and diester blend. This innovative refining concept requires negligible energy input (60°C) and no solvents and does not produce waste. It demonstrates that the pressing challenge of increasing the fraction of renewables in engine fuel may be addressed purely chemically rather than by motor engineering.

  9. O olhar dos psiquiatras brasileiros sobre os fenômenos de transe e possessão Brazilian psychiatrists’ approaches on trance and possession phenomena

    Directory of Open Access Journals (Sweden)

    Angélica A. Silva de Almeida

    2007-01-01

    Full Text Available CONTEXTO: Os fenômenos de transe e possessão despertaram o interesse da comunidade psiquiátrica brasileira, gerando posturas diversificadas. OBJETIVOS: Descrever e analisar como os fenômenos de transe e possessão foram tratados pelos psiquiatras brasileiros: seu impacto na teoria, na pesquisa e na prática clínica entre 1900 e 1950. MÉTODO: Análise de artigos científicos e leigos, teses e livros sobre transes e possessões produzidos pelos psiquiatras brasileiros entre 1900 e 1950. RESULTADOS: Identificam-se duas correntes de pensamento entre os psiquiatras. A primeira, vinculada às Faculdades de Medicina do Rio de Janeiro e São Paulo, sob forte influência de autores franceses, deteve-se mais na periculosidade do espiritismo para a saúde mental. Defendia a adoção de medidas repressivas com o poder público. O segundo grupo de psiquiatras, ligado às Faculdades de Medicina da Bahia e Pernambuco, embora não desconsiderasse o caráter patológico ou "primitivo" dos fenômenos de transe e possessão, apresentou uma visão mais antropológica e culturalista. Considerando tais fenômenos como manifestações étnicas ou culturais, alguns defenderam o controle médico e a educação do povo para o abandono dessas práticas "primitivas". Outros não consideravam os fenômenos mediúnicos como desencadeadores da loucura, mas manifestações não-patológicas de um universo cultural, além de não vinculá-los ao atraso cultural da população. CONCLUSÕES: As religiões mediúnicas foram objeto de estudo por longo período, resultando hipóteses e práticas diferenciadas por parte da comunidade psiquiátrica brasileira, constituindo-se oportunidade privilegiada para o estudo do impacto dos fatores socioculturais na atividade psiquiátrica.BACKGROUND: Trance and possession experiences have raised interest among Brazilian psychiatrists resulting in a variety of approaches. OBJECTIVES: To describe and analyze how Brazilian psychiatrists

  10. Co-possession of phosphodiesterase type-5 inhibitors (PDE5-I) with nitrates.

    Science.gov (United States)

    Chang, Li-Ling; Ma, Mark; Allmen, Heather von; Henderson, Scott C; Harper, Kristine; Hornbuckle, Kenneth

    2010-06-01

    Estimate the proportion of phosphodiesterase type-5 inhibitor (PDE5-I) patients who co-possess nitrates and compare the proportion of tadalafil patients dispensed nitrates to a matched control group. Secondarily, examine the percentage of co-possession of PDE5-Is and nitrates where the products were dispensed on the same day or written by the same prescriber. Male patients aged 18+ years filling PDE5-I prescriptions between December 2003 and March 2006 were identified using a U.S. longitudinal prescription database (IMS Health LRx). Similar patients not dispensed a PDE5-I during this period were matched to the tadalafil-dispensed cohort using a propensity score approach. Co-possession, as a proxy for concurrent use, was defined as an overlap in time on therapy for a PDE5-I and nitrate and was compared for the three PDE5-Is and for tadalafil to the matched control group. Among 601,063 tadalafil patients, 3.31% were dispensed a nitrate during the study period, compared to 6.18% in control patients (n = 601,063). When co-possessed prescriptions were defined by overlapping exposure periods, the proportion of PDE5-I patients with co-possessed nitrates ranged from 1.44% (tadalafil) to 1.72% (vardenafil) and 2.13% (sildenafil). Co-possession percentages of PDE5-I prescriptions were 0.83% for tadalafil and 1.07% for sildenafil and vardenafil. The majority (54.29%) of co-possessed PDE5-I and nitrate prescriptions had the nitrate dispensed prior to the PDE5-I prescription identified in the study cohort. Keeping in mind the limitations of observational studies, these results suggest that co-dispensing of nitrates and PDE5-Is is low. Compared to control patients, the proportion of nitrate co-possession was lowest for patients filling tadalafil. Tadalafil patients also had the lowest co-possessed proportion among the three PDE5-I cohorts. While the majority of co-possessed drug pairs were prescribed by different providers, the highest percentage of co-prescribing from the same

  11. The influence of constitutional isomerism and change on molecular recognition processes.

    Science.gov (United States)

    Williams, Avril R; Northrop, Brian H; Houk, Kendall N; Stoddart, J Fraser; Williams, David J

    2004-10-25

    Three constitutionally isomeric bis(naphthylmethyl)ammonium ions, in which the two naphthyl groups are substituted 1) both at their 1-positions, 2) one at its 1-position and the other at its 2-position, and 3) both at their 2-positions, have been investigated separately in solution for their propensities to undergo spontaneous self-assembly with three different [24]crown-8 derivatives, namely, pyrido[24]crown-8 (P24C8), dipyrido[24]crown-8 (DP24C8) and dibenzo[24]crown-8 (DB24C8), in turn to form [2]pseudorotaxanes. The strengths of the 1:1 complexes depend on the composition of the secondary dialkylammonium ions and on the nature of the crown ether hosts; generally, as far as the guest cation is concerned, the 1/1- and 2/2-isomers form stronger complexes, as indicated by stability constant measurements, than the 1/2-isomer and, as far as the crown ethers are concerned, the more flexible P24C8 is a much more efficient host than either DP24C8 or DB24C8. The rates of formation of the [2]pseudorotaxanes are fast (i.e., taking no more than a few minutes) in solution with the exception of one case, that is, in which the crown ether host is DB24C8 and the guest cation is the 1/1-isomer, when it can take upwards of one month for the complexation-decomplexation equilibrium to be established at room temperature. In all cases, the equilibrium between complexed and uncomplexed species is slow on the NMR timescale, allowing the determination of stability constants to be made readily using the single-point method. X-ray crystallography and molecular modeling have been used to gain insight into ground and transition state interactions, respectively, in some of the [2]pseudorotaxanes. The relative stabilities of the three [2]pseudorotaxanes formed by each guest cation in the presence of the three crown ether hosts were also evaluated in solution by competition experiments that were monitored by (1)H NMR spectroscopy. By and large the results of the competition experiments could

  12. Effects of Weak Intermolecular Interactions on the Molecular Isomerism of Tricobalt Metal Chains

    International Nuclear Information System (INIS)

    Poulsen, R.; Overgaard, J.; Schulman, A.; Stergaard, C.; Murillo, C.; Spackman, M.; Iversen, B.

    2009-01-01

    Depending on the number of interstitial solvent molecules, n, crystals of the linear chain compound Co3(dipyridylamide)4Cl2·nCH2Cl2 adopt either symmetrical or unsymmetrical metal chain structures. We explore here the possible reasons for such behavior using Hirshfeld surface analysis of intermolecular interactions as well as the charge density determined from 100(1) K X-ray diffraction data on the unsymmetrical complex Co3(dipyridylamide)4Cl2·2.11CH2Cl2, u-1, and crystal structures of u-1 determined from single crystal synchrotron X-ray diffraction data at 20, 150, and 300 K. The new crystal structures are compared with previous structural results on a crystal with slightly different solvent content. This change in solvent content only affects the bond distances to atom Co(3), which are also strongly affected by temperature changes due to a spin crossover transition. Large differences in intermolecular interactions are revealed by the Hirshfeld surface analysis between symmetrical (s-1) and unsymmetrical (u-1) crystal solvates, suggesting that the molecular isomerism is strongly influenced by crystal packing effects. Topological analysis of the static electron density of u-1 suggests that there is direct metal-metal bonding for both the shorter Co(1)-Co(2) and the longer Co(2)-Co(3) contact. The approximate description of the system as a (Co2)2+-dimer and an isolated Co2+-ion is reflected in the character of the metal-ligand interactions, which are more ionic for the isolated Co(3) atom, and the topological charges Co(1)+0.50, Co(2)+0.77, and Co(3)+1.36. The two termini of u-1 are found to be very different, both in terms of structural surroundings as well as topology. The central Co(2) atom is similar to a cobalt atom in a tetragonally distorted octahedral environment resulting in preferred occupancy in the t2g orbitals. The Co(1) atom has significant deformation in the xz and yz planes (z along the chain axis, x and y toward ligands) reflecting covalent

  13. Ruthenium Hydride/Brønsted Acid-Catalyzed Tandem Isomerization/N-Acyliminium Cyclization Sequence for the Synthesis of Tetrahydro-β-carbolines

    DEFF Research Database (Denmark)

    Hansen, Casper Lykke; Clausen, Janie Regitse Waël; Ohm, Ragnhild Gaard

    2013-01-01

    This paper describes an efficient tandem sequence for the synthesis of 1,2,3,4-tetrahydro-β-carbolines (THBCs) relying on a ruthenium hydride/Brønsted acid- catalyzed isomerization of allylic amides to N-acyliminium ion intermediates which are trapped by a tethered indolenucleophile. The methodol...... the Suzuki cross-coupling reaction to the isomerization/N-acyliminium cyclization sequence. Finally, diastereo- and enantioselective versions of the title reaction have been examined using substrate control (with dr >15: 1) and asymmetric catalysis (ee up to 57%), respectively...

  14. Synthesis of zeolite-zeolite (mfi-fau) composite catalysts for the isomerization of n-hexane

    International Nuclear Information System (INIS)

    Ghouri, A.S; Usman, M.R.

    2017-01-01

    In this research work, the aim is to produce a relatively novel zeolite-zeolite (MFI-FAU) composite catalyst having better potential of catalyzing isomerization of lighter hydrocarbons such as light naphtha, n-pentane, n-hexane, n-heptane and mixture thereof. A series of zeolite-zeolite (MFI-FAU) composite catalysts have been synthesized by incorporating previous practices and techniques. The catalytic performance of as-synthesized zeolite-zeolite (MFI-FAU) composite catalysts have been investigated by isomerizing 95% pure n-hexane in conventional fixed bed flow micro-reactor at temperature 200-240 ºC under atmospheric pressure. In order to explore chemical and physical features of zeolite-zeolite (MFI-FAU) composite catalysts, they are examined and characterized using powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectrometry (EDX), N2 adsorption-desorption measurements (BET, BJH, t-plot measurements) and Fourier transform infrared (FTIR) spectroscopy equipped with attenuated total reflectance (ATR) arrangements. (author)

  15. Acidic ionic liquids for n-alkane isomerization in a liquid-liquid or slurry-phase reaction mode

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, C.; Hager, V.; Geburtig, D.; Kohr, C.; Wasserscheid, P. [Erlangen-Nuernberg Univ. (Germany). Lehrstuhl fuer Chemische Reaktionstechnik; Haumann, M. [Chemical Reaction Engineering, FAU Busan Campus, Korea (Korea, Republic of)

    2011-07-01

    Highly acidic ionic liquid (IL) catalysts offer the opportunity to convert n-alkanes at very low reaction temperatures. The results of IL catalyzed isomerization and cracking reactions of pure n-octane are presented. Influence of IL composition, [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / H{sub 2}SO{sub 4} and [C{sub 4}C{sub 1}Im]Cl / AlCl{sub 3} / 1-chlorooctane, on catalyst activity and selectivities to branched alkanes was investigated. Acidic chloroaluminate IL catalysts form liquid-liquid biphasic systems with unpolar organic product mixtures. Thus, recycling of the acidic IL is enabled by simple phase separation in the liquid-liquid biphasic reaction mode or the IL can be immobilized on an inorganic support with a large specific surface area. These supported ionic liquid phase (SILP) catalysts offer the advantage to get a macroscopically heterogeneous system while still preserving all benefits of the homogeneous catalyst which can be used for the slurry-phase n-alkane isomerization. The interaction of the solid support and acidic IL influences strongly the catalytic activity. (orig.)

  16. General and Facile Route to Isomerically Pure Tricyclic Peptides Based on Templated Tandem CLIPS/CuAAC Cyclizations.

    Science.gov (United States)

    Richelle, Gaston J J; Ori, Sumeet; Hiemstra, Henk; van Maarseveen, Jan H; Timmerman, Peter

    2018-01-08

    We report a one-pot ligation/cyclization technology for the rapid and clean conversion of linear peptides into tricyclic peptides that is based on using tetravalent scaffolds containing two benzyl bromide and two alkyne moieties. These react via CLIPS/CuAAC reactions with cysteines and azides in the peptide. Flexibility in the scaffolds is key to the formation of isomerically pure products as the flexible scaffolds T4 1 and T4 2 mostly promote the formation of single isomeric tricycles while the rigid scaffolds T4 3 and T4 4 do not yield clean products. There seems to be no limitation to the number and types of amino acids present as 18 canonical amino acids were successfully implemented. We also observed that azides at the peptide termini and cysteine residues in the center gave better results than compounds with the functional groups placed the other way round. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Half-lives of ground and isomeric states in {sup 97}Cd and the astrophysical origin of {sup 96}Ru

    Energy Technology Data Exchange (ETDEWEB)

    Lorusso, G., E-mail: lorusso@ribf.riken.j [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Joint Institute for Nuclear Astrophysics, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Becerril, A.; Amthor, A. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Joint Institute for Nuclear Astrophysics, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Baumann, T.; Bazin, D. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Berryman, J.S. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States); Brown, B.A. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Joint Institute for Nuclear Astrophysics, Michigan State University, East Lansing, MI 48824 (United States); Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States); Cyburt, R.H. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Joint Institute for Nuclear Astrophysics, Michigan State University, East Lansing, MI 48824 (United States); Crawford, H.L. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States)

    2011-05-09

    First experimental evidence for a high-spin isomer (25/2{sup +}) in {sup 97}Cd, a waiting point in the astrophysical rapid proton capture process, is presented. The data were obtained in {beta}-decay studies at NSCL using the new RF Fragment Separator system and detecting {beta}-delayed protons and {beta}-delayed {gamma} rays. Decays from ground and isomeric states were disentangled, and proton emission branches were determined for the first time. We find half-lives of 1.10(8) s and 3.8(2) s, and {beta}-delayed proton emission branches of 12(2)% and 25(4)% were deduced for the ground and isomeric states, respectively. With these results, the nuclear data needed to determine an rp-process contribution to the unknown origin of solar {sup 96}Ru are in place. When the new data are included in astrophysical rp-process calculations, one finds that an rp-process origin of {sup 96}Ru is unlikely.

  18. Multi-arrangement quantum dynamics in 6D: cis-trans isomerization and 1,3-hydrogen transfer in HONO

    International Nuclear Information System (INIS)

    Luckhaus, David

    2004-01-01

    The overtone spectrum and wave packet dynamics of nitrous acid (HONO) are studied with a global six-dimensional potential energy function interpolated directly from density functional calculations together with the corresponding dipole hypersurfaces. The quantum dynamics for the cis-trans isomerization and the symmetric 1,3-hydrogen transfer are treated in full dimensionality in terms of the generalized Z-matrix discrete variable representation. For the quantum mechanical description of complicated rearrangements a new approach to multi-arrangement quantum dynamics is introduced and applied to the symmetric hydrogen exchange tunneling in cis-HONO. The cis-trans isomerization is found to be dominated by adiabatic barrier crossing with only minor tunneling contributions, but with pronounced mode selectivity. The OH-stretching overtones of trans-HONO are adiabatically almost completely separated from the OH torsional dynamics with extremely slow intramolecular energy redistribution. The 1,3-hydrogen transfer, by contrast, proceeds largely via coherent tunneling even significantly below the barrier. The process is clearly non-adiabatic (at least in terms of valence coordinates) but remains highly state specific. While the absorption spectrum of trans-HONO remains largely unaffected, OH-stretching overtones of cis-HONO (above the barrier between 2ν OH and 3ν OH ) decompose into highly fragmented absorption patterns with corresponding tunneling periods on the picosecond time scale

  19. Along the N=126 closed shell: study of $^{205}$Au through its $\\pi h_{11/2}^{-1}$ isomeric decay

    CERN Multimedia

    2002-01-01

    Excited states have been identified in only three of the N=126 closed shell nuclei 'below' $^{208}$Pb, $^{207}$Tl, $^{206}$Hg and very recently $^{204}$Pt. We aim to extend our knowledge of the neutron-rich N=126 nuclei by observing the internal decay of the $\\pi h^{-1}_{11/2}$ excited state in $^{205}$Au, which is expected to be isomeric. In addition, the decay of the analogous states in the N=122 and N=124 $^{201,203}$Au will be studied. The lifetimes of the expected isomeric states are crucial for the success of the experiment, and they are estimated to be in the range of 0.3-20 s. These are long enough to enable the extraction from the source, but shorter than the $\\beta$-decay half-lives. Proton single-particle energies and transition rates will be extracted, providing information about the robustness of the N=126 shell-closure. Three days of beam-time is requested.

  20. Hydrotreating NiMo/sepiolite catalysts: influence of catalyst preparation on activity for HDS, hydrogenation and chain isomerization reactions

    International Nuclear Information System (INIS)

    Melo, F.V.; Sanz, E.; Corma, A.; Mifsud, A.

    1987-01-01

    A series of NiMo catalysts supported on a sepiolite: a) in its natural state, b) modified by acid leaching, and c) modified by cation exchange, have been prepared. The preparation variables studied were: Method of metal deposition, amount of active phase, sepiolite pretreatment, and temperature and time of sulfurization. The catalytic activity for HDS, hydrogenation, and cracking-isomerization has been studied by feeding a thiophene-cyclohexene-cyclohexane mixture and carrying out the reaction in the following conditions: 300 0 and 400 0 C reaction temperature, 20 Kg.cm -2 total pressure, and 3 to 1 molar ratio of H 2 to hydrocarbons. An optimium for HDS and hydrogenation activity was found for a 12% wt MoO 3 , and 5% wt NiO, prepared by simultaneous impregnation by the pore volume method at Ph = 5.0. The optimum conditions with these catalysts are 400 0 C and 3 hours of sulfurization. An increase in the acidity of the support produces a decrease of HDS and hydrogenation and an increase of the cracking-isomerization activities. A good correlation between HDS and the concentration of an XNiO.MoO 3 phase is found. The XNiO.MoO 3 phase is completely sulfurized to a modified MoS 2 , while NiMoO 4 and MoO 3 are only slightly sulfurized. 31 refs.; 7 figs.; 1 table

  1. Synthesis, crystal structure and photo physical properties of isomeric fluorinated s-shaped polyaromatic dibenzo[c,l]chrysene derivatives

    Science.gov (United States)

    Moriguchi, Tetsuji; Tabuchi, Daichi; Yakeya, Daisuke; Tsuge, Akihiko; Jalli, Venkataprasad; Yoza, Kenji

    2018-01-01

    Two s-shaped fluorinated isomeric polyaromatic dibenzo[c,l]chrysene derivatives have been synthesized by a two step process using the Wittig, Heck and iodine promoted cyclization reactions. These cyclized compounds were characterized by 1H NMR and EI-MS. Further, absolute configurations of isomeric 4a and 4b were determined by X-ray diffraction analysis. Compound 4a crystallized under monoclinic system with space group P21/c and compound 4b crystallized under monoclinic system with space group Cc. They have good solubility in common organic solvents such as dichloromethane, chloroform and THF. Photophysical properties of 4a and 4b were evaluated by using UV-Visible and Fluorescence spectrophotometer. Compounds 4a and 4b showed strong absorption maximum wavelength at 317 nm. The emission spectra of 4a and 4b displayed sharp peaks in the visible region from 417 to 441 nm. The shape of the UV-Visible and Fluorescence spectra of 4a and 4b looks almost identical. But compound 4a exhibited better fluorescence intensity than compound 4b. This difference may be due to the difference in the configuration of compounds 4a and 4b.

  2. Use of Isomerization and Hydroisomerization Reactions to Improve the Cold Flow Properties of Vegetable Oil Based Biodiesel

    Directory of Open Access Journals (Sweden)

    Stephen J. Reaume

    2013-01-01

    Full Text Available Biodiesel is a promising alternative to petroleum diesel with the potential to reduce overall net CO2 emissions. However, the high cloud point of biodiesel must be reduced when used in cold climates. We report on the use of isomerization and hydroisomerization reactions to reduce the cloud point of eight different fats and oils. Isomerization was carried out at 260 °C and 1.5 MPa H2 pressure utilizing beta zeolite catalyst, while hydroisomerization was carried out at 300 °C and 4.0 MPa H2 pressure utilizing 0.5 wt % Pt-doped beta zeolite catalyst. Reaction products were tested for cloud point and flow properties, in addition to catalyst reusability and energy requirements. Results showed that high unsaturated fatty acid biodiesels increased in cloud point, due to the hydrogenation side reaction. In contrast, low unsaturated fatty acid biodiesels yielded cloud point reductions and overall improvement in the flow properties. A maximum cloud point reduction of 12.9 °C was observed with coconut oil as the starting material. Results of the study have shown that branching can reduce the cloud point of low unsaturated fatty acid content biodiesel.

  3. An Investigation of the Enolization and Isomeric Products Distribution in the Water Promoted Aldol Reaction of Tropinone and Granatanone

    Directory of Open Access Journals (Sweden)

    Ryszard Lazny

    2016-01-01

    Full Text Available The exo,anti/exo,syn-diastereoselectivity of water promoted direct aldol reactions of tropinone and granatanone (pseudopelletierine is strongly dependent on the amount of water added and aromatic aldehyde used. DFT methods were applied to calculate the free energies of tropinone and granatanone enols, transition states, and isomeric aldol products. A theoretical model was verified by comparison of results from several DFT methods and functionals with experiments. The 6-31g(d/CPCM method proved most suited to the problem, although all methods tested predicted similar trends. Explicit inclusion of a water molecule bonded to the amino ketones resulted in increased stability of the enol forms. The dependence of the anti/syn-diastereoselectivity on the amount of water used may be rationalized on the basis of change in the polarity of the reaction medium. The predicted stabilities of competing products agreed with experimental results supporting the notion of thermodynamic control. The isomeric products distributions for the aldol reaction of several aromatic aldehydes in solventless (neat conditions were accurately calculated from free energies of the aldol addition step in the gas phase using B3LYP/6-31g(d method and in aqueous conditions using the CPCM-B3LYP/6-31g(d model. Our methodology can be useful for predicting the outcome of this type of aldol reactions.

  4. Isomerization of 2-butene-1,4-diol in aqueous solutions catalyzed by palladium(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kalabin, S.M.; Novikov, N.A.; Belov, A.P.

    1989-02-01

    The authors studied the isomerization of 2-butene-1,4-diol into 3-butene-1,2-diol at 18-25/degree/C. The concentrations of the diol and PdCl/sub 2/ were (1.0-5.0) /times/ 10/sup /minus/2/ mole/liter at 5-10-fold excess amounts of HCl and NaCl. These additives were used because of their inhibiting action on the oxidation of olefinic compounds. 3-Butene-1,2-diol was identified by /sup 1/H NMR method directly in the reaction solutions in which the reaction solutions in which the reactions in D/sub 2/O were carried out. It was found that palladium(II) complexes catalyze the isomerization of 2-butene-1,4-diol into 3-butene-1,2-diol. A mechanism is proposed for the reaction, which includes the intermediate formation of /eta//sup 3/-allyl complex of palladium with a coordinated hydroxyl group.

  5. Investigating the Impact of Possession-Way of a Smartphone on Action Recognition

    Directory of Open Access Journals (Sweden)

    Zae Myung Kim

    2016-06-01

    Full Text Available For the past few decades, action recognition has been attracting many researchers due to its wide use in a variety of applications. Especially with the increasing number of smartphone users, many studies have been conducted using sensors within a smartphone. However, a lot of these studies assume that the users carry the device in specific ways such as by hand, in a pocket, in a bag, etc. This paper investigates the impact of providing an action recognition system with the information of the possession-way of a smartphone, and vice versa. The experimental dataset consists of five possession-ways (hand, backpack, upper-pocket, lower-pocket, and shoulder-bag and two actions (walking and running gathered by seven users separately. Various machine learning models including recurrent neural network architectures are employed to explore the relationship between the action recognition and the possession-way recognition. The experimental results show that the assumption of possession-ways of smartphones do affect the performance of action recognition, and vice versa. The results also reveal that a good performance is achieved when both actions and possession-ways are recognized simultaneously.

  6. Gun possession among American youth: a discovery-based approach to understand gun violence.

    Science.gov (United States)

    Ruggles, Kelly V; Rajan, Sonali

    2014-01-01

    To apply discovery-based computational methods to nationally representative data from the Centers for Disease Control and Preventions' Youth Risk Behavior Surveillance System to better understand and visualize the behavioral factors associated with gun possession among adolescent youth. Our study uncovered the multidimensional nature of gun possession across nearly five million unique data points over a ten year period (2001-2011). Specifically, we automated odds ratio calculations for 55 risk behaviors to assemble a comprehensive table of associations for every behavior combination. Downstream analyses included the hierarchical clustering of risk behaviors based on their association "fingerprint" to 1) visualize and assess which behaviors frequently co-occur and 2) evaluate which risk behaviors are consistently found to be associated with gun possession. From these analyses, we identified more than 40 behavioral factors, including heroin use, using snuff on school property, having been injured in a fight, and having been a victim of sexual violence, that have and continue to be strongly associated with gun possession. Additionally, we identified six behavioral clusters based on association similarities: 1) physical activity and nutrition; 2) disordered eating, suicide and sexual violence; 3) weapon carrying and physical safety; 4) alcohol, marijuana and cigarette use; 5) drug use on school property and 6) overall drug use. Use of computational methodologies identified multiple risk behaviors, beyond more commonly discussed indicators of poor mental health, that are associated with gun possession among youth. Implications for prevention efforts and future interdisciplinary work applying computational methods to behavioral science data are described.

  7. Demonic possessions and mental illness: discussion of selected cases in late medieval hagiographical literature.

    Science.gov (United States)

    Espí Forcén, Carlos; Espí Forcén, Fernando

    2014-01-01

    During the Middle Ages, demonic possession constituted an explanation for an erratic behavior in society. Exorcism was the treatment generally applied to demoniacs and seems to have caused some alleviation in the suffering of mentally distressed people. We have selected and analyzed some cases of demonic possession from thirteenth-century hagiographical literature. In the description of demoniacs we have been able to find traits of psychotic, mood, neurotic, personality disorders and epilepsy. The exorcisms analyzed in our article are the result of literary invention more than the description of a contemporary event. Nevertheless, the writers were witnesses of their time, transferred their knowledge about exorcism and possession in their narrative and presumably incorporated their actual experience with demoniacs.

  8. Prepositions in Use: Prepositions of Standard, Prepositions of Possession and Prepositions of Accompaniment

    Directory of Open Access Journals (Sweden)

    Naji Masned AlQbailat

    2016-08-01

    Full Text Available The current research paper attempted at investigating the use of prepositions of standard, prepositions of possession and prepositions of accompaniment by some Jordanian learners of English. A total of 53 Jordanian English Majors participated in the study from the department of English language at Princess Alia University College. In collecting the needed data for the purpose of the study, the researchers employed fifteen items of a multiple choice test. The results of the study showed that Jordanian learners of English encountered moderate difficulty in learning the three aforesaid usages of prepositions. This difficulty is ascribed mainly to first language interference more than intralingual interference. It was also found that prepositions of standard are the most difficult to learn by the participants, followed by prepositions of accompaniment and prepositions of possession respectively.       Keywords: First language Interference, Intralingual Interference, Prepositions of Standard, Prepositions of Accompaniment, Prepositions of Possession

  9. Does possession of assets increase women's participation in reproductive decision-making? Perceptions of Nigerian women.

    Science.gov (United States)

    Omeje, Joachim C; Oshi, Sarah N; Oshi, Daniel C

    2011-01-01

    This study is based on a population-based, descriptive questionnaire survey, the objective of which was to elicit the perceptions of women in south-eastern Nigeria on whether possession of economic/household assets by women enhanced their capacity to negotiate reproductive issues with their husbands. The findings show that the respondents believed that possession of economic/household assets by women in their communities might not necessarily increase their negotiation power in their reproductive decision-making. Other factors tend to attenuate the effects of women's possession of economic/household assets on their reproductive bargaining power. Notable among these may be social norms that implicitly arrogate control of the assets owned by the conjugal couple to the man, even when they are bought by the women. Planners of reproductive health intervention projects, policy-makers and researchers need to be aware of such sociocultural specific phenomena, which do not fit with widely held international beliefs.

  10. Rulings in Argentinean and Colombian courts decriminalize possession of small amounts of narcotics.

    Science.gov (United States)

    Cozac, David

    2009-12-01

    Two recent court decisions in South America have reflected a growing backlash in the region against the so-called, U.S.-led "war on drugs". In Argentina, the Supreme Court of Justice ruled unanimously on 25 August 2009 that the second paragraph of Article 14 of the country's drug control legislation, which punishes the possession of drugs for personal consumption, was unconstitutional. In Colombia, the Supreme Court of Justice ruled on 8 July 2009 that the possession of illegal drugs for personal use was not a criminal offence.

  11. Transient-Absorption Spectroscopy of Cis-Trans Isomerization of N,N-dimethyl-4,4'-Azodianiline with 3D-Printed Temperature-Controlled Sample Holder

    Science.gov (United States)

    Kosenkov, Dmytro; Shaw, James; Zuczek, Jennifer; Kholod, Yana

    2016-01-01

    The laboratory unit demonstrates a project based approach to teaching physical chemistry laboratory where upper-division undergraduates carry out a transient-absorption experiment investigating the kinetics of cis-trans isomerization of N,N-dimethyl-4,4'-azodianiline. Students participate in modification of a standard flash-photolysis spectrometer…

  12. Surface Collisions of the Acetonitrile Molecular Ion: Evidence for Isomerization of CD3CN center dot+ to the Ketenimine Cation CD2=C=ND center dot+

    Czech Academy of Sciences Publication Activity Database

    Mair, C.; Roithová, Jana; Fedor, J.; Lezius, M.; Herman, Zdeněk; Märk, T. D.

    223-224, 1/3 (2003), s. 279-290 ISSN 1387-3806 R&D Projects: GA ČR GA203/00/0632 Institutional research plan: CEZ:AV0Z4040901 Keywords : acetonitrile cation * surface reactions * isomerization Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.361, year: 2003

  13. From laboratory catalysts to a new prototype: a novel real candidate for the isomerization of C5–C6 paraffins

    Czech Academy of Sciences Publication Activity Database

    Hidalgo, J. M.; Kaucký, Dalibor; Bortnovsky, O.; Černý, R.; Sobalík, Zdeněk

    2015-01-01

    Roč. 5, JUN 2015 (2015), s. 56625-56628 ISSN 2046-2069 R&D Projects: GA MPO FR-TI3/316 Institutional support: RVO:61388955 Keywords : C5-C6 paraffins * isomeration * Pt/WO3–ZrO2 materials Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.289, year: 2015

  14. Bicyclic Guanidine Catalyzed Asymmetric Tandem Isomerization Intramolecular-Diels-Alder Reaction: The First Catalytic Enantioselective Total Synthesis of (+)-alpha-Yohimbine.

    Science.gov (United States)

    Feng, Wei; Jiang, Danfeng; Kee, Choon-Wee; Liu, Hongjun; Tan, Choon-Hong

    2016-02-04

    Hydroisoquinoline derivatives were prepared in moderate to good enantioselectivities via a bicyclic guanidine-catalyzed tandem isomerization intramolecular-Diels-Alder (IMDA) reaction of alkynes. With this synthetic method, the first enantioselective synthesis of (+)-alpha-yohimbine was completed in 9 steps from the IMDA products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Quantification of isomerically summed hydrocarbon contributions to crude oil by carbon number, double bond equivalent, and aromaticity using gas chromatography with tunable vacuum ultraviolet ionization.

    Science.gov (United States)

    Nowak, Jeremy A; Weber, Robert J; Goldstein, Allen H

    2018-03-12

    The ability to structurally characterize and isomerically quantify crude oil hydrocarbons relevant to refined fuels such as motor oil, diesel, and gasoline represents an extreme challenge for chromatographic and mass spectrometric techniques. This work incorporates two-dimensional gas chromatography coupled to a tunable vacuum ultraviolet soft photoionization source, the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source at the Lawrence Berkeley National Laboratory, with a time-of-flight mass spectrometer (GC × GC-VUV-TOF) to directly characterize and isomerically sum the contributions of aromatic and aliphatic species to hydrocarbon classes of four crude oils. When the VUV beam is tuned to 10.5 ± 0.2 eV, both aromatic and aliphatic crude oil hydrocarbons are ionized to reveal the complete chemical abundance of C 9 -C 30 hydrocarbons. When the VUV beam is tuned to 9.0 ± 0.2 eV only aromatic hydrocarbons are ionized, allowing separation of the aliphatic and aromatic fractions of the crude oil hydrocarbon chemical classes in an efficient manner while maintaining isomeric quantification. This technique provides an effective tool to determine the isomerically summed aromatic and aliphatic hydrocarbon compositions of crude oil, providing information that goes beyond typical GC × GC separations of the most dominant hydrocarbon isomers.

  16. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir; Atiqullah, Muhammad; Malaibari, Zuhair O.; Al-Harthi, Mamdouh A.; Emwas, Abdul-Hamid M.; Ul-Hamid, Anwar

    2015-01-01

    -catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion

  17. Fast and Green Microwave-Assisted Conversion of Essential Oil Allylbenzenes into the Corresponding Aldehydes via Alkene Isomerization and Subsequent Potassium Permanganate Promoted Oxidative Alkene Group Cleavage

    DEFF Research Database (Denmark)

    Luu, Thi Xuan Thi; Lam, Trinh To; Le, Thach Ngoc

    2009-01-01

    Essential oil allylbenzenes from have been converted quickly and efficiently into the corresponding benzaldehydes in good yields by a two-step "green" reaction pathway based on a solventless alkene group isomerization by KF/Al2O3 to form the corresponding 1-arylpropene and a subsequent solventles...

  18. Second-chance forward isomerization dynamics of the red/green cyanobacteriochrome NpR6012g4 from Nostoc punctiforme.

    Science.gov (United States)

    Kim, Peter W; Freer, Lucy H; Rockwell, Nathan C; Martin, Shelley S; Lagarias, J Clark; Larsen, Delmar S

    2012-01-11

    The primary ultrafast Z-to-E isomerization photodynamics of the phytochrome-related cyanobacteriochrome NpR6012g4 from Nostoc punctiforme was studied by transient absorption pump-dump-probe spectroscopy. A 2 ps dump pulse resonant with the stimulated emission band depleted 21% of the excited-state population, while the initial photoproduct Lumi-R was depleted by only 11%. We observed a red-shifted ground-state intermediate (GSI) that we assign to a metastable state that failed to isomerize fully. Multicomponent global analysis implicates the generation of additional Lumi-R from the GSI via crossing over the ground-state thermal barrier for full isomerization, explaining the discrepancy between excited-state and Lumi-R depletion by the dump pulse. This second-chance ground-state dynamics provides a plausible explanation for the unusually high quantum yield of 40% for the primary isomerization step in the forward reaction of NpR6012g4. © 2011 American Chemical Society

  19. Trans isomeric octadecenoic acids are related inversely to arachidonic acid and DHA and positively related to mead acid in umbilical vessel wall lipids

    NARCIS (Netherlands)

    Decsi, T; Boehm, G; Tjoonk, HMR; Molnar, S; Dijck-Brouwer, DAJ; Hadders-Algra, M; Martini, IA; Muskiet, FAJ; Boersma, ER

    2002-01-01

    Long-chain PUFA play an important role in early human neurodevelopment. Significant inverse correlations were reported between values of trans isomeric and long-chain PUFA in plasma lipids of preterm infants and children aged 1-15 yr as well as in venous cord blood lipids of full-term infants. Here

  20. Isomerization of Internal Alkynes to Iridium(III Allene Complexes via C–H Bond Activation: Expanded Substrate Scope, and Progress towards a Catalytic Methodology

    Directory of Open Access Journals (Sweden)

    Neha Phadke

    2015-11-01

    Full Text Available The synthesis of a series of allene complexes (POCOPIr(η2-RC=.=CR’ 1b–4b (POCOP = 2,6-bis(di-tert-butylphosphonitobenzene via isomerization of internal alkynes is reported. We have demonstrated that the application of this methodology is viable for the isomerization of a wide variety of alkyne substrates. Deuterium labeling experiments support our proposed mechanism. The structures of the allene complexes 1b–4b were determined using spectroscopic data analysis. Additionally, the solid-state molecular structure of complex 2b was determined using single crystal X-ray diffraction studies and it confirmed the assignment of an iridium-bound allene isomerization product. The rates of isomerization were measured using NMR techniques over a range of temperatures to allow determination of thermodynamic parameters. Finally, we report a preliminary step towards developing a catalytic methodology; the allene may be liberated from the metal center by exposure of the complex to an atmosphere of carbon monoxide.

  1. In-tube collision-induced dissociation for selected ion flow-drift tube mass spectrometry, SIFDT-MS: a case study of NO+ reactions with isomeric monoterpenes

    Czech Academy of Sciences Publication Activity Database

    Spesyvyi, Anatolii; Sovová, Kristýna; Španěl, Patrik

    2016-01-01

    Roč. 30, č. 18 (2016), s. 2009-2016 ISSN 0951-4198 R&D Projects: GA ČR GA13-28882S Institutional support: RVO:61388955 Keywords : mass spectroscopy * SIFDT-MS * isomeric monoterpenes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.998, year: 2016

  2. Thermal decay of rhodopsin: role of hydrogen bonds in thermal isomerization of 11-cis retinal in the binding site and hydrolysis of protonated Schiff base.

    Science.gov (United States)

    Liu, Jian; Liu, Monica Yun; Nguyen, Jennifer B; Bhagat, Aditi; Mooney, Victoria; Yan, Elsa C Y

    2009-07-01

    Although thermal stability of the G protein-coupled receptor rhodopsin is directly related to its extremely low dark noise level and has recently generated considerable interest, the chemistry behind the thermal decay process of rhodopsin has remained unclear. Using UV-vis spectroscopy and HPLC analysis, we have demonstrated that the thermal decay of rhodopsin involves both hydrolysis of the protonated Schiff base and thermal isomerization of 11-cis to all-trans retinal. Examining the unfolding of rhodopsin by circular dichroism spectroscopy and measuring the rate of thermal isomerization of 11-cis retinal in solution, we conclude that the observed thermal isomerization of 11-cis to all-trans retinal happens when 11-cis retinal is in the binding pocket of rhodopsin. Furthermore, we demonstrate that solvent deuterium isotope effects are involved in the thermal decay process by decreasing the rates of thermal isomerization and hydrolysis, suggesting that the rate-determining step of these processes involves breaking hydrogen bonds. These results provide insight into understanding the critical role of an extensive hydrogen-bonding network on stabilizing the inactive state of rhodopsin and contribute to our current understanding of the low dark noise level of rhodopsin, which enables this specialized protein to function as an extremely sensitive biological light detector. Because similar hydrogen-bonding networks have also been suggested by structural analysis of two other GPCRs, beta1 and beta2 adrenergic receptors, our results could reveal a general role of hydrogen bonds in facilitating GPCR function.

  3. Amino acid-catalyzed conversion of citral : cis-trans isomerization and its conversion into 6-methyl-5-hepten-2-one and acetaldehyde

    NARCIS (Netherlands)

    Wolken, W.A.M.; Have, R. ten; Werf, M.J. van der

    2000-01-01

    Under alkaline conditions, amino acids or proteins catalyze the deacetylation of citral, a major aroma component, resulting in methylheptenone and acetaldehyde formation. 3-Hydroxycitronellal is an intermediate in this reaction. Amino acids also catalyze the cis-trans isomerization of the pure

  4. Kinetics of isomerization and inversion of aspartate 58 of αA-crystallin peptide mimics under physiological conditions.

    Directory of Open Access Journals (Sweden)

    Kenzo Aki

    Full Text Available Although proteins consist exclusively of L-amino acids, we have reported that aspartyl (Asp 58 and Asp 151 residues of αA-crystallin of eye lenses from elderly cataract donors are highly inverted and isomerized to D-β, D-α and L-β-Asp residues through succinimide intermediates. Of these Asp isomers, large amounts of D-β- and L-β-isomers are present but the amount of D-α-isomer is not significant. The difference in abundance of the Asp isomers in the protein may be due to the rate constants for the formation of the isomers. However, the kinetics have not been well defined. Therefore, in this study, we synthesized a peptide corresponding to human αA-crystallin residues 55 to 65 (T(55VLD(58SGISEVR(65 and its isomers in which L-α-Asp at position 58 was replaced with L-β-, D-β- and D-α-Asp and determined the rate of isomerization and inversion of Asp residues under physiological conditions (37°C, pH7.4. The rate constant for dehydration from L-α-Asp peptide to L-succinimidyl peptide was 3 times higher than the rate constant for dehydration from L-β-Asp peptide to L-succinimidyl peptide. The rate constant for hydrolysis from L-succinimidyl peptide to L-β-Asp peptide was about 5 times higher than the rate constant for hydrolysis from L-succinimidyl peptide to L-α-Asp peptide. The rate constant for dehydration from L-α-Asp peptide to L-succinimidyl peptide was 2 times higher than the rate constant for dehydration from D-α-Asp peptide to D-succinimidyl peptide. The rate constants for hydrolysis from L-succinimidyl peptide to L-β-Asp peptide and for hydrolysis from D-succinimidyl peptide to D-β-Asp peptide were almost equal. Using these rate constants, we calculated the change in the abundance ratios of the 4 Asp isomers during a human lifespan. This result is consistent with the fact that isomerized Asp residues accumulate in proteins during the ageing process.

  5. Solution NMR structure and inhibitory effect against amyloid-β fibrillation of Humanin containing a D-isomerized serine residue

    Energy Technology Data Exchange (ETDEWEB)

    Alsanousi, Nesreen [Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka 565-0871 (Japan); Sugiki, Toshihiko, E-mail: sugiki@protein.osaka-u.ac.jp [Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka 565-0871 (Japan); Furuita, Kyoko; So, Masatomo; Lee, Young-Ho; Fujiwara, Toshimichi [Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka 565-0871 (Japan); Kojima, Chojiro, E-mail: kojima-chojiro-xk@ynu.ac.jp [Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka 565-0871 (Japan); Graduate School of Engineering, Yokohama National University, Tokiwadai 79-5, Hodogaya-ku, Yokohama 240-8501 (Japan)

    2016-09-02

    Humanin comprising 24 amino acid residues is a bioactive peptide that has been isolated from the brain tissue of patients with Alzheimer's disease. Humanin reportedly suppressed aging-related death of various cells due to amyloid fibrils and oxidative stress. There are reports that the cytoprotective activity of Humanin was remarkably enhanced by optical isomerization of the Ser14 residue from L to D form, but details of the molecular mechanism remained unclear. Here we demonstrated that Humanin D-Ser14 exhibited potent inhibitory activity against fibrillation of amyloid-β and remarkably higher binding affinity for amyloid-β than that of the Humanin wild-type and S14G mutant. In addition, we determined the solution structure of Humanin D-Ser14 by nuclear magnetic resonance (NMR) and showed that D-isomerization of the Ser14 residue enables drastic conformational rearrangement of Humanin. Furthermore, we identified an amyloid-β-binding site on Humanin D-Ser14 at atomic resolution by NMR. These biophysical and high-resolution structural analyses clearly revealed structure–function relationships of Humanin and explained the driving force of the drastic conformational change and molecular basis of the potent anti-amyloid-β fibrillation activity of Humanin caused by D-isomerization of the Ser14 residue. This is the first study to show correlations between the functional activity, tertiary structure, and partner recognition mode of Humanin and may lead to elucidation of the molecular mechanisms of the cytoprotective activity of Humanin. - Highlights: • Humanin D-Ser14 showed the strongest inhibitory activity against Aβ40 fibrillation. • NMR structure of Humanin D-Ser14 was determined in alcohol/water mixture solution. • Humanin D-Ser14 directly bound Aβ40 stronger than Humanin wild-type and Humanin S14G. • Aβ40 and zinc ion binding sites of Humanin D-Ser14 were identified. • Structure around Ser14 of Humanin is critical for Aβ40 binding and

  6. Effects of Offense, Defense, and Ball Possession on Mobility Performance in Wheelchair Basketball

    NARCIS (Netherlands)

    de Witte, Annemarie M. H.; Berger, Monique A. M.; Hoozemans, Marco J. M.; Veeger, Dirkjan H. E. J.; van der Woude, Lucas H. V.

    2017-01-01

    The aim of this study was to determine to what extent mobility performance is influenced by offensive or defensive situations and ball possession and to what extent these actions are different for the field positions. From video analysis, the relative duration of the various wheelchair movements

  7. What does it mean to be possessed by a spirit or demon? Some ...

    African Journals Online (AJOL)

    2015-07-08

    Jul 8, 2015 ... Commons Attribution. License. .... Klass (2003:3) I therefore want to ask the question: 'What is actually .... help to categorise possession in terms of possible causal ... control of life. .... a social structure, the complex formed by all his [her] social ... a way to cope with stressful experiences and, together with.

  8. Competences possessed and required by European graduates. REFLEX Report to HEFCE No 4

    OpenAIRE

    Little, Brenda; Braun, Edith; Tang, Win-Yee

    2008-01-01

    The report is based on the results of a major international study of graduate employment some five years after graduation. It presents an analysis of graduates' perceptions of what competences they need to do their current jobs and whether they possess these competences.

  9. 31 CFR 601.5 - Penalty for unauthorized control or possession.

    Science.gov (United States)

    2010-07-01

    ... CURRENCY AND OTHER SECURITIES § 601.5 Penalty for unauthorized control or possession. The Secretary of the... heretofore adopted for the printing of paper currency or other obligations or securities of the United States, is and will be subject to the provisions of 18 U.S.C. 474A which provides, in part, that it is...

  10. 7 CFR 330.300 - Soil from foreign countries or Territories or possessions. 1

    Science.gov (United States)

    2010-01-01

    ... 7 Agriculture 5 2010-01-01 2010-01-01 false Soil from foreign countries or Territories or possessions. 1 330.300 Section 330.300 Agriculture Regulations of the Department of Agriculture (Continued) ANIMAL AND PLANT HEALTH INSPECTION SERVICE, DEPARTMENT OF AGRICULTURE FEDERAL PLANT PEST REGULATIONS; GENERAL; PLANT PESTS; SOIL, STONE, AND QUARRY...

  11. What does it mean to be possessed by a spirit or demon? Some ...

    African Journals Online (AJOL)

    The visible growth in possession and exorcism in Southern Africa can, amongst others, be attributed to the general impression in Christianity that, since Jesus was a successful exorcist, his followers should follow his example. Historical Jesus research generally endorses a view of Jesus as exorcist, which probably also ...

  12. 50 CFR 648.322 - Skate allocation, possession, and landing provisions.

    Science.gov (United States)

    2010-10-01

    ... 50 Wildlife and Fisheries 8 2010-10-01 2010-10-01 false Skate allocation, possession, and landing provisions. 648.322 Section 648.322 Wildlife and Fisheries FISHERY CONSERVATION AND MANAGEMENT, NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION, DEPARTMENT OF COMMERCE FISHERIES OF THE NORTHEASTERN UNITED STATES Management Measures for the NE Skate...

  13. 27 CFR 479.105 - Transfer and possession of machine guns.

    Science.gov (United States)

    2010-04-01

    ... a department, agency, or political subdivision thereof; or any lawful transfer or lawful possession... distribution to any department or agency of the United States or any State or political subdivision thereof, or... entities expressing a need for a particular model or interest in seeing a demonstration of a particular...

  14. Logarithmic residues of analytic Banach algebra valued functions possessing a simply meromorphic inverse

    NARCIS (Netherlands)

    H. Bart (Harm); T. Ehrhardt; B. Silbermann

    2001-01-01

    textabstractA logarithmic residue is a contour integral of a logarithmic derivative (left or right) of an analytic Banach algebra valued function. For functions possessing a meromorphic inverse with simple poles only, the logarithmic residues are identified as the sums of idempotents. With the help

  15. Possession, Transportation, and Use of Firearms by Older Youth in 4-H Shooting Sports Programs

    Science.gov (United States)

    White, David J.; Williver, S. Todd

    2014-01-01

    Thirty years ago we would think nothing of driving to school with a jackknife in our pocket or rifle in the gun rack. Since then, the practices of possessing, transporting, and using firearms have been limited by laws, rules, and public perception. Despite restrictions on youth, the Youth Handgun Safety Act does afford 4-H shooting sports members…

  16. THE RELATIONSHIP BETWEEN RESEARCH AND TEACHING: THE CHART OF POSSESSIVE PRONOUNS IN PORTUGUESE

    Directory of Open Access Journals (Sweden)

    Leonardo Lennertz Marcotulio

    2016-01-01

    Full Text Available The aim of this article is to investigate the relationship between research and teaching, concerning the rearrangements operated in the chart of possessive pronouns,  observing in which way sociolinguistic studies have been applied to the teaching of Portuguese through the didactic material prepared for High School and the courses of Portuguese as a Foreign Language.

  17. Effects of offense, defense, and ball possession on mobility performance in wheelchair basketball

    NARCIS (Netherlands)

    De Witte, Annemarie M.H.; Berger, Monique A.M.; Hoozemans, Marco J.M.; Veeger, H.E.J.; van der Woude, Lucas H.V.

    2017-01-01

    The aim of this study was to determine to what extent mobility performance is influenced by offensive or defensive situations and ball possession and to what extent these actions are different for the field positions. From video analysis, the relative duration of the various wheelchair movements

  18. How Risky Is Marijuana Possession? Considering the Role of Age, Race, and Gender

    Science.gov (United States)

    Nguyen, Holly; Reuter, Peter

    2012-01-01

    Arrest rates per capita for possession of marijuana have increased threefold over the last 20 years and now constitute the largest single arrest offense category. Despite the increase in arrest numbers, rates of use have remained stable during much of the same period. This article presents the first estimates of the arrest probabilities for…

  19. 27 CFR 478.40 - Manufacture, transfer, and possession of semiautomatic assault weapons.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 3 2010-04-01 2010-04-01 false Manufacture, transfer, and... COMMERCE IN FIREARMS AND AMMUNITION Administrative and Miscellaneous Provisions § 478.40 Manufacture, transfer, and possession of semiautomatic assault weapons. (a) Prohibition. No person shall manufacture...

  20. Whose name is it anyway? Varying patterns of possessive usage in eponymous neurodegenerative diseases

    Directory of Open Access Journals (Sweden)

    Michael R. MacAskill

    2013-04-01

    Full Text Available There has been long-standing debate over whether use of the possessive form of the names of eponymous neurological disorders should be abandoned. Which view has actually predominated in practice? We empirically assessed current and historical usage in the scientific literature. The PubMed database was queried for the percentage of titles published each year from 1960–2012 which contained the possessive form of Parkinson’s (PD, Alzheimer’s (AD, Huntington’s (HD, Wilson’s (WD, and Gaucher’s (GD diseases (e.g. Huntington’s disease or chorea vs Huntington disease or chorea. Down syndrome (DS, well known for its changes in terminology, was used as a reference. The possessive form was nearly universal in all conditions from 1960 until the early 1970s. In both DS and GD it then declined at an approximately constant rate of 2 percentage points per year to drop below 15%. The possessive forms of both PD and AD began to decline at the same time but stabilised and have since remained above 80%, with a similar but more volatile pattern in HD. WD, meanwhile, is intermediate between the DS/GD and PD/AD/HD patterns, with a slower decline to its current value of approximately 60%. Declining possessive form usage in GD and DS papers has been remarkably uniform over time and has nearly reached completion. PD and AD appear stable in remaining predominantly possessive. The larger volume of papers published in those fields and their possibly greater public recognition and involvement may make that unlikely to change in the short-term. In a secondary analysis restricted to PD, we found that practices have switched dramatically several times in each of three US-published general neurology journals. Meanwhile, in two UK-published journals, and in the specialist title “Movement Disorders”, the possessive form has been maintained consistently. The use of eponyms in neurology shows systematic variation across time, disorders, and journals.

  1. Relationship between length of A-bomb survivor's health handbook possession and mortality risk

    International Nuclear Information System (INIS)

    Otani, Keiko; Ohtaki, Megu; Satoh, Kenichi; Tonda, Tetsuji

    2012-01-01

    The title handbook was first issued to support the health of A-bomb survivors by Japan MHLW in 1957, and about 220 thousands possess it in 2010. Its major supports contain free medicare, 2 periodic and 2 optional medical examinations/year and other various benefits. This study was performed to elucidate the relationship in the title for evaluation of its life prolonging effect on Hiroshima survivors. The length of handbook possession was defined the period from acquiring it to death. The cohort was 17,335 (7,607 men) registered survivors who had had the handbook for 1 year or more, and before Nov. 1965 or later, until Dec. 2010. Causes of death event were classified to be the cerebrovascular, cardiac and cancerous disease, and others were censored. The objective variable was mortality risk, and predictors were the exposed dose, age at the exposure, chronological age and length of handbook possession. Risk of cerebrovascular or cardiac death was estimated by the model of exponential function, and of cancer death, of power function based on multi-stage theory of carcinogenesis. Results revealed that the cerebrovascular mortality of women and men was 8.1 and 7.2%, respectively; cardiac, 8.7 and 7.2%; and cancerous, 10.1 and 14.9%. Significant reduction of relative risk of cerebrovascular death, about 4% per 1 year handbook possession, was observed in men alone; negative correlations of period effect were seen in cerebrovascular and cardiac death of women; and positive correlation between cancer death and exposed dose was observed. The prophylaxis and continuous treatment of cerebrovascular disease due to the handbook possession were thought effective in men. (T.T.)

  2. Gun possession among American youth: a discovery-based approach to understand gun violence.

    Directory of Open Access Journals (Sweden)

    Kelly V Ruggles

    Full Text Available OBJECTIVE: To apply discovery-based computational methods to nationally representative data from the Centers for Disease Control and Preventions' Youth Risk Behavior Surveillance System to better understand and visualize the behavioral factors associated with gun possession among adolescent youth. RESULTS: Our study uncovered the multidimensional nature of gun possession across nearly five million unique data points over a ten year period (2001-2011. Specifically, we automated odds ratio calculations for 55 risk behaviors to assemble a comprehensive table of associations for every behavior combination. Downstream analyses included the hierarchical clustering of risk behaviors based on their association "fingerprint" to 1 visualize and assess which behaviors frequently co-occur and 2 evaluate which risk behaviors are consistently found to be associated with gun possession. From these analyses, we identified more than 40 behavioral factors, including heroin use, using snuff on school property, having been injured in a fight, and having been a victim of sexual violence, that have and continue to be strongly associated with gun possession. Additionally, we identified six behavioral clusters based on association similarities: 1 physical activity and nutrition; 2 disordered eating, suicide and sexual violence; 3 weapon carrying and physical safety; 4 alcohol, marijuana and cigarette use; 5 drug use on school property and 6 overall drug use. CONCLUSIONS: Use of computational methodologies identified multiple risk behaviors, beyond more commonly discussed indicators of poor mental health, that are associated with gun possession among youth. Implications for prevention efforts and future interdisciplinary work applying computational methods to behavioral science data are described.

  3. Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface

    Science.gov (United States)

    Molla, Mijanur Rahaman; Rangadurai, Poornima; Antony, Lucas; Swaminathan, Subramani; de Pablo, Juan J.; Thayumanavan, S.

    2018-06-01

    Nature has engineered exquisitely responsive systems where molecular-scale information is transferred across an interface and propagated over long length scales. Such systems rely on multiple interacting, signalling and adaptable molecular and supramolecular networks that are built on dynamic, non-equilibrium structures. Comparable synthetic systems are still in their infancy. Here, we demonstrate that the light-induced actuation of a molecularly thin interfacial layer, assembled from a hydrophilic- azobenzene -hydrophobic diblock copolymer, can result in a reversible, long-lived perturbation of a robust glassy membrane across a range of over 500 chemical bonds. We show that the out-of-equilibrium actuation is caused by the photochemical trans-cis isomerization of the azo group, a single chemical functionality, in the middle of the interfacial layer. The principles proposed here are implemented in water-dispersed nanocapsules, and have implications for on-demand release of embedded cargo molecules.

  4. Counting efficiencies by liquid scintillation counting. Single isomeric transitions; Eficiencia de recuento por centelleo liquido. Transiciones isomericas simples

    Energy Technology Data Exchange (ETDEWEB)

    Grau Carles, A.; Grau Malonda, A.

    1995-07-01

    In this work we present liquid scintillation counting efficiency tables for several radionuclides with single isomeric transitions, in which electron conversion and gamma emission processes are competitive. We study the radionuclides: 58mCo, 77mSe, 79mBr, 87mSr, S9mY, 93mNb, 103mRh, 107mAg, 109mAg, 113mIn, 131mXe, I33mXe, 135raBa, 137mBa, 167raEr, for two different scintillators, Ultima-Gold and Insta-Gel. We consider volumes of 10 and 15 mL for Ultima Gold, and 15 mL for Insta-Gel. (Author) 18 refs.

  5. Thermal isomerizations of ketenimines to nitriles: evaluations of sigma-Dot (sigma(*)) constants for spin-delocalizations

    Science.gov (United States)

    Kim; Zhu; Lee

    2000-05-19

    Rate constants (k(Y)) of the isomerizations of 11 diphenyl N-(substituted benzyl) ketenimines were measured at 40, 50, 60, and 70 degrees C. Activation parameters DeltaH()(Y) and DeltaS()(Y) were obtained using the Eyring equation. The relative rates (k(Y)/k(H)) were fitted into Hammett single correlations (log k(Y)/k(H) = rhosigma and log k(Y)/k(H) = rho(*)sigma(*)). The single correlations have been compared with Hammett dual correlations (log k(Y)/k(H) = rhosigma + rho(*)sigma(*) ). Separate treatments of para and meta substituents yielded even better correlations. Para substituents control the rates through spin-delocalizations and inductive effects. The former outweighs the latter when the latter exerts a modest but distinct influence on the rates. On the other hand, inductive effects are the "major" or the sole interactions triggered by meta substituents.

  6. Montecarlo calculation of the isomeric cross sections ratio for the reaction 237Np(n,2n)236Np

    International Nuclear Information System (INIS)

    Cleri, F.

    1988-01-01

    A Montecarlo calculation of the isomeric cross section ratio for the (n,2n) reaction on 237 Np has been carried out based on the Hauser-Feshbach formulation. A standard energy-dependent optical model potential was used, with zero deformation parameters and no spin-orbit coupling. Investigation was made about the role of the energy cut-off value, of the higher multipole (E2) transition, of the gamma-ray versus second neutron emission, of the value of the spin cutt-off parameter. The results give the correct qualitative energy dependence of the branching ratio, with the assumption that the 1 - level is the ground state. The spin cut-off value obtained indicates a less pronounced deviation of the nuclear moment of inertia from the rigid-body value, with respect to older evaluations for high-mass nuclei. (author)

  7. Pt, Re and Pt-Re incorporation in sulfated zirconia as catalysts for n-pentane isomerization

    International Nuclear Information System (INIS)

    Aboul-Gheit, A.K.; El-Desouki, D.S.; Abdel-Hamid, S.M.; Ghoneim, S.A.; Ibrahim, A.H.; Gad, F.K.; Abdel-Aleem, G.M.

    2010-01-01

    Two groups of modified Sulfated Zirconia (S Z) catalysts were prepared by the sol-gel method. The first group was modified by four different concentrations of Pt metal (0.15, 0.30, 0.45 and 0.60 wt %), whereas the second group contained Pt-Re combinations on SZ. All the prepared catalysts were characterized by XRD, TPR, TEM, TGA, IR spectroscopy as well as surface properties using the BET method. The catalytic activity of the catalysts was examined for the hydro isomerization of n-pentane to iso-pentane. The catalytic activity was found to increase with increasing Pt concentration in the mono metallic catalysts. The combination of Re ion with Pt on SZ results in significant changes in the characters and activities of the catalysts. The 0.45 wt % Pt + 0.15 wt % Re/SZ catalyst exhibited the highest selective compared to other metal ratios investigated

  8. Isomeric and high-spin states of 94Tc and the search for yrast isomers near N~50

    Science.gov (United States)

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

    1981-07-01

    A search for isomers in the N~50 region has produced no evidence of high-spin yrast isomerism. A new 4.5-ns low-multiplicity isomer has been identified and assigned to 94Tc, while the yrast sequence of 94Tc has been established to more than 5 MeV in excitation energy. [NUCLEAR REACTIONS 76Ge, 78Se(20Ne,xnypγ), E=80.9 MeV, 89Y, 93Nb(10B,xnypγ), E=52.0,58.4,62.8 MeV; measured Eγ, Iγ, γ-γ prompt and delayed coin, γ-X coin; deduced levels, t12 of 94Tc isomer, yrast states.

  9. Angular momentum distribution of primary fission fragments by measurement of the relative yield of isomeric fission products

    International Nuclear Information System (INIS)

    Dornhoefer, H.

    1980-01-01

    The fission products 132 I and 136 I produced in the fission reactions 238 U(α,f) and 238 U(d,f) were spectroscoped using a gas transport system. Thereby was taken advantage of the fact that at the transport with pure helium without aerosols only iodine activities were collected in a membrane filter. The relative independent yields of the isomeric fission products of 132 I and 136 I were determined for different excitation energies. Thereby was taken advantage of the fact that the transport yield of the gas transport system for 136 I directly produced from the fission was greater than for iodine indirectly produced by β-decay. (orig./HSI) [de

  10. Structural analysis of isomeric chondroitin sulfate oligosaccharides using regioselective 6-O-desulfation method and tandem mass spectrometry.

    Science.gov (United States)

    Chen, Shu-Ting; Her, Guor-Rong

    2014-09-16

    A strategy based on a regioselective 6-O-desulfation reaction and negative ion electrospray ionization tandem mass spectrometry (ESI-MS(n)) was developed for the structural delineation of isomeric chondroitin sulfate oligosaccharides. Product ions resulting from the glycosidic cleavage provided information about the number of sulfate groups in each sugar residue. After the regioselective 6-O-desulfation reaction, the number of sulfate groups on each residue was obtained using a tandem mass spectrometry analysis of the reaction product. The sulfation pattern could be obtained based on the product ions of analytes before and after the desulfation reaction. The strategy was demonstrated using a series of tetrasaccharides prepared from shark cartilage chondroitin sulfate D. Among the 12 identified tetrasaccharides, six structures had not been reported before. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. The effect of playing tactics and situational variables on achieving score-box possessions in a professional soccer team.

    Science.gov (United States)

    Lago-Ballesteros, Joaquin; Lago-Peñas, Carlos; Rey, Ezequiel

    2012-01-01

    The aim of this study was to analyse the influence of playing tactics, opponent interaction and situational variables on achieving score-box possessions in professional soccer. The sample was constituted by 908 possessions obtained by a team from the Spanish soccer league in 12 matches played during the 2009-2010 season. Multidimensional qualitative data obtained from 12 ordered categorical variables were used. Sampled matches were registered by the AMISCO PRO system. Data were analysed using chi-square analysis and multiple logistic regression analysis. Of 908 possessions, 303 (33.4%) produced score-box possessions, 477 (52.5%) achieved progression and 128 (14.1%) failed to reach any sort of progression. Multiple logistic regression showed that, for the main variable "team possession type", direct attacks and counterattacks were three times more effective than elaborate attacks for producing a score-box possession (P tactics on producing score-box possessions.

  12. Quantum optimal control pathways of ozone isomerization dynamics subject to competing dissociation: A two-state one-dimensional model

    International Nuclear Information System (INIS)

    Kurosaki, Yuzuru; Ho, Tak-San; Rabitz, Herschel

    2014-01-01

    We construct a two-state one-dimensional reaction-path model for ozone open → cyclic isomerization dynamics. The model is based on the intrinsic reaction coordinate connecting the cyclic and open isomers with the O 2 + O asymptote on the ground-state 1 A ′ potential energy surface obtained with the high-level ab initio method. Using this two-state model time-dependent wave packet optimal control simulations are carried out. Two possible pathways are identified along with their respective band-limited optimal control fields; for pathway 1 the wave packet initially associated with the open isomer is first pumped into a shallow well on the excited electronic state potential curve and then driven back to the ground electronic state to form the cyclic isomer, whereas for pathway 2 the corresponding wave packet is excited directly to the primary well of the excited state potential curve. The simulations reveal that the optimal field for pathway 1 produces a final yield of nearly 100% with substantially smaller intensity than that obtained in a previous study [Y. Kurosaki, M. Artamonov, T.-S. Ho, and H. Rabitz, J. Chem. Phys. 131, 044306 (2009)] using a single-state one-dimensional model. Pathway 2, due to its strong coupling to the dissociation channel, is less effective than pathway 1. The simulations also show that nonlinear field effects due to molecular polarizability and hyperpolarizability are small for pathway 1 but could become significant for pathway 2 because much higher field intensity is involved in the latter. The results suggest that a practical control may be feasible with the aid of a few lowly excited electronic states for ozone isomerization

  13. Purification and Quantification of an Isomeric Compound in a Mixture by Collisional Excitation in Multistage Mass Spectrometry Experiments.

    Science.gov (United States)

    Jeanne Dit Fouque, Dany; Maroto, Alicia; Memboeuf, Antony

    2016-11-15

    The differentiation, characterization, and quantification of isomers and/or isobars in mixtures is a recurrent problem in mass spectrometry and more generally in analytical chemistry. Here we present a new strategy to assess the purity of a compound that is susceptible to be contaminated with another isomeric side-product in trace levels. Providing one of the isomers is available as pure sample, this new strategy allows the detection of isomeric contamination. This is done thanks to a "gas-phase collisional purification" inside an ion trap mass spectrometer paving the way for an improved analysis of at least similar samples. This strategy consists in using collision induced dissociation (CID) multistage mass spectrometry (MS 2 and MS 3 ) experiments and the survival yield (SY) technique. It has been successfully applied to mixtures of cyclic poly( L -lactide) (PLA) with increasing amounts of its linear topological isomer. Purification in gas phase of PLA mixtures was established based on SY curves obtained in MS 3 mode: all samples gave rise to the same SY curve corresponding then to the pure cyclic component. This new strategy was sensitive enough to detect traces of linear PLA (<3%) in a sample of cyclic PLA that was supposedly pure according to other characterization techniques ( 1 H NMR, MALDI-HRMS, and size-exclusion chromatography). Moreover, in this case, the presence of linear isomer was undetectable according to MS/MS or MS/MS/MS analysis only as fragment ions are also of the same m/z values. This type of approach could easily be implemented in hyphenated mass spectrometric techniques to improve the structural and quantitative analysis of complex samples.

  14. Tuning light-emitting properties of N-phenylcarbazole-capped anthrylvinyl derivatives by symmetric and isomeric effects

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Qingli; Wang, Jianfeng; Yin, Ling; Chen, Mingshuai [Key Laboratory of Rubber-Plastics of Ministry of Education/Shandong Province (QUST), School of Polymer Science & Engineering, Qingdao University of Science & Technology, 53-Zhengzhou Road, Qingdao 266042 (China); Xue, Shanfeng, E-mail: sfxue@qust.edu.cn [Key Laboratory of Rubber-Plastics of Ministry of Education/Shandong Province (QUST), School of Polymer Science & Engineering, Qingdao University of Science & Technology, 53-Zhengzhou Road, Qingdao 266042 (China); State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou 510640 (China); Yang, Wenjun, E-mail: ywjph2004@qust.edu.cn [Key Laboratory of Rubber-Plastics of Ministry of Education/Shandong Province (QUST), School of Polymer Science & Engineering, Qingdao University of Science & Technology, 53-Zhengzhou Road, Qingdao 266042 (China)

    2017-03-15

    This paper focuses on effects of molecular symmetry and isomerisation on light-emitting properties based on N-phenylcarbazole-capped anthrylvinyl derivatives. We have designed and synthesized three isomeric 10-(arylvinyl)anthracenes with N-phenylcarbazole as the mono aryl moiety whose 2-, 3-, or carbazole-9-yl-phenyl positions are linked, and their optical and electroluminescence properties are investigated and compared with analogous 9,10-bis(arylvinyl)anthracenes. The results showed that, contrary to the dual N-phenylcarbazole-capped analogues, the three mono N-phenylcarbazole-capped isomers have neither aggregation-induced emission nor mechanofluorochromism although they are characterized by twisted π-backbone and grinding-induced amorphization. It is observed that the mono substitution can significantly blue-shift the emission spectra and greatly improve the electroluminescence performances, accompanying by the remarkably isomeric effect. This finding demonstrates that changing the molecular substitution patterns could effectively alter and tune the light-emitting properties to greatly widen the scope of molecular candidates applicable in optical and optoelectronic fields. - Highlights: • Three monoN-phenylcarbazole-capped 10-vinylanthracenes are designed to investigate the geometric symmetry and isomer effects. • The three backbone-twisted luminogens do not exhibit AIE and MFC activity. • The grinding-induced amorphization does not necessarily cause the change in fluorescence color. • 10-Arylvinylanthracenes show the better EL performances than 9,10-di(aryl- vinyl)anthracenes. • Subtly manipulating molecular geometric symmetry could tune and alter the solid-state aggregation and stimuli-responsive behaviors.

  15. [A nosology for supernatural phenomena and the construction of the 'possessed' brain in the nineteenth century].

    Science.gov (United States)

    Goncalves, Valeria Portugal; Ortega, Francisco

    2013-06-01

    At the end of the twentieth century, supernatural phenomena such as so called trances and possession by spirits received a scientific classification, which includes the numerous diagnoses of the dominant psychiatry. At the end of the nineteenth century we can observe a process of scientific categorization of phenomena considered to have originated in superstition or popular imagination. In this work we show how trances and spiritual possession were studied by Franz Anton Mesmer and his followers when developing the concept of magnetism; by James Braid during the creation of his theory of hypnosis; and by Jean Martin Charcot, which marked the entry of hysteria into nosological classification. Despite the differences between these schools, we identify the use of the brain and cerebral metaphors as the foundation of theories of the mind.

  16. Tourette's syndrome: from demonic possession and psychoanalysis to the discovery of gene

    Directory of Open Access Journals (Sweden)

    Francisco M.B. Germiniani

    2012-07-01

    Full Text Available In this paper we make a brief historical review of the hypothesis concerning the etiology of Tourette's syndrome (TS, focusing on varying trends over time: at first, its presumed relation to witchcraft and demonic possessions, followed by the psychoanalytical theory, which attributed TS to a masturbatory equivalent. Then, progressing to modern time, to the immunological theory and finally the advent of genetics and their role in the etiology of TS.

  17. Logarithmic residues of analytic Banach algebra valued functions possessing a simply meromorphic inverse

    OpenAIRE

    Bart, Harm; Ehrhardt, T.; Silbermann, B.

    2001-01-01

    textabstractA logarithmic residue is a contour integral of a logarithmic derivative (left or right) of an analytic Banach algebra valued function. For functions possessing a meromorphic inverse with simple poles only, the logarithmic residues are identified as the sums of idempotents. With the help of this observation, the issue of left versus right logarithmic residues is investigated, both for connected and nonconnected underlying Cauchy domains. Examples are given to elucidate the subject ...

  18. A mosaic adenovirus possessing serotype Ad5 and serotype Ad3 knobs exhibits expanded tropism

    International Nuclear Information System (INIS)

    Takayama, Koichi; Reynolds, Paul N.; Short, Joshua J.; Kawakami, Yosuke; Adachi, Yasuo; Glasgow, Joel N.; Rots, Marianne G.; Krasnykh, Victor; Douglas, Joanne T.; Curiel, David T.

    2003-01-01

    The efficiency of cancer gene therapy with recombinant adenoviruses based on serotype 5 (Ad5) has been limited partly because of variable, and often low, expression by human primary cancer cells of the primary cellular-receptor which recognizes the knob domain of the fiber protein, the coxsackie and adenovirus receptor (CAR). As a means of circumventing CAR deficiency, Ad vectors have been retargeted by utilizing chimeric fibers possessing knob domains of alternate Ad serotypes. We have reported that ovarian cancer cells possess a primary receptor for Ad3 to which the Ad3 knob binds independently of the CAR-Ad5 knob interaction. Furthermore, an Ad5-based chimeric vector, designated Ad5/3, containing a chimeric fiber proteins possessing the Ad3 knob, demonstrates CAR-independent tropism by virtue of targeting the Ad3 receptor. Based on these findings, we hypothesized that a mosaic virus possessing both the Ad5 knob and the Ad3 knob on the same virion could utilize either primary receptor, resulting in expanded tropism. In this study, we generated a dual-knob mosaic virus by coinfection of 293 cells with Ad5-based and Ad5/3-based vectors. Characterization of the resultant virions confirmed the incorporation of both Ad5 and Ad3 knobs in the same particle. Furthermore, this mosaic virus was able to utilize either receptor, CAR and the Ad3 receptor, for virus attachment to cells. Enhanced Ad infectivity with the mosaic virus was shown in a panel of cell lines, with receptor profiles ranging from CAR-dominant to Ad3 receptor-dominant. Thus, this mosaic virus strategy may offer the potential to improve Ad-based gene therapy approaches by infectivity enhancement and tropism expansion

  19. Provable Data Possession of Resource-constrained Mobile Devices in Cloud Computing

    OpenAIRE

    Jian Yang; Haihang Wang; Jian Wang; Chengxiang Tan; Dingguo Yu

    2011-01-01

    Benefited from cloud storage services, users can save their cost of buying expensive storage and application servers, as well as deploying and maintaining applications. Meanwhile they lost the physical control of their data. So effective methods are needed to verify the correctness of the data stored at cloud servers, which are the research issues the Provable Data Possession (PDP) faced. The most important features in PDP are: 1) supporting for public, unlimited numbers of times of verificat...

  20. Prepositions in Use: Prepositions of Standard, Prepositions of Possession and Prepositions of Accompaniment

    OpenAIRE

    Naji Masned AlQbailat; Islam M. Al-Momani; Yazan Shaker Almahameed

    2016-01-01

    The current research paper attempted at investigating the use of prepositions of standard, prepositions of possession and prepositions of accompaniment by some Jordanian learners of English. A total of 53 Jordanian English Majors participated in the study from the department of English language at Princess Alia University College. In collecting the needed data for the purpose of the study, the researchers employed fifteen items of a multiple choice test. The results of the study showed that J...

  1. The investigation of crimes refering to forgery of documents and possession of forged documents

    OpenAIRE

    Kotovienė, Danutė

    2011-01-01

    THE INVESTIGATION OF CRIMES REFERING TO FORGERY OF DOCUMENTS AND POSSESSION OF FORGED DOCUMENTS Constantly improving informational technologies more and more get into our daily routine: nowadays it is widely spread internet payments, purchases, signing on-line agreements using electronic signatures. However, paper documents or other made of appropriate materials, which have material evidence, still have a very significant impact on our life. Its convey different aspects of states’ public work...

  2. Origin and evolution of retinoid isomerization machinery in vertebrate visual cycle: hint from jawless vertebrates.

    Science.gov (United States)

    Poliakov, Eugenia; Gubin, Alexander N; Stearn, Olivia; Li, Yan; Campos, Maria Mercedes; Gentleman, Susan; Rogozin, Igor B; Redmond, T Michael

    2012-01-01

    In order to maintain visual sensitivity at all light levels, the vertebrate eye possesses a mechanism to regenerate the visual pigment chromophore 11-cis retinal in the dark enzymatically, unlike in all other taxa, which rely on photoisomerization. This mechanism is termed the visual cycle and is localized to the retinal pigment epithelium (RPE), a support layer of the neural retina. Speculation has long revolved around whether more primitive chordates, such as tunicates and cephalochordates, anticipated this feature. The two key enzymes of the visual cycle are RPE65, the visual cycle all-trans retinyl ester isomerohydrolase, and lecithin:retinol acyltransferase (LRAT), which generates RPE65's substrate. We hypothesized that the origin of the vertebrate visual cycle is directly connected to an ancestral carotenoid oxygenase acquiring a new retinyl ester isomerohydrolase function. Our phylogenetic analyses of the RPE65/BCMO and N1pC/P60 (LRAT) superfamilies show that neither RPE65 nor LRAT orthologs occur in tunicates (Ciona) or cephalochordates (Branchiostoma), but occur in Petromyzon marinus (Sea Lamprey), a jawless vertebrate. The closest homologs to RPE65 in Ciona and Branchiostoma lacked predicted functionally diverged residues found in all authentic RPE65s, but lamprey RPE65 contained all of them. We cloned RPE65 and LRATb cDNAs from lamprey RPE and demonstrated appropriate enzymatic activities. We show that Ciona ß-carotene monooxygenase a (BCMOa) (previously annotated as an RPE65) has carotenoid oxygenase cleavage activity but not RPE65 activity. We verified the presence of RPE65 in lamprey RPE by immunofluorescence microscopy, immunoblot and mass spectrometry. On the basis of these data we conclude that the crucial transition from the typical carotenoid double bond cleavage functionality (BCMO) to the isomerohydrolase functionality (RPE65), coupled with the origin of LRAT, occurred subsequent to divergence of the more primitive chordates (tunicates, etc

  3. N-Succinimidyl guanidinomethyl iodobenzoate protein radiohalogenation agents: Influence of isomeric substitution on radiolabeling and target cell residualization

    International Nuclear Information System (INIS)

    Choi, Jaeyeon; Vaidyanathan, Ganesan; Koumarianou, Eftychia; McDougald, Darryl; Pruszynski, Marek; Osada, Takuya; Lahoutte, Tony; Lyerly, H. Kim; Zalutsky, Michael R.

    2014-01-01

    Introduction: N-succinimidyl 4-guanidinomethyl-3-[ ⁎ I]iodobenzoate ([ ⁎ I]SGMIB) has shown promise for the radioiodination of monoclonal antibodies (mAbs) and other proteins that undergo extensive internalization after receptor binding, enhancing tumor targeting compared to direct electrophilic radioiodination. However, radiochemical yields for [ 131 I]SGMIB synthesis are low, which we hypothesize is due to steric hindrance from the Boc-protected guanidinomethyl group ortho to the tin moiety. To overcome this, we developed the isomeric compound, N-succinimidyl 3-guanidinomethyl-5-[ 131 I]iodobenzoate (iso-[ 131 I]SGMIB) wherein this bulky group was moved from ortho to meta position. Methods: Boc 2 -iso-SGMIB standard and its tin precursor, N-succinimidyl 3-((1,2-bis(tert-butoxycarbonyl)guanidino)methyl)-5-(trimethylstannyl) benzoate (Boc 2 -iso-SGMTB), were synthesized using two disparate routes, and iso-[*I]SGMIB synthesized from the tin precursor. Two HER2-targeted vectors — trastuzumab (Tras) and a nanobody 5 F7 (Nb) — were labeled using iso-[ ⁎ I]SGMIB and [ ⁎ I]SGMIB. Paired-label internalization assays in vitro with both proteins, and biodistribution in vivo with trastuzumab, labeled using the two isomeric prosthetic agents were performed. Results: When the reactions were performed under identical conditions, radioiodination yields for the synthesis of Boc 2 -iso-[ 131 I]SGMIB were significantly higher than those for Boc 2 -[ 131 I]SGMIB (70.7 ± 2.0% vs 56.5 ± 5.5%). With both Nb and trastuzumab, conjugation efficiency also was higher with iso-[ 131 I]SGMIB than with [ 131 I]SGMIB (Nb, 33.1 ± 7.1% vs 28.9 ± 13.0%; Tras, 45.1 ± 4.5% vs 34.8 ± 10.3%); however, the differences were not statistically significant. Internalization assays performed on BT474 cells with 5 F7 Nb indicated similar residualizing capacity over 6 h; however, at 24 h, radioactivity retained intracellularly for iso-[ 131 I]SGMIB-Nb was lower than for [ 125 I]SGMIB-Nb (46

  4. Revisiting the polytopal rearrangements in penta-coordinate d7-metallocomplexes: modified Berry pseudorotation, octahedral switch, and butterfly isomerization.

    Science.gov (United States)

    Asatryan, Rubik; Ruckenstein, Eli; Hachmann, Johannes

    2017-08-01

    This paper provides a first-principles theoretical investigation of the polytopal rearrangements and fluxional behavior of five-coordinate d 7 -transition metal complexes. Our work is primarily based on a potential energy surface analysis of the iron tetracarbonyl hydride radical HFe˙(CO) 4 . We demonstrate the existence of distorted coordination geometries in this prototypical system and, for the first time, introduce three general rearrangement mechanisms, which account for the non-ideal coordination. The first of these mechanisms constitutes a modified version of the Berry pseudorotation via a square-based pyramidal C 4v transition state that connects two chemically identical edge-bridged tetrahedral stereoisomers of C 2v symmetry. It differs from the classical Berry mechanism, which involves two regular D 3h equilibrium structures and a C 4v transition state. The second mechanism is related to the famous "tetrahedral jump" hypothesis, postulated by Muetterties for a number of d 6 HML 4 and H 2 ML 4 complexes. Here, our study suggests two fluxional rearrangement pathways via distinct types of C 2v transition states. Both pathways of this mechanism can be described as a single-ligand migration to a vacant position of an "octahedron", thus interchanging (switching) the apical and basal ligands of the initial quasi-square pyramidal isomer, which is considered as an idealized octahedron with a vacancy. Accordingly, we call this mechanism "octahedral switch". The third mechanism follows a butterfly-type isomerization featuring a key-angle deformation, and we thus call it "butterfly isomerization". It connects the quasi-square pyramidal and edge-bridged tetrahedral isomers of HFe˙(CO) 4 through a distorted edge-bridged tetrahedral transition state of C s symmetry. Our paper discusses the overall features of the isomers and rearrangement mechanisms as well as their implications. We rationalize the existence of each stationary point through an electronic structure

  5. Application of cinchona-sulfonate-based chiral zwitterionic ion exchangers for the separation of proline-containing dipeptide rotamers and determination of on-column isomerization parameters from dynamic elution profiles.

    Science.gov (United States)

    Wernisch, Stefanie; Trapp, Oliver; Lindner, Wolfgang

    2013-09-17

    The interconversion of cis and trans isomers of dipeptides containing C-terminal proline was studied by dynamic chromatography on zwitterionic chiral stationary phases at temperatures ranging from -15°C to +45°C The cis-trans isomers could be separated below 0°C and above 0-10°C plateau formation and peak coalescence phenomena occurred, which is characteristic for a dynamic process at the time-scale of partitioning. At and above room temperature, full coalescence was observed, which allowed separations of enantiomers without interference from interconversion effects. Analysis of the dynamic elution profiles of the interconverting peptides allowed the determination of isomerization rate constants and thermodynamic activation parameters (isomerization enthalpy, entropy and activation energy). In accordance with established results, isomerization rates and thermodynamic parameters were found to depend on the nature of the N-terminal amino acid. Isomerization barriers were only slightly lower than values determined with other methods but significant differences in the relative contributions of the activation enthalpy and entropy as well as isomerization rates pointed toward selector-moderated isomerization dynamics. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Isomerization and self-condensation reactions subsequent the. beta. -decay of tritiated naphthalene in the presence of liquid and gaseous benzene

    Energy Technology Data Exchange (ETDEWEB)

    Angelini, G.; Keheyan, Y.; Lilla, E.; Perez, G. (Consiglio Nazionale delle Ricerche, Rome (Italy). Ist. di Chimica Nucleare)

    1990-01-01

    Tritiated napththylium ions, generated by spontaneous {beta}-decay of (1,4-{sup 3}H) naphthalene, have been allowed to react with benzene molecules in gaseous and liquid phase. The isomeric phenylnaphthalenes and fluoranthene have been found among the reaction products. The differences between the reactivity pattern of naphthylium ion in the two phases can be explained by the different efficiency of collisional stabilization of the excited reaction intermediates. (orig.).

  7. Superior activity of non-interacting close acidic protons in Al-rich Pt/H-*BEA zeolite in isomerization of n-hexane

    Czech Academy of Sciences Publication Activity Database

    Sazama, Petr; Kaucký, Dalibor; Morávková, Jaroslava; Pilař, Radim; Klein, Petr; Pastvová, Jana; Tabor, Edyta; Sklenák, Štěpán; Jakubec, Ivo; Mokrzycki, Lukasz

    2017-01-01

    Roč. 533, MAR 2017 (2017), s. 28-37 ISSN 0926-860X R&D Projects: GA ČR GA15-12113S; GA MŠk(CZ) LM2015073 Institutional support: RVO:61388955 ; RVO:61388980 Keywords : Isomerization * Alkanes Hexane * Zeolites * Al-rich beta (*BEA) * Mordenite Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T) OBOR OECD: Physical chemistry; Inorganic and nuclear chemistry (UACH-T) Impact factor: 4.339, year: 2016

  8. Determination of the quadrupole moment of the fission-isomeric state in 238U by a modified charge-plunger method

    International Nuclear Information System (INIS)

    Pedersen, J.; Goerlach, U.; Habs, D.; Just, M.; Metag, V.; Mosler, E.; Schukraft, J.; Singer, P.; Specht, H.J.; Ulfert, G.

    1978-01-01

    A modified version of the charge plunger method has been developed which, by utilizing electrostatic fields, renders possible the separation of low- and high-charge recoil ions over short flight distances. With this technique the quadrupole moment of the 200 ns fission isomer in 238 U has been determined to be (29 +- 3) b. The corresponding deformation of c/a = (1.8 +- 0.1) provides another quantitative proof for shape isomerism in the actinide region. (orig.) [de

  9. Tautomerism and isomerism in some antitrichinellosis active benzimidazoles: Morphological study in polarized light, quantum chemical computations

    Science.gov (United States)

    Anichina, Kameliya; Mavrova, Anelia; Yancheva, Denitsa; Tsenov, Jordan; Dimitrov, Rasho

    2017-12-01

    (6)-substituted-1H-benzimidazol-2-thiols crystallized in two different crystal structures while the unsubstituted 1H-benzimidazol-2-thiol possess one type of crystal structure.

  10. The Humanitarian Bailment of Foreign Possessed Territories: A Proactive Method of Legal Analysis

    Science.gov (United States)

    1996-04-01

    entrusts an employee with the employer’s lawn mower to mow the employer’s lawn .220 This is analogous to the permissive entry situation where a host...accompanying text. 82 If an employee feloniously takes the lawn mower from the employer’s place of business to the employee’s house the servant has...committed larceny because the employee never had 230possession of the mower, only custody. If the employee picked up the lawn mower from the repair

  11. Optimal Scheduling of Railway Track Possessions in Large-Scale Projects with Multiple Construction Works

    DEFF Research Database (Denmark)

    Li, Rui; Roberti, Roberto

    2017-01-01

    satisfying different operational constraints and minimizing the total construction cost. To find an optimal solution of the RTPSP, this paper proposes an approach that, first, transfers the nominal market prices into track-possession-based real prices, and then generates a schedule of the construction works...... by solving a mixed-integer linear-programming model for the given track blocking proposal. The proposed approach is tested on a real-life case study from the Danish railway infrastructure manager. The results show that, in 2 h of computing time, the approach is able to provide solutions that are within 0...

  12. Power, slavery, and spirit possession in East Africa: A few reflections

    Directory of Open Access Journals (Sweden)

    Beatrice Nicolini

    2014-02-01

    Full Text Available Spirit possession and its relationship with power aims to offer here a better understanding not only of East African societies, but, most of all, of their historical role in numerous political and military conflicts and also within peace-building processes that represent a continuation of a topic of longstanding concern in East African history. The relationships between religions, local cultures and institutional powers throughout contemporary East African history will be re-read through regional and transnational, as well as international dynamics.

  13. The Lived Space: Possession, Ownership, and Land Sales on the Chilean Frontier (Valdivia, 1790-1830

    Directory of Open Access Journals (Sweden)

    Manuel Bastias Saavedra

    2018-01-01

    Full Text Available By looking into sales of indigenous land in the territory of Valdivia between 1790 and 1830, this article discusses how legal interactions were tied to the local spaces of rural habitation. Since ownership was linked with possession and use in Spanish colonial law, local social relations and shared local knowledge were crucial for determining legal ownership and ensuring the validity of land transfers. This article provides insights into how law operated in newly integrated colonial spaces, and reveals that land transfers did not yet constitute purely contractual relations but were instead socially negotiated transactions involving different levels of authority and dependency.

  14. Differential Selectivity of the Escherichia coli Cell Membrane Shifts the Equilibrium for the Enzyme-Catalyzed Isomerization of Galactose to Tagatose▿

    Science.gov (United States)

    Kim, Jin-Ha; Lim, Byung-Chul; Yeom, Soo-Jin; Kim, Yeong-Su; Kim, Hye-Jung; Lee, Jung-Kul; Lee, Sook-Hee; Kim, Seon-Won; Oh, Deok-Kun

    2008-01-01

    An Escherichia coli galactose kinase gene knockout (ΔgalK) strain, which contains the l-arabinose isomerase gene (araA) to isomerize d-galactose to d-tagatose, showed a high conversion yield of tagatose compared with the original galK strain because galactose was not metabolized by endogenous galactose kinase. In whole cells of the ΔgalK strain, the isomerase-catalyzed reaction exhibited an equilibrium shift toward tagatose, producing a tagatose fraction of 68% at 37°C, whereas the purified l-arabinose isomerase gave a tagatose equilibrium fraction of 36%. These equilibrium fractions are close to those predicted from the measured equilibrium constants of the isomerization reaction catalyzed in whole cells and by the purified enzyme. The equilibrium shift in these cells resulted from the higher uptake and lower release rates for galactose, which is a common sugar substrate, than for tagatose, which is a rare sugar product. A ΔmglB mutant had decreased uptake rates for galactose and tagatose, indicating that a methylgalactoside transport system, MglABC, is the primary contributing transporter for the sugars. In the present study, whole-cell conversion using differential selectivity of the cell membrane was proposed as a method for shifting the equilibrium in sugar isomerization reactions. PMID:18263746

  15. Differential selectivity of the Escherichia coli cell membrane shifts the equilibrium for the enzyme-catalyzed isomerization of galactose to tagatose.

    Science.gov (United States)

    Kim, Jin-Ha; Lim, Byung-Chul; Yeom, Soo-Jin; Kim, Yeong-Su; Kim, Hye-Jung; Lee, Jung-Kul; Lee, Sook-Hee; Kim, Seon-Won; Oh, Deok-Kun

    2008-04-01

    An Escherichia coli galactose kinase gene knockout (DeltagalK) strain, which contains the l-arabinose isomerase gene (araA) to isomerize d-galactose to d-tagatose, showed a high conversion yield of tagatose compared with the original galK strain because galactose was not metabolized by endogenous galactose kinase. In whole cells of the DeltagalK strain, the isomerase-catalyzed reaction exhibited an equilibrium shift toward tagatose, producing a tagatose fraction of 68% at 37 degrees C, whereas the purified l-arabinose isomerase gave a tagatose equilibrium fraction of 36%. These equilibrium fractions are close to those predicted from the measured equilibrium constants of the isomerization reaction catalyzed in whole cells and by the purified enzyme. The equilibrium shift in these cells resulted from the higher uptake and lower release rates for galactose, which is a common sugar substrate, than for tagatose, which is a rare sugar product. A DeltamglB mutant had decreased uptake rates for galactose and tagatose, indicating that a methylgalactoside transport system, MglABC, is the primary contributing transporter for the sugars. In the present study, whole-cell conversion using differential selectivity of the cell membrane was proposed as a method for shifting the equilibrium in sugar isomerization reactions.

  16. Measurement of excitation functions and analysis of isomeric population in some reactions induced by proton on natural indium at low energy

    Science.gov (United States)

    Muhammed Shan, P. T.; Musthafa, M. M.; Najmunnisa, T.; Mohamed Aslam, P.; Rajesh, K. K.; Hajara, K.; Surendran, P.; Nair, J. P.; Shanbagh, Anil; Ghugre, S.

    2018-06-01

    The excitation functions for reaction residues populated via 115In(p , p) 115 mIn, 115In(p , pn) 114 mIn, 115In(p , p 2 n) 113 mIn, 113In(p , p) 113 mIn, 115In(p , nα) 111 mCd, 115In(p , 3 n) 113Sn and 113In(p , n) 113Sn channels were measured over the proton energy range of 8-22 MeV using stacked foil activation technique. Theoretical analysis of the data were performed within the framework of two statistical model codes EMPIRE-3.2 and TALYS-1.8. Isomeric cross section ratio for isomeric pairs m,g 115In, m,g 114In, m,g 113In, 113Sn m,g and m,g 111Cd were determined for the first time. The dependence of isomeric cross section ratio on various factors are analysed.

  17. EFFECT OF TIME AND TEMPERATURE ON ISOMERIZATION REACTION OF ?-PINENEUSING CATALYST ZR 4+ Nanik Wijayati, Supartono, Nuni Widiarti, Tri Handayani /NATURAL ZEOLITE

    Directory of Open Access Journals (Sweden)

    Nanik Wijayati

    2016-03-01

    Full Text Available Effects of time and temperature on ?-pinene isomerization reaction using catalysts Zr/natural zeolitewas studied. Characterization of the catalysts include: crystallinity, observed using X-Ray Diffraction, count Zr 4+ carried observed using X-Ray Fluorescence, area and porosity catalyst was observed using the Surface Area Analyzer, and acidity catalyst observed through gravimetric method. Isomerization reaction carried out in a batch reactor with temperature variations 90, 120 and 150 C and reaction time variations of 60, 90, 120, 150 and 180 minutes. Best results of isomerisation in this study was obtained at 150 derajat C with a reaction time of 180 minutes. Kindsof isomer obtained was observed using GCMS. Catalyst characterization results indicate that modification of the catalyst by cation Zr increases the acidity from 2.76 to 6.64 mmol/g and does not damage the crystal structure significantly. The highest product conversion in this research is 9.24%, less than the maximum results caused by pre-treatment of the catalyst produces a low area. Thus, temperature and reaction time affect the concentration of ? pinene isomerization product in addition to the effect of the catalyst used.

  18. Photoionization and trans-to-cis isomerization of β-cyclodextrin-encapsulated azobenzene induced by two-color two-laser-pulse excitation.

    Science.gov (United States)

    Takeshita, Tatsuya; Hara, Michihiro

    2018-03-15

    Azobenzene (1) and the complex resulting from the incorporation of 1 with cyclodextrin (1/CD) are attractive for light-driven applications such as micromachining and chemical biology tools. The highly sensitive photoresponse of 1 is crucial for light-driven applications containing both 1 and 1/CD to reach their full potential. In this study, we investigated the photoionization and trans-to-cis isomerization of 1/CD induced by one- and two-color two-laser pulse excitation. Photoionization of 1/CD, which was induced by stepwise two-photon absorption, was observed using laser pulse excitation at 266nm. Additionally, simultaneous irradiation with 266 and 532nm laser pulses increased the trans-to-cis isomerization yield (Υ t→c ) by 27%. It was concluded that the increase in Υ t→c was caused by the occurrence of trans-to-cis isomerization in the higher-energy singlet state (S n ), which was reached by S 1 →S n transition induced by laser pulse excitation at 532nm. The results of this study are potentially applicable in light-driven applications such as micromachining and chemical biology tools. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. The role of dissociation channels of excited electronic states in quantum optimal control of ozone isomerization: A three-state dynamical model

    Energy Technology Data Exchange (ETDEWEB)

    Kurosaki, Yuzuru, E-mail: kurosaki.yuzuru@jaea.go.jp [Quantum Beam Science Directorate, Tokai Research and Development Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195 (Japan); Ho, Tak-San, E-mail: tsho@Princeton.EDU [Department of Chemistry, Princeton University, Princeton, NJ 08544 (United States); Rabitz, Herschel, E-mail: hrabitz@Princeton.EDU [Department of Chemistry, Princeton University, Princeton, NJ 08544 (United States)

    2016-05-01

    The prospect of performing the open → cyclic ozone isomerization has attracted much research attention. Here we explore this consideration theoretically by performing quantum optimal control calculations to demonstrate the important role that excited-state dissociation channels could play in the isomerization transformation. In the calculations we use a three-state, one-dimensional dynamical model constructed from the lowest five {sup 1}A′ potential energy curves obtained with high-level ab initio calculations. Besides the laser field-dipole couplings between all three states, this model also includes the diabatic coupling between the two excited states at an avoided crossing leading to competing dissociation channels that can further hinder the isomerization process. The present three-state optimal control simulations examine two possible control pathways previously considered in a two-state model, and reveal that only one of the pathways is viable, achieving a robust ∼95% yield to the cyclic target in the three-state model. This work represents a step towards an ultimate model for the open → cyclic ozone transformation capable of giving adequate guidance about the necessary experimental control field resources as well as an estimate of the ro-vibronic spectral character of cyclic ozone as a basis for an appropriate probe of its formation.

  20. Assessment of Management Competencies Possessed by Postgraduate University Business Education Students to Handle Entrepreneurship Business Challenges in Nigeria

    Science.gov (United States)

    Okoro, James

    2015-01-01

    University Business Education graduates, by the nature of their programme, ought to possess relevant management competencies for successful entrepreneurship but casual observation and empirical reports indicate that they are not doing well in this aspect. Therefore, this study assessed the management competencies possessed by the university…

  1. 75 FR 58993 - Migratory Bird Hunting; Late Seasons and Bag and Possession Limits for Certain Migratory Game Birds

    Science.gov (United States)

    2010-09-24

    ... Part V Department of the Interior Fish and Wildlife Service 50 CFR Part 20 Migratory Bird Hunting; Late Seasons and Bag and Possession Limits for Certain Migratory Game Birds; Final Rule #0;#0;Federal...-1231-9BPP-L2] RIN 1018-AX06 Migratory Bird Hunting; Late Seasons and Bag and Possession Limits for...

  2. 26 CFR 1.937-3 - Income effectively connected with the conduct of a trade or business in a possession.

    Science.gov (United States)

    2010-04-01

    ... operates an active financing business from offices in, Possession I. Interests in G are owned by D, a bona... of a trade or business in a possession. 1.937-3 Section 1.937-3 Internal Revenue INTERNAL REVENUE... United States § 1.937-3 Income effectively connected with the conduct of a trade or business in a...

  3. Assessment of Accounting Competencies Possessed by Postgraduate University Business Education Students to Handle Entrepreneurship Business Challenges in Nigeria

    Science.gov (United States)

    Okoro, James

    2014-01-01

    University Business Education graduates, by the nature of their programme, ought to possess relevant accounting competencies for successful entrepreneurship but casual observation and empirical reports indicate that they are not doing well in this aspect. Therefore, this study assessed the accounting competencies possessed by university…

  4. Hierarchical remote data possession checking method based on massive cloud files

    Directory of Open Access Journals (Sweden)

    Ma Haifeng

    2017-06-01

    Full Text Available Cloud storage service enables users to migrate their data and applications to the cloud, which saves the local data maintenance and brings great convenience to the users. But in cloud storage, the storage servers may not be fully trustworthy. How to verify the integrity of cloud data with lower overhead for users has become an increasingly concerned problem. Many remote data integrity protection methods have been proposed, but these methods authenticated cloud files one by one when verifying multiple files. Therefore, the computation and communication overhead are still high. Aiming at this problem, a hierarchical remote data possession checking (hierarchical-remote data possession checking (H-RDPC method is proposed, which can provide efficient and secure remote data integrity protection and can support dynamic data operations. This paper gives the algorithm descriptions, security, and false negative rate analysis of H-RDPC. The security analysis and experimental performance evaluation results show that the proposed H-RDPC is efficient and reliable in verifying massive cloud files, and it has 32–81% improvement in performance compared with RDPC.

  5. Resolution No. 96/03 About possession of ionic smoke detectors

    International Nuclear Information System (INIS)

    2004-01-01

    The resolution states that: first: all the entities of the country having Ionic smoke detectors in use are to be communicated to the National Center for Nuclear safety in correspondence with the format that is shown in the annex to the present. This formation must be updated every three years. Second: Entities possessing Ionic smoke detectors in use, must be corresponding management as radioactive waste of such detectors in the term of one year from the entry into force of this resolution with the center of protection and of radiation hygiene purposes ensure safe and proper management as radioactive material into disuse. Third: Importing entities, distributors, and that made the Assembly of ionic smoke detectors, continue to be governed by the provisions of the resolution No.. 25/98 of this Ministry, R ules for the authorization of practices associated the employment of las radiation ionizing . Fourth: Entities in which ionic smoke detectors are installed must complete information according to the annex to the present format and send it to the National Center for Nuclear safety within a period of 30 days from the installation of such detectors. Fifth: Entities that possess Ionic smoke detectors and decide to continue using them should not be the evacuation of the same with the center of protection and hygiene of radiation, for the purpose of ensuring a safe and proper management as radioactive material in disuse, notifying this Act to the National Center for Nuclear safety.

  6. The effects of solvents and structure on the electronic absorption spectra of the isomeric pyridine carboxylic acid N-oxides

    Directory of Open Access Journals (Sweden)

    Drmanić Saša Ž.

    2013-01-01

    Full Text Available The ultraviolet absorption spectra of the carboxyl group of three isomeric pyridine carboxylic acids N-oxides (picolinic acid N-oxide, nicotinic acid N-oxide and isonicotinic acid N-oxide were determined in fourteen solvents in the wavelength range from 200 to 400 nm. The position of the absorption maxima (λmax of the examined acids showed that the ultraviolet absorption maximum wavelengths of picolinic acid N-oxide are the shortest, and those of isonicotinic acid N-oxide acid are the longest. In order to analyze the solvent effect on the obtained absorption spectra, the ultraviolet absorption frequencies of the electronic transitions in the carboxylic group of the examined acids were correlated using a total solvatochromic equation of the form max = v0 + sπ + aα+ bβ, where υmax is the absorption frequency (1/λmax, p is a measure of the solvent polarity, β represents the scale of solvent hydrogen bond acceptor basicities and α represent the scale of solvent hydrogen bond donor acidities. The correlation of the spectroscopic data was carried out by means of multiple linear regression analysis. The solvent effects on the ultraviolet absorption maximums of the examined acids were discussed.

  7. Chirality- and pH-Controlled Supramolecular Isomerism in Cobalt Phosphonates and Its Impact on the Magnetic Behavior.

    Science.gov (United States)

    Feng, Jian-Shen; Bao, Song-Song; Ren, Min; Cai, Zhong-Sheng; Zheng, Li-Min

    2015-11-23

    Two pairs of enantiomeric compounds with formulas (S)- or (R)-Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅4 H2 O [(S)-1 or (R)-1], (S)- or (R)-Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅3 H2 O [(S)- or (R)-2), and related racemic compound Co3 (ppap)2 (4,4'-bpy)2 (H2 O)2 ⋅4 H2 O (rac-3; 4,4'-bpy=4,4'-bipyridine, H3 ppap=3-phenyl-2-[(phosphonomethyl)amino]propanoic acid) are reported. Compounds 1 and rac-3 show identical three-dimensional framework structures, whereas compounds 2 have two-dimensional layer structures. Compounds 1 and 2 are catenation isomers, formation of which is controlled solely by the pH of the reaction mixtures, whereas the formation of isomeric compounds 1 and rac-3 is controlled purely by the chirality of the phosphonate ligand. The magnetic properties of fully dehydrated (S)-1, (S)-2, and rac-3 are highly dependent on both structure and chirality. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Gamma radiation and temperature influence on the chemical effect produced by isomeric transition in the telluric acid

    International Nuclear Information System (INIS)

    Muriel G, M.

    1976-01-01

    When the gamma radiation due to the isomeric transition is internally converted an autoionization is produced. For atoms with a high atomic number this autoionization can be a large one and produce a fragmentation in a molecule. In the specific case of the solid state these fragments remain trapped in different places of the crystalline system. This can be considered as chemical change in the original molecule. These damages produced by the nuclear transformation can be measured by different methods: heating, gamma rays, pressure, etc. In this work the results of an experimental measurement of the behavior of the crystalline telluric acid molecule fragments under gamma radiation (0 to 20 Mrads) with controlled temperature of 2 0 C (-196 0 C to 50 0 C) it is presented. It was observed that the values of the mentioned behavior vary rapidly at first for relatively low doses and that for larger doses these values remained constant. Besides with a lower temperature these variation are progressively lower. (author)

  9. Elution-extrusion counter-current chromatography for the separation of two pairs of isomeric monoterpenes from Paeoniae Alba Radix.

    Science.gov (United States)

    Chu, Chu; Zhang, Shidi; Tong, Shengqiang; Li, Xingnuo; Li, Qingyong; Yan, Jizhong

    2015-09-01

    In this work, a simple and efficient protocol for the rapid separation of two pairs of isomeric monoterpenes from Paeoniae Alba Radix was developed by combining macroporous resin and elution-extrusion counter-current chromatography. The crude extract was firstly subjected to a D101 macroporous resin column eluted with water and a series of different concentrations of ethanol. Then, effluents of 30 and 95% ethanol were collected as sample 1 and sample 2 for further counter-current chromatography purification. Finally, a pair of isomers, 96 mg of compound 1 and 48 mg of compound 2 with purities of 91.1 and 96.2%, respectively, was isolated from 200 mg of sample 1. The other pair of isomers, 14 mg of compound 3 and 8 mg of compound 4 with purities of 93.6 and 88.9%, respectively, was isolated from 48 mg of sample 2. Their purities were analyzed by high-performance liquid chromatography, and their chemical structures were identified by mass spectrometry and (1) H NMR spectroscopy. Compared to a normal counter-current chromatography separation, the separation time and solvent consumption of elution-extrusion counter-current chromatography were reduced while the resolutions were still good. The established protocol is promising for the separation of natural products with great disparity of content in herbal medicines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Observation of an isomeric level in 239U by means of the 238U(n,γ)239U reaction

    International Nuclear Information System (INIS)

    Thomas, B.W.; Murray, J.; Rae, E.R.

    1970-01-01

    Low-energy-capture gamma-ray spectra ( 238 U up to a neutron energy of 350 eV. The data were obtained using a 25-cm 3 Ge(Li) detector at the Harwell 45 MeV Electron Linac. Capture events were recorded as functions of gamma-ray energy and neutron time-of-flight, and by suitable analysis of the data time-of-flight spectra have been obtained for individual gamma-rays. The strongest low-energy gamma-ray, at 134 keV, depopulates a level in 239 U at the same energy by an E2-transition to the ground state. The time-of-flight spectrum for this transition indicates that the 134-keV level is isomeric with a half-life of approximately 1 microsecond. This is evident from the long tails on the low-energy side of each resonance, which are not present for other regions of the gamma-ray spectrum. The possibility of using low-energy gamma-rays as a measure of the total capture cross-section is investigated by comparing the time-of-flight spectrum for the 134-keV transition with that for a Moxon-Rae detector under the same experimental conditions. (author)

  11. Remind of the classification of some known isomeric transitions; Rappel de la classification des transitions isomeriques connues

    Energy Technology Data Exchange (ETDEWEB)

    Ballini, R; Levi, C; Papineau, L [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1953-07-01

    Relations of Berthelot (model of the liquid drop) and of Weisskopf (odd core to 'single' proton), between l'energie of a transition and her 'partial period' of emission of a {alpha} photon, are represented by easily usable diagrams. These relations are compared to the empiric relations for a certain number of groups of transitions. With regard to the M4 transitions, a rectification is given to the mode of treatment of the experimental results who had been proposed by Goldhaber and SUNYAR (1951). A test of systematic has been done, concerning the energy of isomeric transitions (grouping around some energies, variation of the nature, and of the energy of the transitions with Z, N and A). (author) [French] Les relations de Berthelot (modele de la goutte liquide) et de Weisskopf (noyau impair a proton ''celibataire''), entre l'energie d'une transition et la ''periode partielle'' d'emission d'un photon {alpha}, sont representees par des graphiques facilement utilisables. Ces relations sont comparees aux relations empiriques pour un certain nombre de groupes de transitions. En ce qui concerne les transitions M4, une rectification est donnee au mode de traitement des resultats experimentaux qui avait ete propose par GOLDHABER et SUNYAR (1951). Un essai de systematique a ete effectue, concernant l'energie des transitions isomeriques (groupement autour de certaines energies, variation de la nature et de l'energie des transitions avec Z, N et A). (auteur)

  12. Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

    Energy Technology Data Exchange (ETDEWEB)

    D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Liu, Jiumeng; Shilling, John E.; Lee, Ben Hwan; Kjaergaard, Henrik G.; Thornton, Joel A.

    2017-04-11

    We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

  13. Photonic crystals possessing multiple Weyl points and the experimental observation of robust surface states

    Science.gov (United States)

    Chen, Wen-Jie; Xiao, Meng; Chan, C. T.

    2016-01-01

    Weyl points, as monopoles of Berry curvature in momentum space, have captured much attention recently in various branches of physics. Realizing topological materials that exhibit such nodal points is challenging and indeed, Weyl points have been found experimentally in transition metal arsenide and phosphide and gyroid photonic crystal whose structure is complex. If realizing even the simplest type of single Weyl nodes with a topological charge of 1 is difficult, then making a real crystal carrying higher topological charges may seem more challenging. Here we design, and fabricate using planar fabrication technology, a photonic crystal possessing single Weyl points (including type-II nodes) and multiple Weyl points with topological charges of 2 and 3. We characterize this photonic crystal and find nontrivial 2D bulk band gaps for a fixed kz and the associated surface modes. The robustness of these surface states against kz-preserving scattering is experimentally observed for the first time. PMID:27703140

  14. Novel Imidazopyridine Derivatives Possess Anti-Tumor Effect on Human Castration-Resistant Prostate Cancer Cells.

    Directory of Open Access Journals (Sweden)

    Matthew A Ingersoll

    Full Text Available Prostate cancer (PCa is the second leading cause of cancer-related death afflicting United States males. Most treatments to-date for metastatic PCa include androgen-deprivation therapy and second-generation anti-androgens such as abiraterone acetate and enzalutamide. However, a majority of patients eventually develop resistance to these therapies and relapse into the lethal, castration-resistant form of PCa to which no adequate treatment option remains. Hence, there is an immediate need to develop effective therapeutic agents toward this patient population. Imidazopyridines have recently been shown to possess Akt kinase inhibitory activity; thus in this study, we investigated the inhibitory effect of novel imidazopyridine derivatives HIMP, M-MeI, OMP, and EtOP on different human castration-resistant PCa cells. Among these compounds, HIMP and M-MeI were found to possess selective dose- and time-dependent growth inhibition: they reduced castration-resistant PCa cell proliferation and spared benign prostate epithelial cells. Using LNCaP C-81 cells as the model system, these compounds also reduced colony formation as well as cell adhesion and migration, and M-MeI was the most potent in all studies. Further investigation revealed that while HIMP primarily inhibits PCa cell growth via suppression of PI3K/Akt signaling pathway, M-MeI can inhibit both PI3K/Akt and androgen receptor pathways and arrest cell growth in the G2 phase. Thus, our results indicate the novel compound M-MeI to be a promising candidate for castration-resistant PCa therapy, and future studies investigating the mechanism of imidazopyridine inhibition may aid to the development of effective anti-PCa agents.

  15. Novel Imidazopyridine Derivatives Possess Anti-Tumor Effect on Human Castration-Resistant Prostate Cancer Cells.

    Science.gov (United States)

    Ingersoll, Matthew A; Lyons, Anastesia S; Muniyan, Sakthivel; D'Cunha, Napoleon; Robinson, Tashika; Hoelting, Kyle; Dwyer, Jennifer G; Bu, Xiu R; Batra, Surinder K; Lin, Ming-Fong

    2015-01-01

    Prostate cancer (PCa) is the second leading cause of cancer-related death afflicting United States males. Most treatments to-date for metastatic PCa include androgen-deprivation therapy and second-generation anti-androgens such as abiraterone acetate and enzalutamide. However, a majority of patients eventually develop resistance to these therapies and relapse into the lethal, castration-resistant form of PCa to which no adequate treatment option remains. Hence, there is an immediate need to develop effective therapeutic agents toward this patient population. Imidazopyridines have recently been shown to possess Akt kinase inhibitory activity; thus in this study, we investigated the inhibitory effect of novel imidazopyridine derivatives HIMP, M-MeI, OMP, and EtOP on different human castration-resistant PCa cells. Among these compounds, HIMP and M-MeI were found to possess selective dose- and time-dependent growth inhibition: they reduced castration-resistant PCa cell proliferation and spared benign prostate epithelial cells. Using LNCaP C-81 cells as the model system, these compounds also reduced colony formation as well as cell adhesion and migration, and M-MeI was the most potent in all studies. Further investigation revealed that while HIMP primarily inhibits PCa cell growth via suppression of PI3K/Akt signaling pathway, M-MeI can inhibit both PI3K/Akt and androgen receptor pathways and arrest cell growth in the G2 phase. Thus, our results indicate the novel compound M-MeI to be a promising candidate for castration-resistant PCa therapy, and future studies investigating the mechanism of imidazopyridine inhibition may aid to the development of effective anti-PCa agents.

  16. Association between socio-economic status and childhood undernutrition in Bangladesh; a comparison of possession score and poverty index.

    Science.gov (United States)

    Mohsena, Masuda; Mascie-Taylor, C G Nicholas; Goto, Rie

    2010-10-01

    To determine how much of the variation in nutritional status of Bangladeshi children under 5 years old can be attributed to the socio-economic status of the family. Nutritional status used reference Z-scores of weight-for-age (WAZ), height-for-age (HAZ) and weight-for-height (WHZ). A 'possession score' was generated based on ownership of a radio, television, bicycle, motorcycle and telephone, and the availability of electricity, with categories of 0 to 4+ possessions. A five-point (quintile) 'poverty index' was created using principal component analysis. The Bangladesh Demographic and Health Survey 2004 was the source of data. A sample of 4891 children aged <5 years was obtained. Some 57.8 % of the sample was either stunted, wasted or underweight (7.7 % were stunted, wasted and underweight). Of those stunted (48.4 %), 25.7 % were also underweight. Underweight and wasting prevalences were 40.7 % and 14.3 %, respectively. Mean WAZ, HAZ and WHZ did not differ by sex. Children of mothers with no education or no possessions were, on average, about 1 sd more underweight and stunted than those with higher educated mothers or with 4+ possessions. The possession score provided much greater discrimination of undernutrition than the poverty index. Nearly 50 % of children from households with no possessions were stunted, wasted or underweight (only 27 % in the poorest quintile), compared with only 3-6 % of children from households with 4+ possessions (over 13 % in the richest quintile). Maternal education and possession score were the main predictors of a child's nutritional status. Possession score was a much better indicator of undernutrition than the poverty index.

  17. Review: Lisa Mackenrodt, Swahili Spirit Possession and Islamic Healing in Contemporary Tanzania: The Jinn Fly on Friday (2011 Buchbesprechung: Lisa Mackenrodt, Swahili Spirit Possession and Islamic Healing in Contemporary Tanzania: The Jinn Fly on Friday (2011

    Directory of Open Access Journals (Sweden)

    Jigal Beez

    2013-01-01

    Full Text Available Review of the monograph:Lisa Mackenrodt, Swahili Spirit Possession and Islamic Healing in Contemporary Tanzania: The Jinn Fly on Friday, Hamburg: Verlag Dr. Kovač, 2011, ISBN 978-3-8300-5806-9, 216 pagesBesprechung der Monographie:Lisa Mackenrodt, Swahili Spirit Possession and Islamic Healing in Contemporary Tanzania: The Jinn Fly on Friday, Hamburg: Verlag Dr. Kovač, 2011, ISBN 978-3-8300-5806-9, 216 Seiten

  18. Visually impaired researchers get their hands on quantum chemistry: application to a computational study on the isomerization of a sterol

    Science.gov (United States)

    Lounnas, Valère; Wedler, Henry B.; Newman, Timothy; Schaftenaar, Gijs; Harrison, Jason G.; Nepomuceno, Gabriella; Pemberton, Ryan; Tantillo, Dean J.; Vriend, Gert

    2014-11-01

    In molecular sciences, articles tend to revolve around 2D representations of 3D molecules, and sighted scientists often resort to 3D virtual reality software to study these molecules in detail. Blind and visually impaired (BVI) molecular scientists have access to a series of audio devices that can help them read the text in articles and work with computers. Reading articles published in this journal, though, is nearly impossible for them because they need to generate mental 3D images of molecules, but the article-reading software cannot do that for them. We have previously designed AsteriX, a web server that fully automatically decomposes articles, detects 2D plots of low molecular weight molecules, removes meta data and annotations from these plots, and converts them into 3D atomic coordinates. AsteriX-BVI goes one step further and converts the 3D representation into a 3D printable, haptic-enhanced format that includes Braille annotations. These Braille-annotated physical 3D models allow BVI scientists to generate a complete mental model of the molecule. AsteriX-BVI uses Molden to convert the meta data of quantum chemistry experiments into BVI friendly formats so that the entire line of scientific information that sighted people take for granted—from published articles, via printed results of computational chemistry experiments, to 3D models—is now available to BVI scientists too. The possibilities offered by AsteriX-BVI are illustrated by a project on the isomerization of a sterol, executed by the blind co-author of this article (HBW).

  19. Orientation dependence in collision induced electronic relaxation studied through van der Waals complexes with isomeric structures. Invited feature article

    International Nuclear Information System (INIS)

    Cheng, P.Y.; Lapierre, L.; Ju, S.S.; DeRose, P.; Dai, H.L.

    1994-01-01

    Weakly bound molecular complexes with more than one well-defined structures provide us with an unique opportunity to investigate dynamic processes induced by intermolecular interactions with specific orientations. The relative orientation of the two interacting molecules or atoms is defined by the complex structure. The effect of the orientation in the spin changing collisions glyoxal (S 1 ) + Ar → glyoxal (T 1 ) + Ar and acetylene (S 1 ) + Ar → acetylene (T) + Ar have been studied by measuring the intersystem crossing (ISC) rates of the glyoxal(S 1 ).Ar and acetylene(S 1 ).Ar complexes with different isomeric structures. Results show that there is a strong orientation dependence in the ISC of glyoxal(S 1 ) induced by interaction with the Ar atom: the Ar atom positioned in the molecular plane is much more effective than in the out-of-plane position in inducing the S 1 → T 1 transition of glyoxal. On the other hand, studies of acetylene(S 1 ).Ar complexes indicate that the Ar-induced ISC rates are nearly identical for the in-plane and out-of-plane positions. Orientation dependence in the collision induced vibrational relaxation process C 2 H 2 (S 1 , v i ) + Ar → C 2 H 2 (S 1 , v f i ) + Ar is also studied by measuring the vibrational predissociation rates of the acetylene(S 1 ).Ar complex isomers. The results indicate that collisions of C 2 H 2 (S 1 , v 3 = 3, 4) with Ar at two orthogonal orientations are equally effective in causing vibrational relaxation of C 2 H 2 . (orig.)

  20. The incidence and characteristics of supraventricular tachycardia in left atrial isomerism: a high incidence of atrial fibrillation in young patients.

    Science.gov (United States)

    Miyazaki, Aya; Sakaguchi, Heima; Ohuchi, Hideo; Yamamoto, Tetsuya; Igarashi, Takehiro; Negishi, Jun; Toyota, Naoki; Kagisaki, Koji; Yagihara, Toshikatsu; Yamada, Osamu

    2013-06-20

    In left atrial isomerism (LAI), both atria show left atrial morphology. Although bradyarrhythmias are frequent and highly complex in LAI patients, previous studies have reported a low incidence of supraventricular tachycardia (SVT). To evaluate the incidence and characteristics of SVT in LAI, we retrospectively evaluated the clinical characteristics of SVTs in 83 patients with LAI (age at last follow-up, 15.3±10.5 years). There were 27 SVTs in 19 patients (23%), including nine episodes of atrial fibrillation (AF) and eight non-reentrant SVTs. Sixteen of the 19 patients with SVT had histories of atriotomy, but the three patients with AF or non-reentrant tachycardia had no history of atriotomy. The rates of freedom from SVT were 66% and 59% at ages of 20 and 30 years, respectively; the corresponding rates for freedom from AF were 89% and 74%. In multivariate analysis, the predictors of SVT were age (OR, 1.14; 95% CI, 1.06-1.26; p=0.003) and sinus node dysfunction (SND) (OR, 3.88; 95% CI, 1.57-13.34; p=0.01). In patients with LAI, SVTs are common, and AF and non-reentrant SVTs are the major type of SVTs. The incidence of AF was high in young patients with LAI. The lack of anatomical barriers in the atria that allow the formation of macro-reentrant circuits may account for the higher incidence of AF and non-reentrant SVT than macro-reentrant tachycardia. Moreover, the increasing prevalence of SND with age should contribute to a higher incidence of SVT. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  1. A hydrogen-bonding network is important for oxidation and isomerization in the reaction catalyzed by cholesterol oxidase

    International Nuclear Information System (INIS)

    Lyubimov, Artem Y.; Chen, Lin; Sampson, Nicole S.; Vrielink, Alice

    2009-01-01

    The importance of active-site electrostatics for oxidative and reductive half-reactions in a redox flavoenzyme (cholesterol oxidase) have been investigated by a combination of biochemistry and atomic resolution crystallography. A detailed examination of active-site dynamics demonstrates that the oxidation of substrate and the re-oxidation of the flavin cofactor by molecular oxygen are linked by a single active-site asparagine. Cholesterol oxidase is a flavoenzyme that catalyzes the oxidation and isomerization of 3β-hydroxysteroids. Structural and mutagenesis studies have shown that Asn485 plays a key role in substrate oxidation. The side chain makes an NH⋯π interaction with the reduced form of the flavin cofactor. A N485D mutant was constructed to further test the role of the amide group in catalysis. The mutation resulted in a 1800-fold drop in the overall k cat . Atomic resolution structures were determined for both the N485L and N485D mutants. The structure of the N485D mutant enzyme (at 1.0 Å resolution) reveals significant perturbations in the active site. As predicted, Asp485 is oriented away from the flavin moiety, such that any stabilizing interaction with the reduced flavin is abolished. Met122 and Glu361 form unusual hydrogen bonds to the functional group of Asp485 and are displaced from the positions they occupy in the wild-type active site. The overall effect is to disrupt the stabilization of the reduced FAD cofactor during catalysis. Furthermore, a narrow transient channel that is shown to form when the wild-type Asn485 forms the NH⋯π interaction with FAD and that has been proposed to function as an access route of molecular oxygen, is not observed in either of the mutant structures, suggesting that the dynamics of the active site are altered

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

    Science.gov (United States)

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

    2016-09-15

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

  3. Dissociative trance disorder: clinical and Rorschach findings in ten persons reporting demon possession and treated by exorcism.

    Science.gov (United States)

    Ferracuti, S; Sacco, R; Lazzari, R

    1996-06-01

    Although dissociative trance disorders, especially possession disorder, are probably more common than is usually though, precise clinical data are lacking. Ten persons undergoing exorcisms for devil trance possession state were studied with the Dissociative Disorders Diagnostic Schedule and the Rorschach test. These persons had many traits in common with dissociative identity disorder patients. They were overwhelmed by paranormal experiences. Despite claiming possession by a demon, most of them managed to maintain normal social functioning. Rorschach findings showed that these persons had a complex personality organization: Some of them displayed a tendency to oversimplify stimulus perception whereas others seemed more committed to psychological complexity. Most had severe impairment of reality testing, and 6 of the participants had an extratensive coping stile. In this group of persons reporting demon possession, dissociative trance disorder seems to be a distinct clinical manifestation of a dissociative continuum, sharing some features with dissociative identity disorder.

  4. Global mental health and trauma exposure: the current evidence for the relationship between traumatic experiences and spirit possession.

    Science.gov (United States)

    Hecker, Tobias; Braitmayer, Lars; van Duijl, Marjolein

    2015-01-01

    We present a literature review on trauma exposure and spirit possession in low- and middle-income countries (LMICs). Despite the World Health Organization's objective of culturally appropriate mental health care in the Mental Health Action Plan 2013-2020, and the recommendations of the Inter-Agency Standing Committee to consider local idioms of distress and to collaborate with local resources, this topic still receives very little attention. Pathological spirit possession is commonly defined as involuntary, uncontrollable, and occurring outside of ritual settings. It is often associated with stigmatization, suffering, and dysfunctional behavior. While spirit possession has been discussed as an idiom of distress in anthropological literature, recent quantitative studies have presented support for a strong relationship between traumatic experiences and pathological possession states. The aim of this review was to investigate this relationship systematically in LMICs, in view of the debate on how to address the mental health gap in LMICs. Twenty-one articles, published in peer-reviewed English-language journals between 1994 and 2013, were identified and analyzed with regard to prevalence of possessive trance disorders, patients' sociodemographic characteristics, and its relation to traumatic experiences. The review and analysis of 917 patients with symptoms of possessive trance disorders from 14 LMICs indicated that it is a phenomenon occurring worldwide and with global relevance. This literature review suggests a strong relationship between trauma exposure and spirit possession with high prevalence rates found especially in postwar areas in African countries. More attention for possessive trance disorders in mental health and psychosocial intervention programs in humanitarian emergency settings as well as in societies in transition in LMICs is needed and justified by the results of this systematic literature review.

  5. Global mental health and trauma exposure: the current evidence for the relationship between traumatic experiences and spirit possession

    Science.gov (United States)

    Hecker, Tobias; Braitmayer, Lars; van Duijl, Marjolein

    2015-01-01

    Background We present a literature review on trauma exposure and spirit possession in low- and middle-income countries (LMICs). Despite the World Health Organization's objective of culturally appropriate mental health care in the Mental Health Action Plan 2013–2020, and the recommendations of the Inter-Agency Standing Committee to consider local idioms of distress and to collaborate with local resources, this topic still receives very little attention. Pathological spirit possession is commonly defined as involuntary, uncontrollable, and occurring outside of ritual settings. It is often associated with stigmatization, suffering, and dysfunctional behavior. While spirit possession has been discussed as an idiom of distress in anthropological literature, recent quantitative studies have presented support for a strong relationship between traumatic experiences and pathological possession states. Objective The aim of this review was to investigate this relationship systematically in LMICs, in view of the debate on how to address the mental health gap in LMICs. Methods Twenty-one articles, published in peer-reviewed English-language journals between 1994 and 2013, were identified and analyzed with regard to prevalence of possessive trance disorders, patients’ sociodemographic characteristics, and its relation to traumatic experiences. Results The review and analysis of 917 patients with symptoms of possessive trance disorders from 14 LMICs indicated that it is a phenomenon occurring worldwide and with global relevance. This literature review suggests a strong relationship between trauma exposure and spirit possession with high prevalence rates found especially in postwar areas in African countries. Conclusions More attention for possessive trance disorders in mental health and psychosocial intervention programs in humanitarian emergency settings as well as in societies in transition in LMICs is needed and justified by the results of this systematic literature review

  6. Global mental health and trauma exposure: the current evidence for the relationship between traumatic experiences and spirit possession

    Directory of Open Access Journals (Sweden)

    Tobias Hecker

    2015-11-01

    Full Text Available Background: We present a literature review on trauma exposure and spirit possession in low- and middle-income countries (LMICs. Despite the World Health Organization's objective of culturally appropriate mental health care in the Mental Health Action Plan 2013–2020, and the recommendations of the Inter-Agency Standing Committee to consider local idioms of distress and to collaborate with local resources, this topic still receives very little attention. Pathological spirit possession is commonly defined as involuntary, uncontrollable, and occurring outside of ritual settings. It is often associated with stigmatization, suffering, and dysfunctional behavior. While spirit possession has been discussed as an idiom of distress in anthropological literature, recent quantitative studies have presented support for a strong relationship between traumatic experiences and pathological possession states. Objective: The aim of this review was to investigate this relationship systematically in LMICs, in view of the debate on how to address the mental health gap in LMICs. Methods: Twenty-one articles, published in peer-reviewed English-language journals between 1994 and 2013, were identified and analyzed with regard to prevalence of possessive trance disorders, patients’ sociodemographic characteristics, and its relation to traumatic experiences. Results: The review and analysis of 917 patients with symptoms of possessive trance disorders from 14 LMICs indicated that it is a phenomenon occurring worldwide and with global relevance. This literature review suggests a strong relationship between trauma exposure and spirit possession with high prevalence rates found especially in postwar areas in African countries. Conclusions: More attention for possessive trance disorders in mental health and psychosocial intervention programs in humanitarian emergency settings as well as in societies in transition in LMICs is needed and justified by the results of this

  7. Silver Nanoparticles Complexed with Bovine Submaxillary Mucin Possess Strong Antibacterial Activity and Protect against Seedling Infection.

    Science.gov (United States)

    Makarovsky, Daria; Fadeev, Ludmila; Salam, Bolaji Babajide; Zelinger, Einat; Matan, Ofra; Inbar, Jacob; Jurkevitch, Edouard; Gozin, Michael; Burdman, Saul

    2018-02-15

    A simple method for the synthesis of nanoparticles (NPs) of silver (Ag) in a matrix of bovine submaxillary mucin (BSM) was reported previously by some of the authors of this study. Based on mucin characteristics such as long-lasting stability, water solubility, and surfactant and adhesive characteristics, we hypothesized that these compounds, named BSM-Ag NPs, may possess favorable properties as potent antimicrobial agents. The goal of this study was to assess whether BSM-Ag NPs possess antibacterial activity, focusing on important plant-pathogenic bacterial strains representing both Gram-negative ( Acidovorax and Xanthomonas ) and Gram-positive ( Clavibacter ) genera. Growth inhibition and bactericidal assays, as well as electron microscopic observations, demonstrate that BSM-Ag NPs, at relatively low concentrations of silver, exert strong antimicrobial effects. Moreover, we show that treatment of melon seeds with BSM-Ag NPs effectively prevents seed-to-seedling transmission of Acidovorax citrulli , one of the most threatening pathogens of cucurbit production worldwide. Overall, our findings demonstrate strong antimicrobial activity of BSM-Ag NPs and their potential application for reducing the spread and establishment of devastating bacterial plant diseases in agriculture. IMPORTANCE Bacterial plant diseases challenge agricultural production, and the means available to manage them are limited. Importantly, many plant-pathogenic bacteria have the ability to colonize seeds, and seed-to-seedling transmission is a critical route by which bacterial plant diseases spread to new regions and countries. The significance of our study resides in the following aspects: (i) the simplicity of the method of BSM-Ag NP synthesis, (ii) the advantageous chemical properties of BSM-Ag NPs, (iii) the strong antibacterial activity of BSM-Ag NPs at relatively low concentrations of silver, and (iv) the fact that, in contrast to most studies on the effects of metal NPs on plant pathogens

  8. Nuclear isomerism in fission fragments produced by the spontaneous fission of {sup 252}Cf; Isomerisme nucleaire dans les fragments de fission produits dans la fission spontanee du {sup 252}Cf

    Energy Technology Data Exchange (ETDEWEB)

    Gautherin, C

    1997-09-01

    This thesis is devoted to the study of the nuclear structure of neutron-rich nuclei, via the search of isomeric nuclear states. Neutron-rich nuclei were produced in the spontaneous fission of {sup 252}Cf. The experimental study of isomeric states in these nuclei was performed with the {gamma}-array EUROGAM II, coupled to an additional and original fission fragment detector composed by photovoltaic cells, SAPhIR. The photovoltaic cells are well adapted to detect low energy heavy ions and have good energy and time resolutions to obtain a good fission fragment detection. This experiment led to the discovery of new isomeric states in {sup 135}Xe, {sup 104}Mo, {sup 146,147,148}Ce and {sup 152,154,156}Nd, with lifetimes between 60 ns and 2 {mu}s. Level schemes of these nuclei have been completed. An interpretation of the isomeric states in the nuclei {sup 154,156}Nd and {sup 156,158}Sm was performed by Hartree-Fock-Bogolyubov calculations using the DIS Gogny force with two quasi-particles excitations. The confrontation with the experimental results led to an interpretation of these isomeric states as K-isomers. (author)

  9. The possession game? A comparative analysis of ball retention and team success in European and international football, 2007-2010.

    Science.gov (United States)

    Collet, Christian

    2013-01-01

    Possession is thought of as central to success in modern football, but questions remain about its impact on positive team outcomes (Bate, 1988; Hughes & Franks, 2005; Pollard & Reep, 1997; Stanhope, 2001). Recent studies (e.g. Bloomfield, Polman, & O'Donoghue, 2005; Carling, Williams, & Reilly, 2005; James, Mellallieu, & Holley, 2002; Jones, James, & Mellalieu, 2004; Lago, 2009; Lago & Martin, 2007; Lago-Peñas & Dellal, 2010; Lago-Peñas, Lago-Ballesteros, Dellal, & Gómez, 2010; Taylor, Mellalieu, & James, 2005; Tucker, Mellalieu, James, & Taylor, 2005) that have examined these questions have often been constrained by an exclusive focus on English or Spanish domestic play. Using data from five European leagues, UEFA and FIFA tournaments, the study found that while possession time and passing predicted aggregated team success in domestic league play, both variables were poor predictors at the individual match level once team quality and home advantage were accounted for. In league play, the effect of greater possession was consistently negative; in the Champions League, it had virtually no impact. In national team tournaments, possession failed to reach significance when offensive factors were accounted for. Much of the success behind the 'possession game' was thus a function of elite teams confined in geographic and competitive space. That ball hegemony was not consistently tied to success suggests that a nuanced approach to possession is needed to account for variant strategic environments (e.g. James et al., 2002) and compels match analysts to re-examine the metric's overall value.

  10. Cis-to- Trans Isomerization of Azobenzene Derivatives Studied with Transition Path Sampling and Quantum Mechanical/Molecular Mechanical Molecular Dynamics.

    Science.gov (United States)

    Muždalo, Anja; Saalfrank, Peter; Vreede, Jocelyne; Santer, Mark

    2018-04-10

    Azobenzene-based molecular photoswitches are becoming increasingly important for the development of photoresponsive, functional soft-matter material systems. Upon illumination with light, fast interconversion between a more stable trans and a metastable cis configuration can be established resulting in pronounced changes in conformation, dipole moment or hydrophobicity. A rational design of functional photosensitive molecules with embedded azo moieties requires a thorough understanding of isomerization mechanisms and rates, especially the thermally activated relaxation. For small azo derivatives considered in the gas phase or simple solvents, Eyring's classical transition state theory (TST) approach yields useful predictions for trends in activation energies or corresponding half-life times of the cis isomer. However, TST or improved theories cannot easily be applied when the azo moiety is part of a larger molecular complex or embedded into a heterogeneous environment, where a multitude of possible reaction pathways may exist. In these cases, only the sampling of an ensemble of dynamic reactive trajectories (transition path sampling, TPS) with explicit models of the environment may reveal the nature of the processes involved. In the present work we show how a TPS approach can conveniently be implemented for the phenomenon of relaxation-isomerization of azobenzenes starting with the simple examples of pure azobenzene and a push-pull derivative immersed in a polar (DMSO) and apolar (toluene) solvent. The latter are represented explicitly at a molecular mechanical (MM) and the azo moiety at a quantum mechanical (QM) level. We demonstrate for the push-pull azobenzene that path sampling in combination with the chosen QM/MM scheme produces the expected change in isomerization pathway from inversion to rotation in going from a low to a high permittivity (explicit) solvent model. We discuss the potential of the simulation procedure presented for comparative calculation of

  11. Does the copolymer poly(vinylidene cyanide-tricyanoethylene) possess piezoelectricity?

    Science.gov (United States)

    Wang, Zhi-Yin; Su, Ke-He; Xu, Qiong

    2012-10-01

    The geometry, energy, internal rotation barrier, dipole moment, and molecular polarizability of the α- and β-chain models of poly(vinylidene cyanide-tricyanoethylene) [P(VDCN-TrCN)] were studied with density functional theory at the B3PW91/6-31G(d) level. The effects of the chain length and the TrCN content on the copolymer chain stability, the chain conformation, and the electrical properties of P(VDCN-TrCN) were examined and compared with those of poly(vinylidene fluoride-trifluoroethylene) and PVDCN to gauge whether P(VDCN-TrCN) would be expected to possess substantial piezoelectricity. The results of this study showed that the stability of the β conformation increases and the energy difference per monomer unit between the β- and α-chains decreases with increasing TrCN. However, introducing TrCN into VDCN will not significantly enhance the radius of curvature of the P(VDCN-TrCN) chains. The average dipole moment per monomer unit in the β-chain is affected by the chain curvature and the TrCN content. The amount of piezoelectricity present in P(VDCN-TrCN) is slightly smaller than that in PVDCN, and is less than that in poly(vinylidene fluoride-trifluoroethylene).

  12. Steady nanofluid flow with variable fluid possessions over a linearly extending surface: A Lie group exploration

    Directory of Open Access Journals (Sweden)

    Kalidas Das

    2018-03-01

    Full Text Available The temperament of stream characteristic, heat and mass transfer of MHD forced convective flow over a linearly expanding porous medium has been scrutinized in the progress exploration. The germane possessions of the liquid like viscosity along with thermal conductivity are believed to be variable in nature, directly influenced by the temperature of flow. As soon as gaining the system of leading equations of the stream, Lie symmetric group transformations have been employed to come across the fitting parallel conversions to alter the central PDEs into a suit of ODEs. The renovated system of ODE with appropriate boundary conditions is numerically solved with the assistance of illustrative software MAPLE 17. The consequences of the relevant factors of the system have been exemplified through charts and graphs. An analogous qualified survey has been prepared among present inquiry and subsisting reads and achieved an admirable accord between them. The variable viscosity parameter has more significant effect on nanofluid velocity than regular fluid and temporal profile as well as nanoparticle concentration is also influenced with variable viscosity. Keywords: Nanofluid, Stretching sheet, Variable viscosity, Variable thermal conductivity, Lie symmetry group

  13. Facile approach to the fabrication of a micropattern possessing nanoscale substructure.

    Science.gov (United States)

    Ji, Qiang; Jiang, Xuesong; Yin, Jie

    2007-12-04

    On the basis of the combined technologies of photolithography and reaction-induced phase separation (RIPS), a facile approach has been successfully developed for the fabrication of a micropattern possessing nanoscale substructure on the thin film surface. This approach involves three steps. In the first step, a thin film was prepared by spin coating from a solution of a commercial random copolymer, polystyrene-r-poly(methyl methacrylate) (PS-r-PMMA) and a commercial crosslinker, trimethylolpropane triacrylate (TMPTA). In the second step, photolithograph was performed with the thin film using a 250 W high-pressure mercury lamp to produce the micropattern. Finally, the resulting micropattern was annealed at 200 degrees C for a certain time, and reaction-induced phase separation occurred. After soaking in chloroform for 4 h, nanoscale substructure was obtained. The whole processes were traced by atomic force microscopy (AFM), X-ray photoelectron spectrometry (XPS), and Fourier transform infrared (FTIR) spectroscopy, and the results supported the proposed structure.

  14. Highly tilted liquid crystalline materials possessing a direct phase transition from antiferroelectric to isotropic phase

    Energy Technology Data Exchange (ETDEWEB)

    Milewska, K.; Drzewiński, W. [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Czerwiński, M., E-mail: mczerwinski@wat.edu.pl [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Dąbrowski, R. [Institute of Chemistry, Military University of Technology, 00-908 Warsaw (Poland); Piecek, W. [Institute of Applied Physics, Military University of Technology, 00-908 Warsaw (Poland)

    2016-03-01

    Pure compounds and multicomponent mixtures with a broad temperature range of high tilted liquid crystalline antiferroelectric phase and a direct phase transition from antiferroelectric to isotropic phase, were obtained. X-ray diffraction analysis confirms these kinds of materials form a high tilted anticlinic phase, with a fixed layer spacing and very weak dependency upon temperature, after the transition from the isotropic phase. Due to this, not only pure orthoconic antiferroelectric liquid crystals but also those with a moderate tilt should generate a good dark state. Furthermore, due to the increased potential for forming anticlinic forces, such materials could minimize a commonly observed asymmetry of a rise and fall switching times at a surface stabilized geometry. - Highlights: • The new class of liquid crystalline materials with the direct SmC{sub A}*. • Iso phase transition were obtained. • Materials possess the layer spacing fixed and very weak dependent upon temperature. • Smectic layers without shrinkage are observed. • A good dark state can be generate in SSAFLC.

  15. Skeletal muscle myoblasts possess a stretch-responsive local angiotensin signalling system.

    Science.gov (United States)

    Johnston, Adam P W; Baker, Jeff; De Lisio, Michael; Parise, Gianni

    2011-06-01

    A paucity of information exists regarding the presence of local renin-angiotensin systems (RASs) in skeletal muscle and associated muscle stem cells. Skeletal muscle and muscle stem cells were isolated from C57BL/6 mice and examined for the presence of a local RAS using quantitative reverse transcriptase polymerase chain reaction (qRT-PCR), immunohistochemistry (IHC), Western blotting and liquid chromatography-mass spectrometry (LC-MS). Furthermore, the effect of mechanical stimulation on RAS member gene expression was analysed. Whole skeletal muscle, primary myoblasts and C2C12 derived myoblasts and myotubes differentially expressed members of the RAS including angiotensinogen, angiotensin-converting enzyme (ACE), angiotensin II (Ang II) type 1 (AT(1)) and type 2 (AT(2)). Renin transcripts were never detected, however, mRNA for the 'renin-like' enzyme cathepsin D was observed and Ang I and Ang II were identified in cell culture supernatants from proliferating myoblasts. AT(1) appeared to co-localise with polymerised actin filaments in proliferating myoblasts and was primarily found in the nucleus of terminally differentiated myotubes. Furthermore, mechanical stretch of proliferating and differentiating C2C12 cells differentially induced mRNA expression of angiotensinogen, AT(1) and AT(2). Proliferating and differentiated muscle stem cells possess a local stress-responsive RAS in vitro. The precise function of a local RAS in myoblasts remains unknown. However, evidence presented here suggests that Ang II may be a regulator of skeletal muscle myoblasts.

  16. Criminal history and future offending of juveniles convicted of the possession of child pornography.

    Science.gov (United States)

    Aebi, Marcel; Plattner, Belinda; Ernest, Melanie; Kaszynski, Katie; Bessler, Cornelia

    2014-08-01

    Most child pornography is distributed online. It is estimated that 3% to 15% of child pornography consumers are juveniles. The present study analyzed a consecutive sample of 54 male juveniles convicted of the possession of child pornography. Demographic characteristics, criminal history, and subsequent offending were assessed from criminal files and official reports. Juvenile possessors of child pornography were compared to three different groups of juveniles: Juvenile possessors of other illegal pornography (n = 42), juveniles who committed a sexual contact offense against a child (n = 64), and juveniles who committed a sexual contact offense against a peer or adult (n = 104). Juvenile possessors of child pornography were found to have downloaded the illegal material more frequently and over a longer time period than juvenile possessors of other illegal pornography. Furthermore, juvenile possessors of child pornography differed from juveniles who had committed a sexual contact offense in terms of demographics and showed fewer previous and subsequent offending than juveniles who sexually offended against a peer or adult. We conclude that juvenile possessors of child pornography need a specific target intervention focusing on dysfunctional Internet use and sexually deviant arousal. © The Author(s) 2013.

  17. Tribological and corrosion behaviour of electroless Ni-B coating possessing a blackberry like structure

    Science.gov (United States)

    Bülbül, Ferhat; Altun, Hikmet; Küçük, Özkan; Ezirmik, Vefa

    2012-08-01

    This study aims to evaluate the tribological and corrosion properties of the electroless Ni-B coating deposited on AISI 304 stainless steels. The microstructure of the coating was characterized using x-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectrometry (SEM-EDS). XRD analysis revealed that the prepared coating possessed an amorphous character. SEM-EDS investigation also indicated that a non-stoichiometric Ni-B coating was deposited with a columnar growth mechanism on the stainless steel substrate and the morphology of the growth surface was blackberry-like. The hardness and tribological properties were characterized by microhardness and a pin-on-disc wear test. The electroless Ni-B coated sample had a higher degree of hardness, a lower friction coefficient and a lower wear rate than the uncoated substrate. The electrochemical potentiodynamic polarization method was used to evaluate the corrosion resistance of the coating. The electroless Ni-B coating offered cathodic protection on the substrate by acting as a sacrificial anode although it was electrochemically more reactive than the stainless steel substrate.

  18. Stereotypes possess heterogeneous directionality: a theoretical and empirical exploration of stereotype structure and content.

    Science.gov (United States)

    Cox, William T L; Devine, Patricia G

    2015-01-01

    We advance a theory-driven approach to stereotype structure, informed by connectionist theories of cognition. Whereas traditional models define or tacitly assume that stereotypes possess inherently Group → Attribute activation directionality (e.g., Black activates criminal), our model predicts heterogeneous stereotype directionality. Alongside the classically studied Group → Attribute stereotypes, some stereotypes should be bidirectional (i.e., Group ⇄ Attribute) and others should have Attribute → Group unidirectionality (e.g., fashionable activates gay). We tested this prediction in several large-scale studies with human participants (NCombined = 4,817), assessing stereotypic inferences among various groups and attributes. Supporting predictions, we found heterogeneous directionality both among the stereotype links related to a given social group and also between the links of different social groups. These efforts yield rich datasets that map the networks of stereotype links related to several social groups. We make these datasets publicly available, enabling other researchers to explore a number of questions related to stereotypes and stereotyping. Stereotype directionality is an understudied feature of stereotypes and stereotyping with widespread implications for the development, measurement, maintenance, expression, and change of stereotypes, stereotyping, prejudice, and discrimination.

  19. A novel dioxygenation product of arachidonic acid possesses potent chemotactic activity for human polymorphonuclear leukocytes.

    Science.gov (United States)

    Shak, S; Perez, H D; Goldstein, I M

    1983-12-25

    We have found that a novel dioxygenation product of arachidonic acid, 8(S),15(S)-dihydroxy-5,11-cis-9,13-trans-eicosatetraenoic acid (8,15-diHETE), possesses chemotactic activity for human polymorphonuclear leukocytes comparable to that of leukotriene B4. Authentic 8,15-diHETE, identified by gas chromatography-mass spectrometry, was prepared by treating arachidonic acid with soybean lipoxygenase and was purified by reverse-phase high performance liquid chromatography. Using a "leading front" assay, 8,15-diHETE exhibited significant chemotactic activity at a concentration of 5.0 ng/ml. Maximum chemotactic activity was observed at a concentration of 30 ng/ml. The 8,15-diHETE generated by mixed human leukocytes after stimulation with arachidonic acid and the calcium ionophore, A23187, exhibited quantitatively similar chemotactic activity. Two synthetic all-trans conjugated isomers of 8,15-diHETE, however, were not chemotactic at concentrations up to 500 ng/ml. In contrast to its potent chemotactic activity, 8,15-diHETE (at concentrations up to 10 micrograms/ml) was relatively inactive with respect to its ability to provoke either degranulation or generation of superoxide anion radicals by cytochalasin B-treated leukocytes. Both leukotriene B4 and 8,15-diHETE may be important mediators of inflammation.

  20. Mild one-pot Horner-Wadsworth-Emmons olefination and intramolecular N-arylation for the syntheses of indoles, all regio-isomeric azaindoles, and thienopyrroles.

    Science.gov (United States)

    Choi, Ji Hye; Lim, Hwan Jung

    2015-05-14

    The syntheses of various N-protected aromatic-ring fused pyrrole-2-carboxylate derivatives have been accomplished using mild one-pot Horner-Wadsworth-Emmons olefination and Cu-catalyzed intramolecular N-arylation reactions. The optimized mild one-pot reaction conditions of various 2-bromo arylcarboxaldehydes with commercially available N-protected phosphonoglycine trimethylesters gave the desired aromatic-ring fused pyrrole-2-carboxylates, such as substituted indole-, all regio-isomeric azaindole-, and thienopyrrole-2-carboxylates, in good to excellent yields. These conditions showed broad substrate compatibility, without the loss of the protecting group.

  1. Form coexistence in light krypton nuclei. Isomeric spectroscopy of 72,74Kr nuclei and Coulomb excitation of the 76Kr radioactive beam

    International Nuclear Information System (INIS)

    Bouchez, Emmanuelle

    2003-01-01

    The first part of this research thesis proposes an overview of the different theoretical calculations elaborated in the region of light krypton nuclei, and of published experimental results. The second part reports the electron and gamma isomeric spectroscopy of 72,74 Kr nuclei after fragmentation of the projectile by a magnetic separator (experimental installation, experimental results, discussion). The third part reports the study of the Coulomb excitation of the 76 Kr radioactive beam (method and experimental installation, data analysis and results in terms of germanium and silicon spectra, and form of the 76 Kr)

  2. Experiences of possession and paranormal phenomena among women in the general population: are they related to traumatic stress and dissociation?

    Science.gov (United States)

    Sar, Vedat; Alioğlu, Firdevs; Akyüz, Gamze

    2014-01-01

    This study sought to determine the prevalence of experiences of possession and paranormal phenomena (PNP) in the general population and their possible relations to each other and to traumatic stress and dissociation. The study was conducted on a representative female sample recruited from a town in central eastern Turkey. The Dissociative Disorders Interview Schedule, the posttraumatic stress disorder (PTSD) and borderline personality disorder sections of the Structured Clinical Interviews for DSM-IV Axis-I and Personality Disorders, and the Childhood Abuse and Neglect Questionnaire were administered to 628 women. Of these, 127 (20.2%) women reported at least 1 type of PNP and 13 (2.1%) women reported possession. Women with a dissociative disorder reported all types of possession and PNP (except telepathy) more frequently than those without. Whereas women with a trauma history in childhood and adulthood or PTSD reported possession more frequently than those without, PNP were associated with childhood trauma only. Factor analysis yielded 4 dimensions: possession by and/or contact with nonhuman entities, extrasensory communications, possession by a human entity, and precognition. These factors correlated with number of secondary features of dissociative identity disorder and Schneiderian symptoms. Latent class analysis identified 3 groups. The most traumatized group, with predominantly dissociative and trauma-related disorders, had the highest scores on all factors. Notwithstanding their presence in healthy individuals, possession and PNP were associated with trauma and dissociation in a subgroup of affected participants. Both types of experience seem to be normal human capacities of experiencing that may be involved in response to traumatic stress. Given the small numbers, this study should be considered preliminary.

  3. Characterizing the Effective Bandwidth of Nonlinear Vibratory Energy Harvesters Possessing Multiple Stable Equilibria

    Science.gov (United States)

    Panyam Mohan Ram, Meghashyam

    In the last few years, advances in micro-fabrication technologies have lead to the development of low-power electronic devices spanning critical fields related to sensing, data transmission, and medical implants. Unfortunately, effective utilization of these devices is currently hindered by their reliance on batteries. In many of these applications, batteries may not be a viable choice as they have a fixed storage capacity and need to be constantly replaced or recharged. In light of such challenges, several novel concepts for micro-power generation have been recently introduced to harness, otherwise, wasted ambient energy from the environment and maintain these low-power devices. Vibratory energy harvesting is one such concept which has received significant attention in recent years. While linear vibratory energy harvesters have been well studied in the literature and their performance metrics have been established, recent research has focused on deliberate introduction of stiffness nonlinearities into the design of these devices. It has been shown that, nonlinear energy harvesters have a wider steady-state frequency bandwidth as compared to their linear counterparts, leading to the premise that they can used to improve performance, and decrease sensitivity to variations in the design and excitation parameters. This dissertation aims to investigate this premise by developing an analytical framework to study the influence of stiffness nonlinearities on the performance and effective bandwidth of nonlinear vibratory energy harvesters. To achieve this goal, the dissertation is divided into three parts. The first part investigates the performance of bi-stable energy harvesters possessing a symmetric quartic potential energy function under harmonic excitations and carries out a detailed analysis to define their effective frequency bandwidth. The second part investigates the relative performance of mono- and bi-stable energy harvesters under optimal electric loading

  4. Novel rod-shaped viruses isolated from garlic, Allium sativum, possessing a unique genome organization.

    Science.gov (United States)

    Sumi, S; Tsuneyoshi, T; Furutani, H

    1993-09-01

    Rod-shaped flexuous viruses were partially purified from garlic plants (Allium sativum) showing typical mosaic symptoms. The genome was shown to be composed of RNA with a poly(A) tail of an estimated size of 10 kb as shown by denaturing agarose gel electrophoresis. We constructed cDNA libraries and screened four independent clones, which were designated GV-A, GV-B, GV-C and GV-D, using Northern and Southern blot hybridization. Nucleotide sequence determination of the cDNAs, two of which correspond to nearly one-third of the virus genomic RNA, shows that all of these viruses possess an identical genomic structure and that also at least four proteins are encoded in the viral cDNA, their M(r)s being estimated to be 15K, 27K, 40K and 11K. The 15K open reading frame (ORF) encodes the core-like sequence of a zinc finger protein preceded by a cluster of basic amino acid residues. The 27K ORF probably encodes the viral coat protein (CP), based on both the existence of some conserved sequences observed in many other rod-shaped or flexuous virus CPs and an overall amino acid sequence similarity to potexvirus and carlavirus CPs. The 11K ORF shows significant amino acid sequence similarities to the corresponding 12K proteins of the potexviruses and carlaviruses. On the other hand, the 40K ORF product does not resemble any other plant virus gene products reported so far. The genomic organization in the 3' region of the garlic viruses resembles, but clearly differs from, that of carlaviruses. Phylogenetic analysis based upon the amino acid sequence of the viral capsid protein also indicates that the garlic viruses have a unique and distinct domain different from those of the potexvirus and carlavirus groups. The results suggest that the garlic viruses described here belong to an unclassified and new virus group closely related to the carlaviruses.

  5. To have and to hold: possessing the sacred in the late renaissance

    Directory of Open Access Journals (Sweden)

    Erin E. Benay

    2015-02-01

    Full Text Available Private devotional art of the early 17th century often found its place in the galleries of noblemen and women whose diverse collections were symbols not only of stylistic taste, but of their owners’ exhaustive curiosity. In these domestic settings, boundaries between sacred and secular were permeable, as the unprecedented physical intimacy portrayed in popular religious subjects such as St Matthew and the Angel, the Stigmatisation of St Francis, or Christ’s Agony in the Garden reveal. Representations of the latter reminded viewers of Christ’s human, corporal suffering and suggested a model of resolve strengthened by prayer. The Agony in the Garden appears on the interior of Jacopo Ligozzi’s virtuosic Portable Altar with Carrying Case (1608, likely a Medici gift presented to the Austrian court in anticipation of the marriage of archduchess Maria Maddalena to soon-to-be grand duke Cosimo II. Adorned with lavish botanical motifs on its exterior, the Altar’s potency as a sacred possession was redoubled by the owner’s tactile revelation of the portrayal of Christ supported by an Angel contained inside the case. Comprised of wood, oil on copper, and pietre dure inlay, it is an object intended to be held, opened, and experienced. This paper suggests that Ligozzi’s selective combination of sumptuous materials and choice of subject matter – botanical illustration and Christological iconography – allowed the object to appeal to the full sensorium, and therefore to function as efficaciously as a devotional aid as it did as a curiosity among other rare collectibles.

  6. Bacillus sp.CDB3 isolated from cattle dip-sites possesses two ars gene clusters

    Institute of Scientific and Technical Information of China (English)

    Somanath Bhat; Xi Luo; Zhiqiang Xu; Lixia Liu; Ren Zhang

    2011-01-01

    Contamination of soil and water by arsenic is a global problem.In Australia, the dipping of cattle in arsenic-containing solution to control cattle ticks in last centenary has left many sites heavily contaminated with arsenic and other toxicants.We had previously isolated five soil bacterial strains (CDB1-5) highly resistant to arsenic.To understand the resistance mechanism, molecular studies have been carried out.Two chromosome-encoded arsenic resistance (ars) gene clusters have been cloned from CDB3 (Bacillus sp.).They both function in Escherichia coli and cluster 1 exerts a much higher resistance to the toxic metalloid.Cluster 2 is smaller possessing four open reading frames (ORFs) arsRorf2BC, similar to that identified in Bacillus subtilis Skin element.Among the eight ORFs in cluster 1 five are analogs of common ars genes found in other bacteria, however, organized in a unique order arsRBCDA instead of arsRDABC.Three other putative genes are located directly downstream and designated as arsTIP based on the homologies of their theoretical translation sequences respectively to thioredoxin reductases, iron-sulphur cluster proteins and protein phosphatases.The latter two are novel of any known ars operons.The arsD gene from Bacillus species was cloned for the first time and the predict protein differs from the well studied E.coli ArsD by lacking two pairs of C-terrninal cysteine residues.Its functional involvement in arsenic resistance has been confirmed by a deletion experiment.There exists also an inverted repeat in the intergenic region between arsC and arsD implying some unknown transcription regulation.

  7. Exosomes carring gag/env of ALV-J possess negative effect on immunocytes.

    Science.gov (United States)

    Wang, Guihua; Wang, Zhenzhen; Zhuang, Pingping; Zhao, Xiaomin; Cheng, Ziqiang

    2017-11-01

    J subgroup avian leukosis virus (ALV-J) is an exogenous retrovirus of avian. A key feature of ALV-J infection is leading to severe immunosuppressive characteristic of diseases. Viral components of retrovirus were reported closely associated with immunosuppression, and several similarities between exosomes and retrovirus preparations have lead to the hypotheses of retrovirus hijacker exosomes pathway. In this study, we purified exosomes from DF-1 cells infected and uninfected by ALV-J. Electron microscopy and mass spectrometry (MS) analysis showed that ALV-J not only increased the production of exosomes from ALV-J infected DF-1 cells (Exo-J) but also stimulated some proteins expression, especially ALV-J components secreted in exosomes. Immunosuppressive domain peptide (ISD) of envelope subunit transmembrane (TM) and gag of ALV-J were secreted in Exo-J. It has been reported that HIV gag was budded from endosome-like domains of the T cell plasma membrane. But env protein was first detected in exosomes from retrovirus infected cells. We found that Exo-J caused negative effects on splenocytes in a dose-dependant manner by flow cytometric analysis. And low dose of Exo-J activated immune activity of splenocytes, while high dose possessed immunosuppressive properties. Interestingly, Exo-J has no significant effects on the immunosuppression induced by ALV-J, and the immunosuppressive effects induced by Exo-J lower than that by ALV-J. Taken together, our data indicated that Exo-J supplied a microenvironment for the replication and transformation of ALV-J. Copyright © 2017. Published by Elsevier Ltd.

  8. Audio-visual interactions uniquely contribute to resolution of visual conflict in people possessing absolute pitch.

    Directory of Open Access Journals (Sweden)

    Sujin Kim

    Full Text Available Individuals possessing absolute pitch (AP are able to identify a given musical tone or to reproduce it without reference to another tone. The present study sought to learn whether this exceptional auditory ability impacts visual perception under stimulus conditions that provoke visual competition in the form of binocular rivalry. Nineteen adult participants with 3-19 years of musical training were divided into two groups according to their performance on a task involving identification of the specific note associated with hearing a given musical pitch. During test trials lasting just over half a minute, participants dichoptically viewed a scrolling musical score presented to one eye and a drifting sinusoidal grating presented to the other eye; throughout the trial they pressed buttons to track the alternations in visual awareness produced by these dissimilar monocular stimuli. On "pitch-congruent" trials, participants heard an auditory melody that was congruent in pitch with the visual score, on "pitch-incongruent" trials they heard a transposed auditory melody that was congruent with the score in melody but not in pitch, and on "melody-incongruent" trials they heard an auditory melody completely different from the visual score. For both groups, the visual musical scores predominated over the gratings when the auditory melody was congruent compared to when it was incongruent. Moreover, the AP participants experienced greater predominance of the visual score when it was accompanied by the pitch-congruent melody compared to the same melody transposed in pitch; for non-AP musicians, pitch-congruent and pitch-incongruent trials yielded equivalent predominance. Analysis of individual durations of dominance revealed differential effects on dominance and suppression durations for AP and non-AP participants. These results reveal that AP is accompanied by a robust form of bisensory interaction between tonal frequencies and musical notation that boosts

  9. Rheum turkestanicum rhizomes possess anti-hypertriglyceridemic, but not hypoglycemic or hepatoprotective effect in experimental diabetes

    Directory of Open Access Journals (Sweden)

    Mousa-Al-Reza Hadjzadeh

    2017-01-01

    Full Text Available Objective: Rheum turkestanicum (R. turkestanicum rhizomes have been used in Iranain traditional medicine as an anti-diabetic agent. The purpose of the present investigation was to evaluate the anti-diabetic and antioxidant activities of R. turkestanicum rhizome extract in streptozotocin-induced diabetic rats.Materials and Methods: Diabetes was induced by a single intraperitoneal injection of 55 mg/kg streptozotocin in male Wistar rats. Diabetic rats received the decoction extract of R. turkestanicum rhizomes at the doses of 200, 400 and 600 mg/kg daily by gavage for 3 weeks. Serum glucose and lipid levels were measured in all groups before diabetes induction and at the end of week 3. Oxidative stress was evaluated in the liver by measurement of malondialdehyde levels and total thiol concentration at the end of the experiment.Results: A significant increase in serum glucose and triglyceride levels was observed in diabetic rats, which was accompanied by increased malondialdehyde levels and decreased total thiol concentration in the liver after 3 weeks. Treatment of diabetic rats with R. turkestanicum rhizome extract at the doses of 200, 400 and 600 mg/kg over a 3-week period did not change serum glucose, hepatic malondialdehyde and total thiol levels in diabetic rats. However, treatment with R. turkestanicum extract significantly decreased serum triglyceride levels in a dose-dependent manner at the end of the experiment.Conclusion: R. turkestanicum rhizome extract possess anti-hypertriglyceridemic, but not hypoglycemic or hepatoprotective effect in diabetic rats. Therefore, R. turkestanicum rhizome should be consumed with more caution by diabetic patients.

  10. Deoxyarbutin Possesses a Potent Skin-Lightening Capacity with No Discernible Cytotoxicity against Melanosomes.

    Directory of Open Access Journals (Sweden)

    Fang Miao

    Full Text Available Safe and effective ingredients capable of removing undesired hyperpigmentation from facial skin are urgently needed for both pharmaceutical and cosmetic purposes. Deoxyarbutin (4-[(tetrahydro-2H-pyran-2-yl oxy] phenol, D-Arb is a glucoside derivative of hydroquinone. Here, we investigated the toxicity and efficacy of D-Arb at the sub-cellular level (directly on melanosomes and skin pigmentation using in vivo and in vitro models to compare with its parent compound hydroquinone (1,4-benzenediol, HQ. At first, we examined the ultrastructural changes of melanosomes in hyperpigmented guinea pig skin induced by 308-nm monochromatic excimer lightand/or treated with HQ and D-Arb using transmission electron microscopy. The results showed that prominent changes in the melanosomal membrane, such as bulb-like structure and even complete rupture of the outer membranes, were found in the skin after topical application of 5% HQ for 10 days. These changes were barely observed in the skin treated with D-Arb. To further clarify whether membrane toxicity of HQ was a direct result of the compound treatment, we also examinedultrastructural changes of individual melanosomes purified from MNT1 human melanoma cells. Similar observations were obtained from the naked melanosome model in vitro. Finally, we determined the effects of melanosomal fractions exposed to HQ or D-Arb on hydroxyl radical generation in the Fenton reaction utilizing an electron spin resonance assay. D-Arb-treated melanosomesexhibit a moderate hydroxyl radical-scavenging activity, whereas HQ-treated melanosomessignificantly generate more hydroxyl free radicals. This study suggests that D-Arb possesses a potent ability in skin lightening and antioxidation with less melanosome cytotoxicity.

  11. Deoxyarbutin Possesses a Potent Skin-Lightening Capacity with No Discernible Cytotoxicity against Melanosomes.

    Science.gov (United States)

    Miao, Fang; Shi, Ying; Fan, Zhi-Feng; Jiang, Shan; Xu, Shi-Zheng; Lei, Tie-Chi

    2016-01-01

    Safe and effective ingredients capable of removing undesired hyperpigmentation from facial skin are urgently needed for both pharmaceutical and cosmetic purposes. Deoxyarbutin (4-[(tetrahydro-2H-pyran-2-yl) oxy] phenol, D-Arb) is a glucoside derivative of hydroquinone. Here, we investigated the toxicity and efficacy of D-Arb at the sub-cellular level (directly on melanosomes) and skin pigmentation using in vivo and in vitro models to compare with its parent compound hydroquinone (1,4-benzenediol, HQ). At first, we examined the ultrastructural changes of melanosomes in hyperpigmented guinea pig skin induced by 308-nm monochromatic excimer lightand/or treated with HQ and D-Arb using transmission electron microscopy. The results showed that prominent changes in the melanosomal membrane, such as bulb-like structure and even complete rupture of the outer membranes, were found in the skin after topical application of 5% HQ for 10 days. These changes were barely observed in the skin treated with D-Arb. To further clarify whether membrane toxicity of HQ was a direct result of the compound treatment, we also examinedultrastructural changes of individual melanosomes purified from MNT1 human melanoma cells. Similar observations were obtained from the naked melanosome model in vitro. Finally, we determined the effects of melanosomal fractions exposed to HQ or D-Arb on hydroxyl radical generation in the Fenton reaction utilizing an electron spin resonance assay. D-Arb-treated melanosomesexhibit a moderate hydroxyl radical-scavenging activity, whereas HQ-treated melanosomessignificantly generate more hydroxyl free radicals. This study suggests that D-Arb possesses a potent ability in skin lightening and antioxidation with less melanosome cytotoxicity.

  12. Cytotoxic protein from the mushroom Coprinus comatus possesses a unique mode for glycan binding and specificity

    Science.gov (United States)

    Zhang, Peilan; Yang, Guang; Xia, Changqing; Polston, Jane E.; Li, Gengnan; Li, Shiwu; Lin, Zhao; Yang, Li-jun; Bruner, Steven D.

    2017-01-01

    Glycans possess significant chemical diversity; glycan binding proteins (GBPs) recognize specific glycans to translate their structures to functions in various physiological and pathological processes. Therefore, the discovery and characterization of novel GBPs and characterization of glycan–GBP interactions are significant to provide potential targets for therapeutic intervention of many diseases. Here, we report the biochemical, functional, and structural characterization of a 130-amino-acid protein, Y3, from the mushroom Coprinus comatus. Biochemical studies of recombinant Y3 from a yeast expression system demonstrated the protein is a unique GBP. Additionally, we show that Y3 exhibits selective and potent cytotoxicity toward human T-cell leukemia Jurkat cells compared with a panel of cancer cell lines via inducing caspase-dependent apoptosis. Screening of a glycan array demonstrated GalNAcβ1–4(Fucα1–3)GlcNAc (LDNF) as a specific Y3-binding ligand. To provide a structural basis for function, the crystal structure was solved to a resolution of 1.2 Å, revealing a single-domain αβα-sandwich motif. Two monomers were dimerized to form a large 10-stranded, antiparallel β-sheet flanked by α-helices on each side, representing a unique oligomerization mode among GBPs. A large glycan binding pocket extends into the dimeric interface, and docking of LDNF identified key residues for glycan interactions. Disruption of residues predicted to be involved in LDNF/Y3 interactions resulted in the significant loss of binding to Jurkat T-cells and severely impaired their cytotoxicity. Collectively, these results demonstrate Y3 to be a GBP with selective cytotoxicity toward human T-cell leukemia cells and indicate its potential use in cancer diagnosis and treatment. PMID:28784797

  13. Cytotoxic protein from the mushroom Coprinus comatus possesses a unique mode for glycan binding and specificity.

    Science.gov (United States)

    Zhang, Peilan; Li, Kunhua; Yang, Guang; Xia, Changqing; Polston, Jane E; Li, Gengnan; Li, Shiwu; Lin, Zhao; Yang, Li-Jun; Bruner, Steven D; Ding, Yousong

    2017-08-22

    Glycans possess significant chemical diversity; glycan binding proteins (GBPs) recognize specific glycans to translate their structures to functions in various physiological and pathological processes. Therefore, the discovery and characterization of novel GBPs and characterization of glycan-GBP interactions are significant to provide potential targets for therapeutic intervention of many diseases. Here, we report the biochemical, functional, and structural characterization of a 130-amino-acid protein, Y3, from the mushroom Coprinus comatus Biochemical studies of recombinant Y3 from a yeast expression system demonstrated the protein is a unique GBP. Additionally, we show that Y3 exhibits selective and potent cytotoxicity toward human T-cell leukemia Jurkat cells compared with a panel of cancer cell lines via inducing caspase-dependent apoptosis. Screening of a glycan array demonstrated GalNAcβ1-4(Fucα1-3)GlcNAc (LDNF) as a specific Y3-binding ligand. To provide a structural basis for function, the crystal structure was solved to a resolution of 1.2 Å, revealing a single-domain αβα-sandwich motif. Two monomers were dimerized to form a large 10-stranded, antiparallel β-sheet flanked by α-helices on each side, representing a unique oligomerization mode among GBPs. A large glycan binding pocket extends into the dimeric interface, and docking of LDNF identified key residues for glycan interactions. Disruption of residues predicted to be involved in LDNF/Y3 interactions resulted in the significant loss of binding to Jurkat T-cells and severely impaired their cytotoxicity. Collectively, these results demonstrate Y3 to be a GBP with selective cytotoxicity toward human T-cell leukemia cells and indicate its potential use in cancer diagnosis and treatment.

  14. Mycobacterium avium Possesses Extracellular DNA that Contributes to Biofilm Formation, Structural Integrity, and Tolerance to Antibiotics.

    Directory of Open Access Journals (Sweden)

    Sasha J Rose

    Full Text Available Mycobacterium avium subsp. hominissuis is an opportunistic pathogen that is associated with biofilm-related infections of the respiratory tract and is difficult to treat. In recent years, extracellular DNA (eDNA has been found to be a major component of bacterial biofilms, including many pathogens involved in biofilm-associated infections. To date, eDNA has not been described as a component of mycobacterial biofilms. In this study, we identified and characterized eDNA in a high biofilm-producing strain of Mycobacterium avium subsp. hominissuis (MAH. In addition, we surveyed for presence of eDNA in various MAH strains and other nontuberculous mycobacteria. Biofilms of MAH A5 (high biofilm-producing strain and MAH 104 (reference strain were established at 22°C and 37°C on abiotic surfaces. Acellular biofilm matrix and supernatant from MAH A5 7 day-old biofilms both possess abundant eDNA, however very little eDNA was found in MAH 104 biofilms. A survey of MAH clinical isolates and other clinically relevant nontuberculous mycobacterial species revealed many species and strains that also produce eDNA. RAPD analysis demonstrated that eDNA resembles genomic DNA. Treatment with DNase I reduced the biomass of MAH A5 biofilms when added upon biofilm formation or to an already established biofilm both on abiotic surfaces and on top of human pharyngeal epithelial cells. Furthermore, co-treatment of an established biofilm with DNase 1 and either moxifloxacin or clarithromycin significantly increased the susceptibility of the bacteria within the biofilm to these clinically used antimicrobials. Collectively, our results describe an additional matrix component of mycobacterial biofilms and a potential new target to help treat biofilm-associated nontuberculous mycobacterial infections.

  15. E2-EPF UCP Possesses E3 Ubiquitin Ligase Activity via Its Cysteine 118 Residue.

    Science.gov (United States)

    Lim, Jung Hwa; Shin, Hee Won; Chung, Kyung-Sook; Kim, Nam-Soon; Kim, Ju Hee; Jung, Hong-Ryul; Im, Dong-Soo; Jung, Cho-Rok

    Here, we show that E2-EPF ubiquitin carrier protein (UCP) elongated E3-independent polyubiquitin chains on the lysine residues of von Hippel-Lindau protein (pVHL) and its own lysine residues both in vitro and in vivo. The initiation of the ubiquitin reaction depended on not only Lys11 linkage but also the Lys6, Lys48 and Lys63 residues of ubiquitin, which were involved in polyubiquitin chain formation on UCP itself. UCP self-association occurred through the UBC domain, which also contributed to the interaction with pVHL. The polyubiquitin chains appeared on the N-terminus of UCP in vivo, which indicated that the N-terminus of UCP contains target lysines for polyubiquitination. The Lys76 residue of UCP was the most critical site for auto-ubiquitination, whereas the polyubiquitin chain formation on pVHL occurred on all three of its lysines (Lys159, Lys171 and Lys196). A UCP mutant in which Cys118 was changed to alanine (UCPC118A) did not form a polyubiquitin chain but did strongly accumulate mono- and di-ubiquitin via auto-ubiquitination. Polyubiquitin chain formation required the coordination of Cys95 and Cys118 between two interacting molecules. The mechanism of the polyubiquitin chain reaction of UCP may involve the transfer of ubiquitin from Cys95 to Cys118 by trans-thiolation, with polyubiquitin chains forming at Cys118 by reversible thioester bonding. The polyubiquitin chains are then moved to the lysine residues of the substrate by irreversible isopeptide bonding. During the elongation of the ubiquitin chain, an active Cys118 residue is required in both parts of UCP, namely, the catalytic enzyme and the substrate. In conclusion, UCP possesses not only E2 ubiquitin conjugating enzyme activity but also E3 ubiquitin ligase activity, and Cys118 is critical for polyubiquitin chain formation.

  16. E2-EPF UCP Possesses E3 Ubiquitin Ligase Activity via Its Cysteine 118 Residue.

    Directory of Open Access Journals (Sweden)

    Jung Hwa Lim

    Full Text Available Here, we show that E2-EPF ubiquitin carrier protein (UCP elongated E3-independent polyubiquitin chains on the lysine residues of von Hippel-Lindau protein (pVHL and its own lysine residues both in vitro and in vivo. The initiation of the ubiquitin reaction depended on not only Lys11 linkage but also the Lys6, Lys48 and Lys63 residues of ubiquitin, which were involved in polyubiquitin chain formation on UCP itself. UCP self-association occurred through the UBC domain, which also contributed to the interaction with pVHL. The polyubiquitin chains appeared on the N-terminus of UCP in vivo, which indicated that the N-terminus of UCP contains target lysines for polyubiquitination. The Lys76 residue of UCP was the most critical site for auto-ubiquitination, whereas the polyubiquitin chain formation on pVHL occurred on all three of its lysines (Lys159, Lys171 and Lys196. A UCP mutant in which Cys118 was changed to alanine (UCPC118A did not form a polyubiquitin chain but did strongly accumulate mono- and di-ubiquitin via auto-ubiquitination. Polyubiquitin chain formation required the coordination of Cys95 and Cys118 between two interacting molecules. The mechanism of the polyubiquitin chain reaction of UCP may involve the transfer of ubiquitin from Cys95 to Cys118 by trans-thiolation, with polyubiquitin chains forming at Cys118 by reversible thioester bonding. The polyubiquitin chains are then moved to the lysine residues of the substrate by irreversible isopeptide bonding. During the elongation of the ubiquitin chain, an active Cys118 residue is required in both parts of UCP, namely, the catalytic enzyme and the substrate. In conclusion, UCP possesses not only E2 ubiquitin conjugating enzyme activity but also E3 ubiquitin ligase activity, and Cys118 is critical for polyubiquitin chain formation.

  17. Crystal structure of a plant albumin from Cicer arietinum (chickpea) possessing hemopexin fold and hemagglutination activity.

    Science.gov (United States)

    Sharma, Urvashi; Katre, Uma V; Suresh, C G

    2015-05-01

    Crystal structure of a reported PA2 albumin from Cicer arietinum shows that it belongs to hemopexin fold family, has four beta-propeller motifs and possesses hemagglutination activity, making it different from known legume lectins. A plant albumin (PA2) from Cicer arietinum, presumably a lectin (CAL) owing to its hemagglutination activity which is inhibited by complex sugars as well as glycoproteins such as fetuin, desialylated fetuin and fibrinogen. The three-dimensional structure of this homodimeric protein has been determined using X-ray crystallography at 2.2 Å in two crystal forms: orthorhombic (P21212) and trigonal (P3). The structure determined using molecular replacement method and refined in orthorhombic crystal form reached R-factors R free 22.6 % and R work 18.2 % and in trigonal form had 22.3 and 17.9 % in the resolution range of 20.0-2.2 and 35.3-2.2 Å, respectively. Interestingly, unlike the known legume lectin fold, the structure of this homodimeric hemagglutinin belonged to hemopexin fold that consisted of four-bladed β-propeller architecture. Each subunit has a central cavity forming a channel, inside of which is lined with hydrophobic residues. The channel also bears binding sites for ligands such as calcium, sodium and chloride ions, iodine atom in the case of iodine derivative and water molecules. However, none of these ligands seem important for the sugar recognition. No monosaccharide sugar specificity could be detected using hemagglutination inhibition. Chemical modification studies identified a potential sugar-binding site per subunit molecule. Comparison of C-alpha atom positions in subunit structures showed that the deviations between the two crystal forms were more with respect to blades I and IV. Differences also existed between subunits in two forms in terms of type and site of ligand binding.

  18. Vector correlation analysis for inelastic and reactive collisions between partners possessing spin and orbital angular momentum.

    Science.gov (United States)

    Balint-Kurti, Gabriel G; Vasyutinskii, Oleg S

    2009-12-31

    A general reactive collision of the type A + B --> C + D is considered where both the collision partners (A and B) or the products (C and D) may possess internal, i.e., spin, orbital or rotational, angular momenta. Compact expressions are derived using a rigorous quantum mechanical analysis for the angular momentum anisotropy of either of the products (C or D) arising from an initially polarized distribution of the reactant angular momentum. The angular momentum distribution of the product is expressed in terms of canonical spherical tensors multiplied by anisotropy-transforming coefficients c(K(i)q(k))(K)(K(r),L). These coefficients act as transformation coefficients between the angular momentum anisotropy of the reactants and that of the product. They are independent of scattering angle but depend on the details of the scattering dynamics. The relationship between the coefficients c(K(i)q(k))(K)(K(r),L) and the body-fixed scattering S matrix is given and the methodology for the quantum mechanical calculation of the anisotropy-transforming coefficients is clearly laid out. The anisotropy-transforming coefficients are amenable to direct experimental measurement in a similar manner to vector correlation and alignment parameters in photodissociation processes. A key aspect of the theory is the use of projections of both reactant and product angular momenta onto the product recoil vector direction. An important new conservation rule is revealed through the analysis, namely that if the state multipole for reactant angular momentum distribution has a projection q(k) onto the product recoil vector the state multipoles for the product angular momentum distribution all have this same projection. Expressions are also presented for the distribution of the product angular momentum when its components are evaluated relative to the space-fixed Z-axis. Notes with detailed derivations of all the formulas are available as Supporting Information.

  19. Dihydrogen phosphate-water tape and layers vs dihydrogen phosphate layers tuned by hydrophobic isomeric pyridine-diamine functionalized molecules

    Science.gov (United States)

    Huang, Jing; Liu, Tong-Peng; Huo, Li-Hua; Deng, Zhao-Peng; Gao, Shan

    2017-01-01

    Assembly of six isomeric pyridine-diamine-based molecules, N,N‧-bis(pyridin-4-ylmethyl)ethane-1,2-diamine (M1), N,N‧-bis(pyridin-3-ylmethyl)ethane-1,2-diamine (M2), N,N‧-bis(pyridin-2-ylmethyl)ethane-1,2-diamine (M3), N,N‧-bis(pyridin-4-ylmethyl)propane-1,3-diamine (M4), N,N‧-bis(pyridin-3-ylmethyl)propane-1,2-diamine (M5), and N,N‧-bis(pyridin-2-ylmethyl)propane-1,3-diamine (M6), with phosphoric acid (H3PO4) in different ratio (1:2 and 1:4), leads to the formation of nine salts, H2M12+·2H2PO4-·4H2O (1), H2M22+·2H2PO4-·2H2O (2), H2M32+·2H2PO4-·2H2O (3), H4M14+·4H2PO4- (4), H4M24+·4H2PO4- (5), H4M34+·4H2PO4- (6), H2M42+·2H2PO4-·3H2O (7), 2H2M52+·4H2PO4-·2H3PO4 (8), and H2M62+·2H2PO4- (9), which have been characterized by elemental analysis, IR, TG, PL, powder and single-crystal X-ray diffraction. Structural analyses indicate that hydrogen-bonding patterns of H2PO4- anions, conformation of protonated cations can effectively influence the supramolecular architectures through diverse non-covalent interactions. Hydrous salts 1-3 and 7 present 2D and 3D host-guest supramolecular networks, in which the connection of H2PO4- anions and water molecules generates diverse tape and layer motifs. H2PO4- anions in anhydrous salts 4-6 interconnect with each other through hydrogen bonds to form two types of layers, which are joined by discrete H4M4+ cations into 3D inorganic-organic hybrid supramolecular networks. Salts 8-9 also present 2D and 3D host-guest supramolecular networks where the interconnection of H2PO4- anions and its combination with H3PO4 molecules leads to diverse layers. Luminescent analyses indicate that salts 1-9 exhibit violet and blue emission maximum in the range of 390-467 nm at room temperature.

  20. Positional isomerism-driven two 3D pillar-layered metal-organic frameworks: Syntheses, topological structures and photoluminescence properties

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yayong; Zhao, Siwei; Ma, Haoran; Han, Yi; Liu, Kang; Wang, Lei, E-mail: inorchemwl@126.com

    2016-06-15

    Two novel three-dimensional (3D) pillar-layered metal-organic frameworks (MOFs), namely [Zn{sub 2}(μ{sub 2}-OH)(boaba)(1,4-bmimb)]{sub n} (1) and {[Zn_5K_2(μ_2-H_2O)_2(boaba)_4(1,2-bmimb)_2(H_2O)_2]·H_2O}{sub n} (2), were prepared by hydrothermal reactions (H{sub 3}boaba=3,5-bis-oxyacetate-benzoic acid; 1,4-bmimb=1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene; 1,2-bmimb =1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene). Notably, 1 exhibits a (3,5)-connected binodal (6{sup 3})(6{sup 9}·8)-gra net with binuclear [Zn{sub 2}(μ{sub 2}-OH)(COO)]{sup 2+} clusters, while 2 shows a novel (4,4,5,9)-connected 4-nodal net constructed from the unique Zn(II)-K(I) heterometal rod-like substructures. The results indicate that the disposition of the 2-methylimidazolyl groups of bis(imidazole) ligands have a significant effect on structural diversity. Moreover, the photoluminescence properties of 1 and 2 have been investigated. - Graphical abstract: Two novel 3D pillar-layered metal-organic coordination networks with aromatic multicarboxylate anion and bis(imidazole) ligands have been synthesized and structurally characterized. Display Omitted - Highlights: • It is rarely reported that metal-organic frameworks prepared with 3,5-bis-oxyacetate-benzoic acid. • Two metal-organic frameworks based on positional isomeric ligands were synthesized and structurally characterized. • Compond 1 displays unique (3,5)-connected binodal gra topology. • Compound 2 exhibits (4,4,5,9)-connected 4-nodal topology based on the Zn(II)-K(I) heterometal rod-like substructures. • The photoluminescence properties of compound 1 and 2 have been investigated.

  1. Catalyst-Directed Diastereoselective Isomerization of Allylic Alcohols for the Stereoselective Construction of C(20) in Steroid Side Chains: Scope and Topological Diversification.

    Science.gov (United States)

    Li, Houhua; Mazet, Clément

    2015-08-26

    The stereoselective construction of C20 in steroidal derivatives by a highly diastereoselective Ir-catalyzed isomerization of primary allylic alcohols is reported. A key aspect of this strategy is a straightforward access to geometrically pure steroidal enol tosylate and enol triflate intermediates for subsequent high yielding stereoretentive Negishi cross-coupling reactions to allow structural diversity to be introduced. A range of allylic alcohols participates in the diastereoselective isomerization under the optimized reaction conditions. Electron-rich and electron-poor aryl or heteroaryl substituents are particularly well-tolerated, and the stereospecific nature of the reaction provides indifferently access to the natural C20-(R) and unnatural C20-(S) configurations. Alkyl containing substrates are more challenging as they affect regioselectivity of iridium-hydride insertion. A rationale for the high diastereoselectivities observed is proposed for aryl containing precursors. The scope of our method is further highlighted through topological diversification in the side chain and within the polycyclic domain of advanced and complex steroidal architectures. These findings have the potential to greatly simplify access to epimeric structural analogues of important steroid scaffolds for applications in biological, pharmaceutical, and medical sciences.

  2. Measurements of isomeric yield ratios of fission products from proton-induced fission on natU and 232Th via direct ion counting

    Directory of Open Access Journals (Sweden)

    Rakopoulos Vasileios

    2017-01-01

    Full Text Available Independent isomeric yield ratios (IYR of 81Ge, 96Y, 97Y, 97Nb, 128Sn and 130Sn have been determined in the 25 MeV proton-induced fission of natU and 232Th. The measurements were performed at the Ion Guide Isotope Separator On-Line (IGISOL facility at the University of Jyväskylä. A direct ion counting measurement of the isomeric fission yield ratios was accomplished for the first time, registering the fission products in less than a second after their production. In addition, the IYRs of natU were measured by means of γ-spectroscopy in order to verify the consistency of the recently upgraded experimental setup. From the obtained results, indications of a dependence of the production rate on the fissioning system can be noticed. These data were compared with data available in the literature, whenever possible. Using the TALYS code and the experimentally obtained IYRs, we also deduced the average angular momentum of the fission fragments after scission.

  3. Simultaneous monitoring of oxidation, deamidation, isomerization, and glycosylation of monoclonal antibodies by liquid chromatography-mass spectrometry method with ultrafast tryptic digestion.

    Science.gov (United States)

    Wang, Yi; Li, Xiaojuan; Liu, Yan-Hui; Richardson, Daisy; Li, Huijuan; Shameem, Mohammed; Yang, Xiaoyu

    Monoclonal antibodies are subjected to a wide variety of post-translational modifications (PTMs) that cause structural heterogeneity. Characterization and control of these modifications or quality attributes are critical to ensure antibody quality and to define any potential effects on the ultimate safety and potency of antibody therapeutics. The biopharmaceutical industry currently uses numerous tools to analyze these quality attributes individually, which requires substantial time and resources. Here, we report a simple and ultrafast bottom-up liquid chromatography-mass spectrometry (uLC-MS) method with 5 min tryptic digestion to simultaneously analyze multiple modifications, including oxidation, deamidation, isomerization, glycation, glycosylation, and N-terminal pyro-glutamate formation, which can occur during antibody production in mammalian cell culture, during purification and/or on storage. Compared to commonly used preparation procedures, this uLC-MS method eliminates assay artifacts of falsely-increased Met oxidation, Asp isomerization, and Asn deamidation, a problem associated with long digestion times in conventional LC-MS methods. This simple, low artifact multi-attribute uLC-MS method can be used to quickly and accurately analyze samples at any stage of antibody drug development, in particular for clone and media selection during cell culture development.

  4. Theoretical and experimental study of the relaxation of excited states of the DCM laser dye. Intra-molecular electron transfer and photo-isomerization. Solvent effects

    International Nuclear Information System (INIS)

    Marguet, Sylvie

    1992-01-01

    This research thesis reports the study of a styrenic laser dye, the 4-(dicyanomethylene)-2-methyl-6-[p-(dimethylamino) styryl]-4H-pyrane or DCM for the characterization of the first electronic states and of the influence of the solvent on efficiencies of different relaxation processes of the first excited state S1 of the DCM. Due to the presence of a combination of a donor group and acceptor group, this compound has interesting properties of intra-molecular charge transfer and of photo-isomerization which highly depend on solvent polarity. Two approaches have been adopted to study these complementary processes: an experimental approach (determination of rate constants of the different deactivation ways of the S1 state by measuring fluorescence quantum efficiencies, photo-isomerization quantum efficiencies, and fluorescence lifetimes of DCM in about twenty solvent of increasing polarity), and a computational approach (a CS-INDO-MRI type quantum chemistry calculation to obtain potential energy curves, charge distributions, and dipolar moments of DCM first electronic states) [fr

  5. Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

    Science.gov (United States)

    Patel, M A; Riley, F; Ashraf-Khorassani, M; Taylor, L T

    2012-04-13

    Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. Zinc oxide and chromia as catalysts for the isomerization of butene, the hydrogenation of ethylene, and the isotopic exchange and allotropic conversion of hydrogen

    International Nuclear Information System (INIS)

    Conner, W.C. Jr.

    1973-01-01

    Hydrogenation of olefins has been studied over metals and metal oxides. Over metals the following observations generalize the characteristics of hydrogenation and isomerization. Metal hydrogenation catalysts are effective for H 2 -D 2 exchange (and para hydrogen conversion) under the same conditions as they effect olefin hydrogenation. This suggests that hydrogen ''activation'' involves formation of hydrogen atoms as a surface intermediate. Addition of deuterium to light ethylene leads to ethane products of the form C 2 H/sub 6-x/D/sub x/ (where 0 less than or equal to x less than or equal to 6). This is a result of the reversal of the alkyl (C 2 H 5 *) formation on the surface. Moreover, efficient isomerization of olefins require hydrogen as a co-catalyst. Both these observations suggest that alkyl formation and its reversal play a major role in hydrogenation and related reactions over metals. In this work it is found that zinc oxide catalyzes the deuteration of ethylene to dideuterioethane selectivity. Furthermore, the hydrogenation of ethylene using mixtures of hydrogen and deuterium indicate that hydrogenation occurs in such a manner as to reflect the molecular identity of the gas phase in the product ethane

  7. On the co-variation between form and function of adnominal possessive modifiers in Dutch and English

    DEFF Research Database (Denmark)

    Rijkhoff, Jan

    2009-01-01

    in the noun phrase (section 3); a tentative explanation is given in section 4. The more general point this paper wants to make is that functional modifier categories like CLASSIFYING MODIFIER or QUALIFYING MODIFIER can be characterized in grammatical terms and, furthermore, that important grammatical...... that the remarkable variation in the grammatical properties of this possessive construction directly correlates with the kind of modifier function it has in the noun phrase. It is first shown that lexical possessive modifiers with van ‘of’ (“adnominal possessives” for short) are used to express most of the modifier...... functions recognized in a semantic, five-layered model of the noun phrase (section 2). I will then argue that the values for certain grammatical parameters (here subsumed under the labels MODIFICATION, PREDICATION, REFERENCE) correlate with the kind of modifier function the adnominal possessive has...

  8. Configurational isomerism in polyoxovanadates

    Energy Technology Data Exchange (ETDEWEB)

    Mahnke, Lisa K.; Naether, Christian; Bensch, Wolfgang [Institut fuer Anorganische Chemie, Christian-Albrechts-Universitaet, Kiel (Germany); Kondinski, Aleksandar; Van Leusen, Jan; Monakhov, Kirill Yu.; Koegerler, Paul [Institut fuer Anorganische Chemie, RWTH Aachen University (Germany); Warzok, Ulrike; Schalley, Christoph A. [Institut fuer Chemie und Biochemie, Freie Universitaet Berlin (Germany)

    2018-03-05

    A water-soluble derivative of the polyoxovanadate {V_1_5E_6O_4_2} (E=semimetal) archetype enables the study of cluster shell rearrangements driven by supramolecular interactions. A reaction unique to E=Sb, induced exclusively by ligand metathesis in peripheral [Ni(ethylenediamine){sub 3}]{sup 2+} counterions, results in the formation of the metastable α{sub 1}* configurational isomer of the {V_1_4Sb_8O_4_2} cluster type. Contrary to all other polyoxovanadate shell architectures, this isomer comprises an inward-oriented vanadyl group and is ca. 50 and 12 kJ mol{sup -1} higher in energy than the previously isolated α and β isomers, respectively. We discuss this unexpected reaction in light of supramolecular Sb-O..V and Sb-O..Sb contacts manifested in {V_1_4Sb_8O_4_2}{sub 2} dimers detected in the solid state. ESI MS experiments confirm the stability of these dimers also in solution and in the gas phase. DFT calculations indicate that other, as of yet elusive isomers of {V_1_4Sb_8}, might be accessible as well. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. SfDredd, a Novel Initiator Caspase Possessing Activity on Effector Caspase Substrates in Spodoptera frugiperda.

    Science.gov (United States)

    Yang, Zhouning; Zhou, Ke; Liu, Hao; Wu, Andong; Mei, Long; Liu, Qingzhen

    2016-01-01

    Sf9, a cell line derived from Spodoptera frugiperda, is an ideal model organism for studying insect apoptosis. The first notable study that attempted to identify the apoptotic pathway in Sf9 was performed in 1997 and included the discovery of Sf-caspase-1, an effector caspase of Sf9. However, it was not until 2013 that the first initiator caspase in Sf9, SfDronc, was discovered, and the apoptotic pathway in Sf9 became clearer. In this study, we report another caspase of Sf9, SfDredd. SfDredd is highly similar to insect initiator caspase Dredd homologs. Experimentally, recombinant SfDredd underwent autocleavage and exhibited different efficiencies in cleavage of synthetic caspase substrates. This was attributed to its caspase activity for the predicted active site mutation blocked the above autocleavage and synthetic caspase substrates cleavage activity. SfDredd was capable of not only cleaving Sf-caspase-1 in vitro but also cleaving Sf-caspase-1 and inducing apoptosis when it was co-expressed with Sf-caspase-1 in Sf9 cells. The protein level of SfDredd was increased when Sf9 cells were treated by Actinomycin D, whereas silencing of SfDredd reduced apoptosis and Sf-caspase-1 cleavage induced by Actinomycin D treatment. These results clearly indicate that SfDredd functioned as an apoptotic initiator caspase. Apoptosis induced in Sf9 cells by overexpression of SfDredd alone was not as obvious as that induced by SfDronc alone, and the cleavage sites of Sf-caspase-1 for SfDredd and SfDronc are different. In addition, despite sharing a sequence homology with initiator caspases and possessing weak activity on initiator caspase substrates, SfDredd showed strong activity on effector caspase substrates, making it the only insect caspase reported so far functioning similar to human caspase-2 in this aspect. We believe that the discovery of SfDredd, and its different properties from SfDronc, will improve the understanding of apoptosis pathway in Sf9 cells.

  10. The impact of possession on legality of mortgage registered on a building under construction: With case law

    Directory of Open Access Journals (Sweden)

    Vicković Tanja

    2016-01-01

    Full Text Available The expansion of the subject of a mortgage to buildings under construction is a considerable step forward in regulating mortgages. It is not possible to register ownership rights on buildings under construction. A person acquiring ownership does not have the possibility to protect his rights. Acquiring ownership rights to a building under construction is tied to possession. This is detrimental to the principle of publicity which in turn erodes the principle of reliance. Validity of the mortgage is tied to the possession over the mortgaged real estate at the time of its registration. Such position of the courts challenges the very essence of mortgage.

  11. Origanum vulgare mediated green synthesis of biocompatible gold nanoparticles simultaneously possessing plasmonic, antioxidant and antimicrobial properties

    Directory of Open Access Journals (Sweden)

    Benedec D

    2018-02-01

    Full Text Available Daniela Benedec,1,* Ilioara Oniga,1,* Flavia Cuibus,1 Bogdan Sevastre,2 Gabriela Stiufiuc,3 Mihaela Duma,4 Daniela Hanganu,1 Cristian Iacovita,1 Rares Stiufiuc,1,5 Constantin Mihai Lucaciu1 1Faculty of Pharmacy, “Iuliu Haţieganu” University of Medicine and Pharmacy, 2Faculty of Veterinary Medicine, University of Agricultural Sciences and Veterinary Medicine, 3Faculty of Physics, “Babeş Bolyai” University, 4State Veterinary Laboratory for Animal Health and Safety, 5Department of Bionanoscopy, MedFuture Research Center for Advance Medicine, “Iuliu Haţieganu” University of Medicine and Pharmacy, Cluj-Napoca, Romania *These authors contributed equally to this work Purpose: The leaves and flowering stem of Origanum vulgare contain essential oils, flavonoids, phenolic acids and anthocyanins. We propose a new, simple, one-pot, O. vulgare extract (OVE mediated green synthesis method of biocompatible gold nanoparticles (AuNPs possessing improved antioxidant, antimicrobial and plasmonic properties.Materials and methods: Different concentrations of OVEs were used to reduce gold ions and to synthetize biocompatible spherical AuNPs. Their morphology and physical properties have been investigated by means of transmission electron microscopy, ultraviolet–visible absorption spectroscopy, photon correlation spectroscopy and Fourier transform infrared spectroscopy, whereas their plasmonic properties have been tested using surface-enhanced Raman spectroscopy (SERS. The antioxidant properties of nanoparticles (NPs have been evaluated by 2,2-diphenyl-1-picrylhydrazyl radical scavenging assay, and the antimicrobial tests were performed using the disk diffusion assay. Their cytotoxicity has been assessed by means of 3-(4,5-dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide assay.Results: The experimental results confirmed the successful synthesis of biocompatible, spherical, plasmonic NPs having a mean diameter of ~40 nm and an outstanding aqueous

  12. Isovanillin derived N-(un)substituted hydroxylamines possessing an ortho-allylic group: valuable precursors to bioactive N-heterocycles.

    Science.gov (United States)

    Dulla, Balakrishna; Tangellamudi, Neelima D; Balasubramanian, Sridhar; Yellanki, Swapna; Medishetti, Raghavender; Kumar Banote, Rakesh; Hari Chaudhari, Girish; Kulkarni, Pushkar; Iqbal, Javed; Reiser, Oliver; Pal, Manojit

    2014-04-28

    The intramolecular 1,3-dipolar cycloaddition of isovanillin derived N-aryl hydroxylamines possessing ortho-allylic dipolarophiles affords novel benzo analogues of tricyclic isoxazolidines that can be readily transformed into functionalized lactams, γ-aminoalcohols and oxazepines. The corresponding N-unsubstituted hydroxylamines give rise to tetrahydroisoquinolines. Anxiogenic properties of these compounds are tested in zebra fish.

  13. Love and Art Strike Back: A.S. Byatt’s Possession: A Romance

    DEFF Research Database (Denmark)

    Mogensen, Tine Engel

    2004-01-01

    Possession can be seen as an enactment of the conflicts between a number of powerful - and quite classic - extremes (anatomy-romance, intellectual experience-sensuous experience, theory-art, reason-love, irony-pathos), which, in the aesthetic experience of the reader, it overcomes and transcends....

  14. Children enacting idioms of witchcraft and spirit possession as a response to trauma: therapeutically beneficial, and for whom?

    NARCIS (Netherlands)

    Reis, R.

    2013-01-01

    This article examines children’s enactment of spirit possession idioms and witchcraft in Africa including the meanings such idioms provide and the local healing resources they mobilize. Idioms of haunting spirits in Northern Uganda and witch-children elsewhere in Africa can be interpreted as

  15. Draft Genome Sequence of Methyloferula stellata AR4, an Obligate Methanotroph Possessing Only a Soluble Methane Monooxygenase.

    Science.gov (United States)

    Dedysh, Svetlana N; Naumoff, Daniil G; Vorobev, Alexey V; Kyrpides, Nikos; Woyke, Tanja; Shapiro, Nicole; Crombie, Andrew T; Murrell, J Colin; Kalyuzhnaya, Marina G; Smirnova, Angela V; Dunfield, Peter F

    2015-03-05

    Methyloferula stellata AR4 is an aerobic acidophilic methanotroph, which, in contrast to most known methanotrophs but similar to Methylocella spp., possesses only a soluble methane monooxygenase. However, it differs from Methylocella spp. by its inability to grow on multicarbon substrates. Here, we report the draft genome sequence of this bacterium. Copyright © 2015 Dedysh et al.

  16. Draft Genome Sequence of Methyloferula stellata AR4, an Obligate Methanotroph Possessing Only a Soluble Methane Monooxygenase

    OpenAIRE

    Dedysh, Svetlana N.; Naumoff, Daniil G.; Vorobev, Alexey V.; Kyrpides, Nikos; Woyke, Tanja; Shapiro, Nicole; Crombie, Andrew T.; Murrell, J. Colin; Kalyuzhnaya, Marina G.; Smirnova, Angela V.; Dunfield, Peter F.

    2015-01-01

    Methyloferula stellata AR4 is an aerobic acidophilic methanotroph, which, in contrast to most known methanotrophs but similar to Methylocella spp., possesses only a soluble methane monooxygenase. However, it differs from Methylocella spp. by its inability to grow on multicarbon substrates. Here, we report the draft genome sequence of this bacterium.

  17. Reactive, anxious and possessive forms of jealousy and their relation to relationship quality among heterosexuals and homosexuals

    NARCIS (Netherlands)

    Barelds, Dick P. H.; Dijkstra, Pieternel

    2006-01-01

    The present study examined the relationship between relational quality and three different types of jealousy-reactive, anxious and possessive jealousy. The sample consisted of 76 gay men, 79 lesbians, 70 heterosexual women and 70 heterosexual men. Findings show that different types of jealousy

  18. Assessing the Degree of Possessing Study Skills by the Students of Tafila Technical University from Their Perspectives

    Science.gov (United States)

    Al-Roud, Atallah A.; Thawabiah, Ahmad

    2016-01-01

    The study aimed to identify the degree of possessing study skills (SS) by the students of Tafila Technical (TTU) University from their perspectives. The population of the study consisted of 5015 students in TTU for the second semester of the academic year 2015/2016. The sample of the study was chosen randomly from the population of the study with…

  19. 76 FR 59271 - Migratory Bird Hunting; Late Seasons and Bag and Possession Limits for Certain Migratory Game Birds

    Science.gov (United States)

    2011-09-26

    ...-0014; 91200-1231-9BPP-L2] RIN 1018-AX34 Migratory Bird Hunting; Late Seasons and Bag and Possession Limits for Certain Migratory Game Birds AGENCY: Fish and Wildlife Service, Interior. ACTION: Final rule... of migratory birds is prohibited unless specifically provided for by annual regulations. This rule...

  20. The attributive possessive in Moroccan Arabic spoken by young bilinguals in the Netherlands and their peers in Morocco

    NARCIS (Netherlands)

    Boumans, L.P.C.

    2006-01-01

    Quantitative evidence shows that the use of the SG in MA depends on the lexical item that heads the possessive, while it is more frequent with pronominal dependents. The AG is used more in Tangier than in Casablanca, Rabat or Oujda, and this is true for both pronominal and NP dependents. Immigrants'