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Sample records for hyperdeformed isomeric states

  1. Abnormal Radioactive Decays out of Long-Lived Super- and Hyper-Deformed Isomeric States

    CERN Document Server

    Marinov, A; Kolb, D

    2000-01-01

    Long-lived high-spin super- and hyper-deformed isomeric states, which exhibit themselves by abnormal radioactive decays, have been observed using the 16O + 197Au and 28Si + 181Ta reactions. They make it possible to understand the production, via secondary reactions, of the long-lived superheavy element with Z = 112 and of the abnormally low energy and very enhanced alpha-particles seen in various actinide sources. They may also explain some puzzling phenomena seen in nature.

  2. Super- and Hyperdeformed Isomeric States and Long-Lived Superheavy Elements

    CERN Document Server

    Marinov, A; Kolb, D; Brandt, R; Gentry, R V; Pape, A

    2004-01-01

    The recent discoveries of the long-lived high spin super- and hyperdeformed isomeric states and their unusual radioactive decay properties are described. Based on their existence a consistent interpretation is given to the production of the long-lived superheavy element with Z = 112, via secondary reactions in CERN W targets, and to the low energy and very enhanced alpha-particle groups seen in various actinide fractions separated from the same W target. In addition, consistent interpretations are suggested for previously unexplained phenomena seen in nature. These are the Po halos, the low-energy enhanced 4.5 MeV alpha-particle group proposed to be due to an isotope of a superheavy element with Z = 108, and the giant halos.

  3. A search for superdeformed and hyperdeformed states in $^{2}^{2}^{2}Th$ and $^{2}^{3}^{2}U$

    CERN Document Server

    Hawcroft, D

    2000-01-01

    sup 2 sup 2 Th potential energy surface which would be emitted prior to a decay out of the well by fission. Nuclear states in sup 2 sup 3 sup 2 U were investigated through conversion electron spectroscopy using the SACRED multi-element electron detection system. The high segmentation of the silicon detector array enabled us to detect multiple electrons simultaneously and therefore enhance the sensitivity of the experiment towards bands with high electron multiplicity. The sup 2 sup 3 sup 2 Th (alpha,4n) sup 2 sup 3 sup 2 U reaction was used with a beam energy of 42 MeV. In all three cases no evidence towards the existence of superdeformed states in sup 2 sup 2 sup 2 Th or sup 2 sup 3 sup 2 U or hyperdeformed states in sup 2 sup 3 sup 2 U were found. The experimental data were used to determine upper limits for the reaction cross sections leading to the population of states in the second or third minima in the potential energy surfaces. These upper limit cross sections were evaluated as: 900 mu b for the popul...

  4. Hyperdeformation and clustering in the actinide region

    NARCIS (Netherlands)

    Krasznahorkay, A; Csatlos, M; Csige, L; Eisermann, Y; Faestermann, T; Gacsi, Z; Graw, G; Gulyas, J; Habs, D; Harakeh, MN; Heil, M; Hertenberger, R; Kappeler, F; Krasznahorkay, A; Maier, HJ; Mate, Z; Reifarth, R; Thirolf, PG; Timar, J; Wirth, HF

    2003-01-01

    The excitation energy spectrum of fission resonances has been measured with high energy resolution using the U-235 (d,pf) reaction in order to study hyperdeformed (HD) rotational bands and HD nuclear shapes. The moments of inertia of the rotational bands and the energy of the ground state in the thi

  5. Nearly degenerate isomeric states of 75Cu

    Science.gov (United States)

    Petrone, C.; Daugas, J. M.; Simpson, G. S.; Stanoiu, M.; Plaisir, C.; Faul, T.; Borcea, C.; Borcea, R.; Cáceres, L.; Calinescu, S.; Chevrier, R.; Gaudefroy, L.; Georgiev, G.; Gey, G.; Kamalou, O.; Negoita, F.; Rotaru, F.; Sorlin, O.; Thomas, J. C.

    2016-08-01

    The decays of two isomeric states in the neutron-rich nucleus 75Cu have been studied via delayed γ -ray spectroscopy. These states were populated by the fragmentation of a 60.4 A MeV 86Kr primary beam, which impinged on a Be target at the LISE2k spectrometer of GANIL. Isomeric half-lives and branching ratios were measured, and a γ -γ coincidence analysis performed. These have allowed a revised level scheme of 75Cu to be proposed. A comparison with large-scale shell-model calculations using different effective interactions and valence spaces shows the importance of proton excitations across the Z =28 shell gap for reproducing the energy spacing between the isomeric states. The coexisting collective and single-particle properties of the (1 /2-) and (3 /2-) states, respectively, are similar to those of the same states in the neighboring 69,71,73Cu. The small energy spacings between the (1 /2-) , (3 /2-) , and 5 /2- states are responsible for the isomerism.

  6. Alpha decay from fission isomeric states

    Energy Technology Data Exchange (ETDEWEB)

    Poenaru, D.N.; Ivascu, M. (Institutul de Fizica si Inginerie Nucleara, Bucharest (Romania))

    1981-07-01

    Alpha-decay half-lives from shape isomeric states of some even-even isotopes of U, Pu and Cm nuclei are calculated by using fission theory in the parametrisation of a spheroid intersected with a sphere. The potential barrier was calculated in the framework of the liquid-drop model of Myers and Swiatecki (Art. Fys.; 36: 343 (1967)) extended for systems with different charge densities; a phenomenological shell correction was introduced. The WKB computed lifetimes are many orders of magnitude longer than that of the spontaneous fission process, in agreement with experimental results.

  7. Selfconsistent calculations for hyperdeformed nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Molique, H.; Dobaczewski, J.; Dudek, J.; Luo, W.D. [Universite Louis Pasteur, Strasbourg (France)

    1996-12-31

    Properties of the hyperdeformed nuclei in the A {approximately} 170 mass range are re-examined using the self-consistent Hartree-Fock method with the SOP parametrization. A comparison with the previous predictions that were based on a non-selfconsistent approach is made. The existence of the {open_quotes}hyper-deformed shell closures{close_quotes} at the proton and neutron numbers Z=70 and N=100 and their very weak dependence on the rotational frequency is suggested; the corresponding single-particle energy gaps are predicted to play a role similar to that of the Z=66 and N=86 gaps in the super-deformed nuclei of the A {approximately} 150 mass range. Selfconsistent calculations suggest also that the A {approximately} 170 hyperdeformed structures have neglegible mass asymmetry in their shapes. Very importantly for the experimental studies, both the fission barriers and the {open_quotes}inner{close_quotes} barriers (that separate the hyperdeformed structures from those with smaller deformations) are predicted to be relatively high, up to the factor of {approximately}2 higher than the corresponding ones in the {sup 152}Dy superdeformed nucleus used as a reference.

  8. Hyperdeformation and clusterization in the actinide region

    NARCIS (Netherlands)

    Krasznahorkay, A; Habs, D; Hunyadi, M; Gassmann, D; Csatlos, M; Eisermann, Y; Faestermann, T; Graw, G; Gulyas, J; Hertenberger, R; Maier, HJ; Mate, Z; Metz, A; Ott, J; Thirolf, PG; van der Werf, SY

    2001-01-01

    The U-233(d,pf)U-234, and the U-235(d,pf)U-236 reactions have been studied with high energy resolution. The observed fission resonances were described as members of rotational bands with rotational parameters characteristic of hyperdeformed nuclear shapes. Information on the K values of the bands an

  9. Mixed Symmetry Isomeric States in Nuclei

    Institute of Scientific and Technical Information of China (English)

    LONG Gui-Lu; RUAN Dong; LI Yan-Song; TU Chang-Cun; TIAN Lin; JI Hua-Ying; ZHU Sheng-Jiang; ZHAO En-Guang; LIU Feng-Ying; ZHANG Jin-Fu

    2002-01-01

    Mixed symmetry states are studied in the framework of the neutron-proton interacting boson model. It is found that some of the mixed symmetry states with moderate high spins change very fast with respect to the Majorana interaction. Under certain conditions, they become the yrast state or yrare state. These states are difficult to decay and become very stable. This study suggests that a possible new mode of isomers may exist due to the special nature in their proton and neutron degrees of freedom.

  10. g-factor measurements of isomeric states in 174W

    Directory of Open Access Journals (Sweden)

    Rocchini M.

    2016-01-01

    Full Text Available The experimental setup GAMIPE used for gyro magnetic factor measurements at Laboratori Nazionali di Legnaro and a recent experimental work regarding K-isomers in 174W are described. Aim of the experiment is to study the detailed structure of the isomeric states wave functions, by the measurement of the magnetic dipole moments. This piece of information can provide interesting hints for theoretical models. Preliminary results concerning the population of the isomers of interest and half-lives are presented.

  11. Isomerism of low-lying states in {sup 86}Y

    Energy Technology Data Exchange (ETDEWEB)

    Rusu, C. [Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest (Romania); University of Texas at Dallas, School of Natural Sciences and Mathematics, Richardson, TX (United States); Bucurescu, D.; Marginean, N.; Ionescu-Bujor, M.; Iordachescu, A.; Cata-Danil, G.; Cata-Danil, I.; Deleanu, D.; Filipescu, D.; Ghita, D.; Glodariu, T.; Ivascu, M.; Mihai, C.; Marginean, R.; Pascu, S.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N.V. [Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest (Romania)

    2010-04-15

    Low-energy isomeric states of {sup 86}Y were populated in the reaction {sup 73}Ge + {sup 16}O at 57MeV and were investigated by means of delayed n {gamma} and {gamma} {gamma} coincidences. A half-life of 70(7)ns was measured for the 5{sup -} state at 208keV, yielding an exceptionally small B(M1) value of 2.0(7) x 10{sup -5} W.u. and a B(E2) value of 0.34({sup +24} {sub -13}) W.u. For the other three known isomeric states at 218, 243, and 302keV, the half-lives extracted from the present experimental data are in very good agreement with previous measurements. Given the newly observed isomeric character of the 5{sup -} 208keV state, the re-analysis of earlier experimental data on the 302keV isomer led to a new spin-parity assignment, 6{sup +}, for this state. In addition, this re-evaluation provided two g -factors, -0.083(3) and +0.63(2), for the 208 and 302keV states, respectively. The results are discussed in terms of spherical-shell model calculations performed with a truncated space of configurations built on the f{sub 5/2}, p{sub 3/2}, p{sub 1/2}, and g{sub 9/2} valence orbitals. Effective spin, orbital, and ''tensor'' g -factors were determined empirically for protons and neutrons in the considered configuration space. (orig.)

  12. Generation of Long-Lived Isomeric States via Bremsstrahlung Irradiation

    CERN Document Server

    Cheng, Y; Tang, C; Liu, Y; Jin, Q; Cheng, Yao; Xia, Bing; Tang, Chuanxiang; Liu, Yinong; Jin, Qingxiu

    2006-01-01

    A method to generate long-lived isomeric states effectively for Mossbauer applications is reported. We demonstrate that this method is better and easier to provide highly sensitive Mossbauer effect of long-lived isomers (>1ms) such as 103Rh. Excitation of (gamma,gamma) process by synchrotron radiation is painful due mainly to their limited linewidth. Instead,(gamma,gamma') process of bremsstrahlung excitation is applied to create these long-lived isomers. Isomers of 45Sc, 107Ag, 109Ag, and 103Rh have been generated from this method. Among them, 103Rh is the only one that we have obtained the gravitational effect at room temperature.

  13. Cross Section of Isomeric States Produced in Photo-Neutron Reactions

    Science.gov (United States)

    Oprea, C.; Oprea, A.; Mihul, A.

    In this work the cross sections of the isomeric states production in (γ,n) reactions and the corresponding isomeric ratios for some isotopes of Cd, Sn, Mo, Sm in the great dipole resonance region with Talys codes using a standard input including Hauser-Feshbach model were evaluated. For the isomeric ratio calculation two methods were proposed, by using the description of incident gamma flux and experimental isomeric ratio. The obtained results are compared with experimental data from nuclear reactions induced by photons obtained by bremsstrahlung.

  14. Single-particle isomeric states in 121Pd and 117Ru

    CERN Document Server

    Lalkovski, S; Bacelar, A M Denis; Gorska, M; Pietri, S; Podolyak, Zs; Bednarczyk, P; Caceres, L; Casarejos, E; Cullen, I J; Doornenbal, P; Farrelly, G F; Garnsworthy, A B; Geissel, H; Gelletly, W; Gerl, J; Grcebosz, J; Hinke, C; Ilie, G; Jaworski, G; Kisyov, S; Kojouharov, I; Kurz, N; Myalski, S; Palacz, M; Prokopowicz, W; Regan, P H; Schaffner, H; Steer, S; Tashenov, S; Walker, P M; Wollersheim, H J; Zhekova, M

    2011-01-01

    Neutron-rich nuclei were populated in a relativistic fission of 238U. Gamma-rays with energies of 135 keV and 184 keV were associated with two isomeric states in 121Pd and 117Ru. Half-lives of 0.63(5) microseconds and 2.0(3) micrisecondss were deduced and the isomeric states were interpreted in terms of deformed single-particle states.

  15. Isomeric state of {sup 80}Y and its role in the rp-process

    Energy Technology Data Exchange (ETDEWEB)

    Novikov, Y.N. [St. Petersburg Nuclear Physics Inst., Gatchina (Russian Federation); Schatz, H.; Dendooven, P.; Beraud, R.; Miehe, C.; Popov, A.V.; Seliverstov, D.M.; Vorobjev, G.K.; Baumann, P.; Borge, M.J.G.; Canchel, G.; Desagne, P.; Emsallem, A.; Huang, W.; Huikari, J.; Jokinen, A.; Knipper, A.; Kolhinen, V.; Nieminen, A.; Oinonen, M.; Penttilae, H.; Peraejaervi, K.; Piqueras, I.; Rinta-Antila, S.; Szerypo, J.; Wang, Y.; Aeystoe, J.

    2003-07-01

    The HIGISOL facility has been used to investigate carefully the isomeric transition 228.5 keV in {sup 80}Y. We have measured the electron internal conversion coefficient for this transition {alpha}{sub K}=0.50{+-}0.07 which gives the value for half-life of ''bare'' isomeric state T{sub 1/2}=6.8{+-}0.5 s. The isomeric state should play an important role in the rp-process calculations. (orig.)

  16. Solution photochemistry of OCIO: excited-state dissociation and isomerization

    Science.gov (United States)

    Dunn, Robert C.; Flanders, Bret N.; Simon, John D.

    1992-04-01

    The photodissociation dynamics of OClO in room temperature water solution were investigated using picosecond transient absorption spectroscopy. The time dependent data are consistent with the conclusion that following excitation at 355 nm, 90% of the OCIO molecules photodissociate forming ClO and 0 and 10% isomerize forming CIOO. The photochemically generated CIOO thermally decomposes into Cl and 02 with a rate constant of -6.7 x 1O9 s-1.

  17. Existence of long-lived isomeric states in naturally-occurring neutron-deficient Th isotopes

    CERN Document Server

    Marinov, A; Kashiv, Y; Halicz, L; Segal, I; Pape, A; Gentry, R V; Miller, H W; Kolb, D; Brandt, R

    2006-01-01

    Evidence for the existence of long-lived neutron-deficient isotopes has been found in a study of naturally-occurring Th using iductively coupled plasma-sector field mass spectrometry. They are interpreted as belonging to the recently discovered class of long-lived high spin super- and hyperdeformed isomers.

  18. First observation of an isomeric state in proton drip-line nucleus 26P

    Directory of Open Access Journals (Sweden)

    Nishimura D.

    2014-03-01

    Full Text Available An isomeric state in the proton drip-line nucleus 26P has been observed by the γ-ray spectroscopy. The γ-ray energy and the half-life are 164.4 ± 0.1 keV and 120 ± 9 ns, respectively. For the isomeric transition of the mirror nucleus 26Na, the γ-ray energy of 82.40 ± 0.04 keV and the half-life of 4.35 ± 0.16 μs are also revised. Comparing the experimental reduced transition probabilities of 26Na and 26P with theoretical ones calculated by the shell model with the USDA interaction, the spin-parity (Jπ of the isomeric state in 26P is most likely to be 1+.

  19. Level density parameters from excitation cross sections of isomeric states

    Science.gov (United States)

    Skakun, E. A.; Batij, V. G.

    1992-03-01

    Cross section ratios were measured for the production of the isomeric pairs99m,gRh,101m,gRh,102m,gRh,104m,gRh and108m,gIn in the (p,n)-reaction,107m,gIn and109m,gIn in the ( p, γ)-reaction over the energy range up to 9 MeV, and116m,gSb and118m,gSb in the (α, n)-reaction up to 24 MeV. The experimental results for these nuclei as well as for other isometric pairs excited in the ( p, n)-reaction were analysed in the frame of the statistical model for extracting the level density parameter values in the vicinity of closed nucleon shells. The level density parameter behaviour is discussed in the range of nuclear mass numbers under study.

  20. Spontaneous fission half-lives of heavy nuclei in ground state and in isomeric state

    Science.gov (United States)

    Ren, Zhongzhou; Xu, Chang

    2005-09-01

    We generalize the formulas of spontaneous fission half-lives of even-even nuclei in their ground state to both the case of odd nuclei and the case of fission isomers [Phys. Rev. C 71 (2005) 014309]. The spontaneous fission half-lives of odd- A nuclei and of odd-odd nuclei in the ground state are calculated by Swiatecki's formula, by its generalized form, and by a new formula where the blocking effect of unpaired nucleon on the half-lives has been taken into account with different mechanisms. By introducing a blocking factor or a generalized seniority in the formulas of the half-lives of even-even nuclei, we can reasonably reproduce the experimental fission half-lives of odd- A nuclei and of odd-odd nuclei with the same parameters used in ground state of even-even nuclei. For spontaneous fission of the isomers in transuranium nuclei the new formula can be simplified into a three-parameter formula and the isomeric half-lives can be well reproduced by the formula. The new formula of the isomeric half-lives is as good as Metag's formula of fission isomers. The half-lives of isomers from these formulas are very accurate and therefore these formulas can give reliable predictions for half-lives of new isomers of neighboring nuclei.

  1. Systematic study of α preformation probability of nuclear isomeric and ground states

    Science.gov (United States)

    Sun, Xiao-Dong; Wu, Xi-Jun; Zheng, Bo; Xiang, Dong; Guo, Ping; Li, Xiao-Hua

    2017-01-01

    In this paper, based on the two-potential approach combining with the isospin dependent nuclear potential, we systematically compare the α preformation probabilities of odd-A nuclei between nuclear isomeric states and ground states. The results indicate that during the process of α particle preforming, the low lying nuclear isomeric states are similar to ground states. Meanwhile, in the framework of single nucleon energy level structure, we find that for nuclei with nucleon number below the magic numbers, the α preformation probabilities of high-spin states seem to be larger than low ones. For nuclei with nucleon number above the magic numbers, the α preformation probabilities of isomeric states are larger than those of ground states. Supported by National Natural Science Foundation of China (11205083), Construct Program of Key Discipline in Hunan Province, Research Foundation of Education Bureau of Hunan Province, China (15A159), Natural Science Foundation of Hunan Province, China (2015JJ3103, 2015JJ2123), Innovation Group of Nuclear and Particle Physics in USC, Hunan Provincial Innovation Foundation for Postgraduate (CX2015B398)

  2. Discovery of a new isomeric state in $^{68}$Ni: Evidence for a highly-deformed proton intruder state

    CERN Document Server

    Dijon, A; De France, G; De Angelis, G; Duchêne, G; Dudouet, J; Franchoo, S; Gadea, A; Gottardo, A; Hüyük, T; Jacquot, B; Kusoglu, A; Lebhertz, D; Lehaut, G; Martini, M; Napoli, D R; Nowacki, F; Péru, S; Poves, A; Recchia, F; Redon, N; Sahin, E; Schmitt, C; Sferrazza, M; Sieja, K; Stezowski, O; Valiente-Dobon, J J; Vancraeyenest, A; Zheng, Y

    2012-01-01

    We report on the observation of a new isomeric state in $^{68}$Ni. We suggest that the newly observed state at 168(1) keV above the first 2$^+$ state is a $\\pi(2p-2h)$ 0$^{+}$ state across the major Z=28 shell gap. Comparison with theoretical calculations indicates a pure proton intruder configuration and the deduced low-lying structure of this key nucleus suggests a possible shape coexistence scenario involving a highly deformed state.

  3. High-Spin Isomeric States in Nuclear Reactions Induced by He Isotopes

    Science.gov (United States)

    Chuvilskaya, Tatjana; Shirokova, Alla

    2010-11-01

    The high-spin states production in nuclear reactions is reviewed. The analysis of various experiments, our estimates and calculations reveal that in different compound nucleus energy regions maximal relative yield of high-spin states can be realized by different projectiles: at low energies -- by neutrons, in ˜ 20 -- 50 MeV region -- by α-particles, at higher energies -- by heavy ions. It was predicted [1] that there are energy ranges in which neutron-rich radioactive ions (^6,8He, for example) are favorable. σm/σg (the ratio between the yields of high-spin Jm and low-spin Jg metastable states of a nucleus in one and the same reaction) e.g. the isomeric cross-section ratio is a very good indicator of high-spin states production capability of a nuclear reaction. These experiments demonstrate that maximal values of isomeric cross-section ratios (up to 30) are obtained in α-particle induced reactions. Experiment with ^6He beam [2] confirms the predictions of the work [1] concerning the prospects of neutron-rich radioactive-ion beams in high-spin states population. The results of calculations of the isomeric cross section ratios using the code EMPIRE-II-18 approach to statistical theory of nuclear reactions demonstrate rather good agreement with the experimental data. Due to that these prediction power of these calculation is confirmed. The results of widespread calculations of the isomeric cross-section ratios of the reactions with ^6,8He are presented. [1] T.V.Chvilskaya et al., AIP-Conference Proceedings ENAM-98 1998. V. 455. P. 482. [2] P.A.DeYoung et al., Phys.Rev.C. 2000. V. 62. P.047601.

  4. Quantum Yields from Stationary States: Cis-Trans Isomerization of Model Retinal

    CERN Document Server

    Tscherbul, T V

    2014-01-01

    Cis-trans isomerization in retinal, the first step in vision, is often computationally studied from a time dependent viewpoint. Motivation for such studies lies in coherent pulsed laser experiments that explore the isomerization dynamics. However, such biological processes take place naturally in the presence of incoherent light, which excites a non-evolving mixture of stationary states. Here the isomerization problem is considered from the latter viewpoint and applied to a standard two-state, two-mode linear vibronic coupling model of retinal that explicitly includes a conical intersection between the ground and first excited electronic states. The calculated quantum yield at 500 nm agrees well with both the previous time-dependent calculations of Hahn and Stock (0.63) and with experiment ($0.65\\pm0.01$), as does its wavelength dependence. Significantly, the effects of environmental relaxation on the quantum yield in this well-established model are found to be negligible. The results make clear the connectio...

  5. Isomerization, Perturbations, Calculations and the S_{1} State of C_{2}H_{2}

    Science.gov (United States)

    Baraban, J. H.; Changala, P. B.; Berk, J. R. P.; Field, R. W.; Stanton, J. F.; Merer, A. J.

    2013-06-01

    Preliminary analysis of the energy region of the cis-trans isomerization transition state on the S_{1} surface of C_{2}H_{2} has revealed novel patterns and surprising perturbations, including unusually large (and high-order) anharmonicities, as well as K-staggerings of several vibrational levels. These effects complicate the analysis considerably, and require new models and calculations to account for and predict features of the observed spectra. The ˜{A}-˜{X} spectrum of acetylene has been studied both experimentally and theoretically for almost a century, and this cycle of unexpected phenomena eliciting innovative responses is found throughout its history. Especially in the last ten years, progress in understanding the S_{1} state rovibrational level structure and cis-trans isomerization has been accelerated by combining the information available from both ab initio computation and spectroscopic observations. The resulting dialogue has then frequently suggested fruitful avenues for further experiments and calculations. Current challenges and recent results in understanding the cis-trans isomerization transition state region will be discussed in this context.

  6. Proton Transfer Isomerization of Pyrazole in the Ground State:σν sπ Mechanism and Water Assisting Effect

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The proton transfer isomerization of pyrazole and the water assisting effect by looping 1 to 4 water molecules on the singlet state potential energy surface have been investigated by using hybrid density functional theory method (B3PW91) with a 6-311++G** basis set. Two mechanisms were proposed to explain the mono- and multi-water assisting effects, respectively. The reactants and products of all groups have been characterized on their potential energy surfaces. For the isomerization of monomolecule pyrazole, the isomerization energy barrier is 46.4 kcal·mol-1. For the monohydration assisting mechanism, the reactant complex is connected to the product complex via two saddle points. The corresponding isomerization barriers are 46.7and 23.0 kcal(mol-1, respectively. As to the multihydration assisting mechanism, the isomerization barriers are 12.0, 10.9 and 13.14 kcal(mol-1 accordingly, when the number of water molecules is 2, 3 and 4, respectively. The multihydration assisting isomerization can occur in water-dominated environments, for example, in the organism, and thereby is crucial to energy transference. The deproton and dehydrogen energies of monomolecule pyrazole and various hydrated pyrazoles were calculated and then found much bigger than the isomerization barriers of their relative complexes, suggesting the impossibility of deprotonation or dehydrogenation. The isomerization of pyrazole is a proton-coupling-electron-migration process, but two different mechanisms are noticed, viz.σ- and π-type mechanisms. The π-bond of pyrazole participates in isomerization in the π-type mechanism, whereas only σelectron takes part in isomerization in the σ-type mechanism.

  7. 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.

  8. Isospin symmetry at high spin studied via nucleon knockout from isomeric states

    OpenAIRE

    2016-01-01

    One-neutron knockout reactions have been performed on a beam of radioactive 53Co in a high-spin isomeric state. The analysis is shown to yield highly-selective population of high-spin states in an exotic nucleus with a significant cross section, and hence represents a technique that is applicable to the planned new generation of fragmentation-based radioactive beam facilities. Additionally, the relative cross sections among the excited states can be predicted to a high level of accuracy when ...

  9. Alpha decay of {sup 184-224}Bi isotopes from the ground state and isomeric state

    Energy Technology Data Exchange (ETDEWEB)

    Santhosh, K.P.; Priyanka, B. [Kannur University, School of Pure and Applied Physics, Kerala (India)

    2013-12-15

    The {alpha} -decay half-lives for the favored and unfavored transitions of the isotopes of Bi (Z = 83) nuclei in the region 184 {<=}A {<=} 224, from both the ground state (g.s.) and the isomeric state (i.s.) have been studied systematically within the Coulomb and proximity potential model (CPPM). The half-lives have been evaluated using the experimental Q-values. The computed half-lives are compared with the experimental data and they are in good agreement. We have modified the assault frequency and redetermined the half-lives and they show a better agreement with the experimental value. The standard deviation of the logarithm of the half-life with the former assault frequency is found to be 1.234 and with the modified assault frequency, it is found to be 0.935. This reveals that the CPPM, with the modified deformation-dependent assault frequency is more apt for the alpha-decay studies. Using our model we could also demonstrate the influence of the N = 126, neutron shell closure in both parent and daughter nuclei on the alpha-decay half-lives. (orig.)

  10. Highly charged ions in Penning traps, a new tool for resolving low lying isomeric states

    CERN Document Server

    Gallant, A T; Brunner, T; Chowdhury, U; Ettenauer, S; Simon, V V; Mané, E; Simon, M C; Andreoiu, C; Delheij, P; Gwinner, G; Pearson, M R; Ringle, R; Dilling, J

    2011-01-01

    The use of highly charged ions greatly increases the precision and resolving power, in particular for short-lived species produced at on-line radio-isotope beam facilities, achievable with Penning trap mass spectrometers. This increase in resolving power provides a new and unique access to resolving low-lying long-lived ($T_{1/2} > 50$ ms) nuclear isomers. Recently, the $111.19(22)$ keV (determined from $\\gamma$-ray spectroscopy) isomeric state in $^{78}$Rb has been resolved from the ground state, in a charge state of $q=8+$ with the TITAN Penning trap at the TRIUMF-ISAC facility. The energy level of the isomer was measured to be $108.7(6.4)$ keV above the ground state. The extracted masses for both the ground and isomeric states, and their difference, agree with the AME2003 and Nuclear Data Sheet values. This proof of principle measurement demonstrates the feasibility of using Penning trap mass spectrometers coupled to charge breeders to study nuclear isomers and opens a new route for isomer searches.

  11. Search for long-lived isomeric states in neutron-deficient thorium isotopes

    CERN Document Server

    Lachner, J; Fästermann, T; Korschinek, G; Poutivtsev, M; Rugel, G; 10.1103/PhysRevC.78.064313

    2009-01-01

    The discovery of naturally occurring long-lived isomeric states (t_1/2 > 10^8 yr) in the neutron-deficient isotopes 211,213,217,218Th [A. Marinov et al., Phys. Rev. C 76, 021303(R) (2007)] was reexamined using accelerator mass spectrometry (AMS). Because AMS does not suffer from molecular isobaric background in the detection system, it is an extremely sensitive technique. Despite our up to two orders of magnitude higher sensitivity we cannot confirm the discoveries of neutron-deficient thorium isotopes and provide upper limits for their abundances.

  12. 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.

  13. Spherical proton-neutron structure of isomeric states in Cd128

    OpenAIRE

    Cáceres, Lucía; Jungclaus, Andrea; Benlliure, J.; Casarejos, E.; Montes, F.; Martínez Pinedo, Gabriel; Wollersheim, H.J.

    2009-01-01

    The γ-ray decay of isomeric states in the even-even nucleus Cd128 has been observed. The nucleus of interest was produced both by the fragmentation of Xe136 and the fission of U238 primary beams. The level scheme was unambiguously constructed based on γγ coincidence relations in conjunction with detailed lifetime analysis employed for the first time on this nucleus. Large-scale shell-model calculations, without consideration of excitations across the N=82 shell closure, were performed and pro...

  14. Reduced Dimension DVR Study of cis-trans Isomerization in the S_1 State of C_2H_2

    CERN Document Server

    Baraban, Joshua H; Steeves, Adam H; Stanton, John F; Field, Robert W

    2011-01-01

    Isomerization between the cis and trans conformers of the S1 state of acetylene is studied using a reduced dimension DVR calculation. Existing DVR techniques are combined with a high accuracy potential energy surface and a kinetic energy operator derived from FG theory to yield an effective but simple Hamiltonian for treating large amplitude motions. The spectroscopic signatures of the S1 isomerization are discussed, with emphasis on the vibrational aspects. The presence of a low barrier to isomerization causes distortion of the trans vibrational level structure and the appearance of nominally electronically forbidden \\~A1A2 \\leftarrow X 1{\\Sigma}+g transitions to vibrational levels of the cis conformer. Both of these effects are modeled in agreement with experimental results, and the underlying mechanisms of tunneling and state mixing are elucidated by use of the calculated vibrational wavefunctions.

  15. Theoretical studies of 2-quinolinol: Geometries, vibrational frequencies, isomerization, tautomerism, and excited states

    Science.gov (United States)

    Pan, Yi; Lau, Kai-Chung; Al-Mogren, Muneerah Mogren; Mahjoub, Ahmed; Hochlaf, Majdi

    2014-10-01

    We treat theoretically 2-quinolinol(lactam), an analog of carbostyril and DNA bases. We characterized the ground state structure of 2-quinolinol and its isomer(lactim) using density functional theory(DFT). The reaction profile and energetics for lactam-lactim tautomerization and cis-lactim to trans-lactim isomerization predicted with explicitly correlated methods. We explored the pattern of the lowest singlet and triplet manifolds of states and electronic S1 ← S0 transitions using multiconfigurational methodologies. The theoretical results are compared with available experimental data and used to interpret the on-going photoelectron study of 2-quinolinol. Our analysis should help to understand the effect of tautomerism and aromaticity on the DNA bases.

  16. Microwave assisted synthesis and solid-state characterization of lithocholyl amides of isomeric aminopyridines.

    Science.gov (United States)

    Ahonen, Kari V; Lahtinen, Manu K; Valkonen, Arto M; Dracínský, Martin; Kolehmainen, Erkki T

    2011-02-01

    Microwave (MW) assisted synthesis and solid state structural characterizations of novel lithocholyl amides of 2-, 3-, and 4-aminopyridine are reported. It is shown that the MW technique is a proper method in the preparation of N-lithocholyl amides of isomeric aminopyridines. It offers many advantages compared to conventional heating. The molecular and crystal structures as well as the polymorphic and hydrated forms of prepared conjugates with their thermodynamic stabilities have been characterized by means of high resolution liquid- and solid-state NMR spectroscopy, single crystal and powder X-ray diffraction, and thermogravimetric analysis. Owing to the many biological functions of bile acids and amino substituted nitrogen heterocycles, knowledge of the crystal packing of these novel conjugates may have relevance for potential pharmaceutical applications.

  17. Isomeric and ground state energy level measurements of natural tellurium isotopes via (γ,n) reaction

    Science.gov (United States)

    Tamkas, M.; Akcali, O.; Durusoy, A.

    2015-04-01

    We have planned to measure isomeric and ground state energy levels in 120Te(γ,n)119m,gTe, 122Te(γ,n)121m,gTe, 128Te(γ,n)127m,gTe, 130Te(γ,n)129m,gTe photonuclear reactions of natural tellurium induced by bremsstrahlung photons with end-point energy at 18 MeV. The sample was irradiated in the clinical linear electron accelerator (Philips SLi-25) at Akdeniz University Hospital. The gamma spectrum of the tellurium sample was measured using HP(Ge) semiconductor detector (ORTEC) and multi channel analyzer. We used both MAESTRO (ORTEC) and home made root based gui program (Theia) for data analyzing. The obtained experimental data values are compared with NUDAT energy values.

  18. Rotational Isomeric State Model of Poly(vinylidene chloride) Based Upon ab Initio Electronic Structure Calculations

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhi-jie; LIU Yu-hua; L(U) Zhong-yuan; LI Ze-sheng

    2009-01-01

    The rotational isomeric state(RIS) model was constructed for poly(vinylidene chloride)(PVDC) based on quantum chemistry calculations. The statistical weighted parameters were obtained from RIS representations and ab initio energies of conformers for model molecules 2,2,4,4-tetrachloropentane(TCP) and 2,2,4,4,6, 6-hexachlorohep-tane(HCH). By employing the RIS method, the characteristic ratio C∞ was calculated for PVDC. The calculated cha-racteristic ratio for PVDC is in good agreement with experiment result. Additionally, we studied the influence of the statistical weighted parameters on C∞ by calculating δC∞/δlnw. According to the values of δC∞/δlnw, the effects of second-order Cl-CH2 pentane type interaction and Cl-Cl long range interaction on C∞ were found to be important. In contrast, first-order interaction is unimportant.

  19. A dipole band above the Iπ= 31/2- isomeric state in 189Pb

    Science.gov (United States)

    Cullen, D. M.

    2016-09-01

    This contribution focuses on the new observation of a dipole band built upon an Iπ=31/2- isomeric state in 189Pb, identified using recoil-isomer tagging at the University of Jyväskylä, Finland. This is the lightest odd-mass Pb isotope in which a dipole band is known. By comparison with the heavier-mass dipole bands, the dipole band in 189Pb was deduced to be based upon a π {≤ft( {s1/2 - 2{h9/2}{i13/2}} right){{11^ - }}} otimes v{≤ft( {i13/2 - 1} right)13/{2^ + }} configuration. However, in the 189Pb dipole band, the initial aligned angular momentum was larger than that exhibited by the dipole bands in the heavier-mass isotopes. This may be evidence for a reduced repulsive proton/neutron-hole interaction in 189Pb.

  20. 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.)

  1. Identification of a millisecond isomeric state in Cd81129 via the detection of internal conversion and Compton electrons

    Directory of Open Access Journals (Sweden)

    J. Taprogge

    2014-11-01

    Full Text Available The decay of an isomeric state in the neutron-rich nucleus 129Cd has been observed via the detection of internal conversion and Compton electrons providing first experimental information on excited states in this nucleus. The isomer was populated in the projectile fission of a 238U beam at the Radioactive Isotope Beam Factory at RIKEN. From the measured yields of γ-rays and internal conversion electrons, a multipolarity of E3 was tentatively assigned to the isomeric transition. A half-life of T1/2=3.6(2 ms was determined for the new state which was assigned a spin of (21/2+, based on a comparison to shell model calculations performed using state-of-the-art realistic effective interactions.

  2. Identification of a millisecond isomeric state in 129Cd81via the detection of internal conversion and Compton electrons

    Energy Technology Data Exchange (ETDEWEB)

    Taprogge, J.; Jungclaus, A.; Grawe, H.; Nishimura, S.; Xu, Z. Y.; Doornenbal, P.; Lorusso, G.; Nacher, E.; Simpson, G. S.; Soderstrom, P. A.; Sumikama, T.; Kondev, F. G.

    2014-11-10

    The decay of an isomeric state in the neutron-rich nucleus 129Cd has been observed via the detection of internal conversion and Compton electrons providing first experimental information on excited states in this nucleus. The isomer was populated in the projectile fission of a 238U beam at the Radioactive Isotope Beam Factory at RIKEN. From the measured yields of γ-rays and internal conversion electrons, a multipolarity of E 3 was tentatively assigned to the isomeric transition. A half-life of T1/2=3.6(2) msT1/2=3.6(2) ms was determined for the new state which was assigned a spin of (21/2+)(21/2+), based on a comparison to shell model calculations performed using state-of-the-art realistic effective interactions.

  3. Remarks to the problem of the isomeric state production in (gamma, gamma') reactions in the giant dipole resonance

    CERN Document Server

    Demekhina, N A; Karapetyan, G S

    2001-01-01

    The population of the isomeric states is considered in nuclei sup 1 sup 1 sup 5 In and sup 1 sup 8 sup 0 Hf in photonuclear (gamma, gamma') reactions at giant dipole resonance energies. The comparison with the earlier published experimental and theoretical data is made. The behavior of the excitation function gives an evidence for possible increase of the high-spin state population in the giant resonance range

  4. Effect of nuclear-reaction mechanisms on the population of excited nuclear states and isomeric ratios

    Science.gov (United States)

    Skobelev, N. K.

    2016-07-01

    Experimental data on the cross sections for channels of fusion and transfer reactions induced by beams of radioactive halo nuclei and clustered and stable loosely bound nuclei were analyzed, and the results of this analysis were summarized. The interplay of the excitation of single-particle states in reaction-product nuclei and direct reaction channels was established for transfer reactions. Respective experiments were performed in stable (6Li) and radioactive (6He) beams of the DRIBs accelerator complex at the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, and in deuteron and 3He beams of the U-120M cyclotron at the Nuclear Physics Institute, Academy Sciences of Czech Republic (Řež and Prague, Czech Republic). Data on subbarrier and near-barrier fusion reactions involving clustered and loosely bound light nuclei (6Li and 3He) can be described quite reliably within simple evaporation models with allowance for different reaction Q-values and couple channels. In reactions involving halo nuclei, their structure manifests itself most strongly in the region of energies below the Coulomb barrier. Neutron transfer occurs with a high probability in the interactions of all loosely bound nuclei with light and heavy stable nuclei at positive Q-values. The cross sections for such reactions and the respective isomeric ratios differ drastically for nucleon stripping and nucleon pickup mechanisms. This is due to the difference in the population probabilities for excited single-particle states.

  5. A dipole band above the Iπ= 31/2− isomeric state in 189Pb

    Directory of Open Access Journals (Sweden)

    Cullen D. M.

    2016-01-01

    Full Text Available This contribution focuses on the new observation of a dipole band built upon an Iπ=31/2− isomeric state in 189Pb, identified using recoil-isomer tagging at the University of Jyväskylä, Finland. This is the lightest odd-mass Pb isotope in which a dipole band is known. By comparison with the heavier-mass dipole bands, the dipole band in 189Pb was deduced to be based upon a π(s1/2−2h9/2i13/211−⊗v(i13/2−113/2+$\\pi {\\left( {s_{1/2}^{ - 2}{h_{9/2}}{i_{13/2}}} \\right_{{{11}^ - }}} \\otimes v{\\left( {i_{13/2}^{ - 1}} \\right_{13/{2^ + }}}$ configuration. However, in the 189Pb dipole band, the initial aligned angular momentum was larger than that exhibited by the dipole bands in the heavier-mass isotopes. This may be evidence for a reduced repulsive proton/neutron-hole interaction in 189Pb.

  6. Coexistence of normal, super-, and hyper-deformation in nuclei: A study with angular momentum projection method

    Institute of Scientific and Technical Information of China (English)

    SUN Yang; ZHANG JingYe; LONG GuiLu; WU ChengLi

    2009-01-01

    Angular-momentum-projected energy surface calculations for A ≈ 110 nuclei indicate three distinct energy minima occurring at different angular-momenta. These correspond to normal, super-, and hy-per-deformed shapes coexisting in one nucleus. 110Pd is studied in detail, with a quantitative prediction on super- and hyper-deformed spectra by the Projected Shell Model calculation. It is found that several other neighboring nuclei in the A-110 mass region, with the neutron number around 64, also exhibit clear super- and hyper-deformation minima in the projected calculation.

  7. High-spin {\\mu}s isomeric states in 96Ag

    CERN Document Server

    Becerril, A D; Amthor, A M; Baumann, T; Bazin, D; Berryman, J S; Brown, B A; Crawford, H L; Estrade, A; Gade, A; Ginter, T; Guess, C J; Hausmann, M; Hitt, G W; Mantica, P F; Matos, M; Meharchand, R; Minamisono, K; Montes, F; Perdikakis, G; Pereira, J; Portillo, M; Schatz, H; Smith, K; Stoker, J; Stolz, A; Zegers, R G T

    2011-01-01

    The isomeric and {\\beta} decays of the N = Z +2 nucleus 96Ag were investigated at NSCL. A cascade of {\\gamma}-ray transitions originating from the de-excitation of a {\\mu}s 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) {\\mu}s, more precise than previously reported. The existence of a second, longer-lived {\\mu}s isomer, associated with a 743-keV 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.

  8. High-spin μs isomeric states in 96Ag

    Science.gov (United States)

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

    2011-10-01

    The isomeric and β decays of the N=Z+2 nucleus 96Ag 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 (p3/2p1/2f5/2g9/2) model space, using the jj44b interaction, reproduced level energies and isomeric decay half-lives reasonably well.

  9. Thorium silicate compound as a solid-state target for production of isomeric thorium-229 nuclei by electron beam irradiation

    Science.gov (United States)

    Borisyuk, P. V.; Vasilyev, O. S.; Lebedinskii, Y. Y.; Krasavin, A. V.; Tkalya, E. V.; Troyan, V. I.; Habibulina, R. F.; Chubunova, E. V.; Yakovlev, V. P.

    2016-09-01

    In this paper, we discuss an idea of the experiment for excitation of the isomeric transition in thorium-229 nuclei by irradiating with electron beam targets with necessary physical characteristics. The chemical composition and bandgap of ThSi10O22 were determined by X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. It was found that the energy gap is equal to 7.7 eV and does not change when the target is exposed to a medium energy electron beam for a long time. This indicates that the compound possesses high electron-beam resistance. A quantitative estimation of the output function of isomeric thorium-229 nuclei generated by interaction of nuclei with the secondary electron flow formed by irradiating the solid-state ThSi10O22-based target is given. The estimation shows that ThSi10O22 is a promising thorium-containing target for investigating excitation of the nuclear low-lying isomeric transition in the thorium-229 isotope using medium-energy electrons.

  10. Thorium silicate compound as a solid-state target for production of isomeric thorium-229 nuclei by electron beam irradiation

    Directory of Open Access Journals (Sweden)

    P. V. Borisyuk

    2016-09-01

    Full Text Available In this paper, we discuss an idea of the experiment for excitation of the isomeric transition in thorium-229 nuclei by irradiating with electron beam targets with necessary physical characteristics. The chemical composition and bandgap of ThSi10O22 were determined by X-ray photoelectron spectroscopy and reflection electron energy loss spectroscopy. It was found that the energy gap is equal to 7.7 eV and does not change when the target is exposed to a medium energy electron beam for a long time. This indicates that the compound possesses high electron-beam resistance. A quantitative estimation of the output function of isomeric thorium-229 nuclei generated by interaction of nuclei with the secondary electron flow formed by irradiating the solid-state ThSi10O22-based target is given. The estimation shows that ThSi10O22 is a promising thorium-containing target for investigating excitation of the nuclear low-lying isomeric transition in the thorium-229 isotope using medium-energy electrons.

  11. The role of dissociation channels of excited electronic states in quantum optimal control of ozone isomerization: A three-state dynamical model

    Science.gov (United States)

    Kurosaki, Yuzuru; Ho, Tak-San; Rabitz, Herschel

    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 1A‧ 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.

  12. Isomeric states in neutron-deficient A~80-90 nuclei populated in the fragmentation of Ag107

    OpenAIRE

    Garnsworthy, A.B.; Cáceres, Lucía; Estévez Aguado, María Esther; Jungclaus, Andrea; Kurtukian Nieto, Teresa; Wieland, O.

    2009-01-01

    The relativistic projectile fragmentation of a 750 MeV per nucleon beam of Ag107 was used to populate isomeric states in neutron-deficient nuclei around A=80-90. Reaction products were separated and unambiguously identified using the GSI FRagment Separator (FRS) and its ancillary detectors. At the final focal plane, the fragments were slowed from relativistic energies by means of an aluminium degrader and implanted in a passive stopper in the center of the high-efficiency, high-granularity St...

  13. A VUV detection system for the direct photonic identification of the first excited isomeric state of $^{229}$Th

    CERN Document Server

    Seiferle, Benedict; Laatiaoui, Mustapha; Thirolf, Peter G

    2015-01-01

    With an expected energy of 7.6(5) eV, $^{229}$Th 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 $^{229}$Th. $^{229(m)}$Th ions originating from a $^{233}$U $\\alpha$-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 $^{229}$Th. 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 opt...

  14. 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.

  15. Half-lives of ground and isomeric states in 97Cd and the astrophysical origin of 96Ru

    Science.gov (United States)

    Lorusso, G.; Becerril, A.; Amthor, A.; Baumann, T.; Bazin, D.; Berryman, J. S.; Brown, B. A.; Cyburt, R. H.; Crawford, H. L.; Estrade, A.; Gade, A.; Ginter, T.; Guess, C. J.; Hausmann, M.; Hitt, G. W.; Mantica, P. F.; Matos, M.; Meharchand, R.; Minamisono, K.; Montes, F.; Perdikakis, G.; Pereira, J.; Portillo, M.; Schatz, H.; Smith, K.; Stoker, J.; Stolz, A.; Zegers, R. G. T.

    2011-05-01

    First experimental evidence for a high-spin isomer (25/2+) in 97Cd, a waiting point in the astrophysical rapid proton capture process, is presented. The data were obtained in β-decay studies at NSCL using the new RF Fragment Separator system and detecting β-delayed protons and β-delayed γ 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 β-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 96Ru are in place. When the new data are included in astrophysical rp-process calculations, one finds that an rp-process origin of 96Ru is unlikely.

  16. Multiconfigurational electronic wavefunctions in the full optimized reaction space: the isomerization of nitrosyl hydride to nitrogen hydroxide in the lowest singlet and triplet states

    Energy Technology Data Exchange (ETDEWEB)

    Dombek, M. G.

    1977-12-01

    Energy curves are determined for the lowest singlet and triplet states of the HNO molecule. The geometry is varied in that the hydrogen moves through 13 positions around the NO core to describe the isomerization reaction HNO yields HON. Quantitatively determined are the stable and metastable equilibrium positions in both states, the energy differences between these two equilibrium positions and between the two states, and the barriers with respect to isomerization. The calculations are carried out using a novel configuration interaction approach called the Full Optimized Reaction Space method, which involves multiconfigurational self-consistent field calculations as an integral part. In order to interpret the bonding changes occurring during the reaction, a novel type of orbital is developed and calculated. These are called Directed Localized Reaction Orbitals. With their help it proves possible to give an interpretation of the isomerization in terms of concepts which fit chemical intuition.

  17. Tuning excited state isomerization dynamics through ground state structural changes in analogous ruthenium and osmium sulfoxide complexes.

    Science.gov (United States)

    Garg, Komal; Engle, James T; Ziegler, Christopher J; Rack, Jeffrey J

    2013-08-26

    The complexes [Ru(bpy)2(pyESO)](PF6)2 and [Os(bpy)2(pyESO)](PF6)2, in which bpy is 2,2'-bipyridine and pyESO is 2-((isopropylsulfinyl)ethyl)pyridine, were prepared and studied by (1)H NMR, UV-visible and ultrafast transient absorption spectroscopy, as well as by electrochemical methods. Crystals suitable for X-ray structural analysis were grown for [Ru(bpy)2(pyESO)](PF6)2. Cyclic voltammograms of both complexes provide evidence for S→O and O→S isomerization as these voltammograms are described by an ECEC (electrochemical-chemical electrochemical-chemical) mechanism in which isomerization follows Ru(2+) oxidation and Ru(3+) reduction. The S- and O-bonded Ru(3+/2+) couples appear at 1.30 and 0.76 V versus Ag/AgCl in propylene carbonate. For [Os(bpy)2(pyESO)](PF6)2, these couples appear at 0.97 and 0.32 V versus Ag/AgCl in acetonitrile, respectively. Charge-transfer excitation of [Ru(bpy)2(pyESO)](PF6)2 results in a significant change in the absorption spectrum. The S-bonded isomer of [Ru(bpy)2(pyESO)](2+) features a lowest energy absorption maximum at 390 nm and the O-bonded isomer absorbs at 480 nm. The quantum yield of isomerization in [Ru(bpy)2(pyESO)](2+) was found to be 0.58 in propylene carbonate and 0.86 in dichloroethane solution. Femtosecond transient absorption spectroscopic measurements were collected for both complexes, revealing time constants of isomerizations of 81 ps (propylene carbonate) and 47 ps (dichloroethane) in [Ru(bpy)2(pyESO)](2+). These data and a model for the isomerizing complex are presented. A striking conclusion from this analysis is that expansion of the chelate ring by a single methylene leads to an increase in the isomerization time constant by nearly two orders of magnitude.

  18. 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.

  19. Identification of a millisecond isomeric state in {sup 129}Cd{sub 81} via the detection of internal conversion and Compton electrons

    Energy Technology Data Exchange (ETDEWEB)

    Taprogge, J. [Instituto de Estructura de la Materia, CSIC, E-28006 Madrid (Spain); Departamento de Física Teórica, Universidad Autónoma de Madrid, E-28049 Madrid (Spain); RIKEN Nishina Center, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198 (Japan); Jungclaus, A., E-mail: andrea.jungclaus@csic.es [Instituto de Estructura de la Materia, CSIC, E-28006 Madrid (Spain); Grawe, H. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Nishimura, S.; Xu, Z.Y.; Doornenbal, P.; Lorusso, G. [RIKEN Nishina Center, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198 (Japan); Nácher, E. [Instituto de Estructura de la Materia, CSIC, E-28006 Madrid (Spain); Simpson, G.S. [LPSC, Université Joseph Fourier Grenoble 1, CNRS/IN2P3, Institut National Polytechnique de Grenoble, F-38026 Grenoble cedex (France); Söderström, P.-A. [RIKEN Nishina Center, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198 (Japan); Sumikama, T. [Department of Physics, Tohoku University, Aoba, Sendai, Miyagi 980-8578 (Japan); Baba, H. [RIKEN Nishina Center, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198 (Japan); Browne, F. [School of Computing, Engineering and Mathematics, University of Brighton, Brighton BN2 4JG (United Kingdom); RIKEN Nishina Center, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198 (Japan); Fukuda, N. [RIKEN Nishina Center, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198 (Japan); Gernhäuser, R. [Physik Department E12, Technische Universität München, D-85748 Garching (Germany); and others

    2014-11-10

    The decay of an isomeric state in the neutron-rich nucleus {sup 129}Cd has been observed via the detection of internal conversion and Compton electrons providing first experimental information on excited states in this nucleus. The isomer was populated in the projectile fission of a {sup 238}U beam at the Radioactive Isotope Beam Factory at RIKEN. From the measured yields of γ-rays and internal conversion electrons, a multipolarity of E3 was tentatively assigned to the isomeric transition. A half-life of T{sub 1/2}=3.6(2) ms was determined for the new state which was assigned a spin of (21/2{sup +}), based on a comparison to shell model calculations performed using state-of-the-art realistic effective interactions.

  20. Cis-trans isomerization in the S1 state of acetylene: identification of cis-well vibrational levels.

    Science.gov (United States)

    Merer, Anthony J; Steeves, Adam H; Baraban, Joshua H; Bechtel, Hans A; Field, Robert W

    2011-06-28

    A systematic analysis of the S(1)-trans (Ã(1)A(u)) state of acetylene, using IR-UV double resonance along with one-photon fluorescence excitation spectra, has allowed assignment of at least part of every single vibrational state or polyad up to a vibrational energy of 4200 cm(-1). Four observed vibrational levels remain unassigned, for which no place can be found in the level structure of the trans-well. The most prominent of these lies at 46 175 cm(-1). Its (13)C isotope shift, exceptionally long radiative lifetime, unexpected rotational selection rules, and lack of significant Zeeman effect, combined with the fact that no other singlet electronic states are expected at this energy, indicate that it is a vibrational level of the S(1)-cis isomer (Ã(1)A(2)). Guided by ab initio calculations [J. H. Baraban, A. R. Beck, A. H. Steeves, J. F. Stanton, and R. W. Field, J. Chem. Phys. 134, 244311 (2011)] of the cis-well vibrational frequencies, the vibrational assignments of these four levels can be established from their vibrational symmetries together with the (13)C isotope shift of the 46 175 cm(-1) level (assigned here as cis-3(1)6(1)). The S(1)-cis zero-point level is deduced to lie near 44 900 cm(-1), and the ν(6) vibrational frequency of the S(1)-cis well is found to be roughly 565 cm(-1); these values are in remarkably good agreement with the results of recent ab initio calculations. The 46 175 cm(-1) vibrational level is found to have a 3.9 cm(-1) staggering of its K-rotational structure as a result of quantum mechanical tunneling through the isomerization barrier. Such tunneling does not give rise to ammonia-type inversion doubling, because the cis and trans isomers are not equivalent; instead the odd-K rotational levels of a given vibrational level are systematically shifted relative to the even-K rotational levels, leading to a staggering of the K-structure. These various observations represent the first definite assignment of an isomer of

  1. Photophysics of the Red Chromophore of HcRed: Evidence for Cis-Trans Isomerization and Protonation-State Changes

    Energy Technology Data Exchange (ETDEWEB)

    Cotlet, M.; Mudalige, K.; Habuchi, S.; Goodwin, P.M.; Pai, R.K.; De Schryver, F.

    2010-03-15

    HcRed is a dimeric intrinsically fluorescent protein with origins in the sea anemone Heteractis crispa. This protein exhibits deep red absorption and emission properties. Using a combination of ensemble and single molecule methods and by varying environmental parameters such as temperature and pH, we found spectroscopic evidence for the presence of two ground state conformers, trans and cis chromophores that are in thermal equilibrium and that follow different excited-state pathways upon exposure to light. The photocycle of HcRed appears to be a combination of both kindling proteins and bright emitting GFP/GFP-like proteins: the trans chromophore undergoes light driven isomerization followed by radiative relaxation with a fluorescence lifetime of 0.5 ns. The cis chromophore exhibits a photocycle similar to bright GFPs and GFP-like proteins such as enhanced GFP, enhanced YFP or DsRed, with radiative relaxation with a fluorescence lifetime of 1.5 ns, singlet-triplet deactivation on a microsecond time scale and solvent controlled protonation/deprotonation in tens of microseconds. Using single molecule spectroscopy, we identify trans and cis conformers at the level of individual moieties and show that it is possible that the two conformers can coexist in a single protein due to the dimeric nature of HcRed.

  2. Isomeric Character of the Lowest Observed 4+ State in 44S

    Science.gov (United States)

    Parker, J. J.; Wiedenhöver, I.; Cottle, P. D.; Baker, J.; McPherson, D.; Riley, M. A.; Santiago-Gonzalez, D.; Volya, A.; Bader, V. M.; Baugher, T.; Bazin, D.; Gade, A.; Ginter, T.; Iwasaki, H.; Loelius, C.; Morse, C.; Recchia, F.; Smalley, D.; Stroberg, S. R.; Whitmore, K.; Weisshaar, D.; Lemasson, A.; Crawford, H. L.; Macchiavelli, A. O.; Wimmer, K.

    2017-02-01

    Previous experiments observed a 4+ state in the N =28 nucleus 44S and suggested that this state may exhibit a hindered E 2 -decay rate, inconsistent with being a member of the collective ground state band. We populate this state via two-proton knockout from a beam of exotic 46Ar projectiles and measure its lifetime using the recoil distance method with the GRETINA γ -ray spectrometer. The result, 76 (14 )stat(20 )syst ps , implies a hindered transition of B (E 2 ;4+→21+)=0.61 (19 ) single-particle or Weisskopf units strength and supports the interpretation of the 4+ state as a K =4 isomer, the first example of a high-K isomer in a nucleus of such low mass.

  3. Resonance raman and absorption spectra of isomeric retinals in their lowest excited triplet states

    DEFF Research Database (Denmark)

    Wilbrandt, Robert Walter; Jensen, N.-H.; Houee-Levin, C.

    1985-01-01

    implications about the size of the energy barriers separating the various triplet species are discussed. The resonance Raman spectra obtained by using either anthracene (ET = 177.7 kJ mol-1) or naphthalene (ET = 254.8 kJ mol-1) as sensitizers were virtually identical for the corresponding triplet states from...

  4. Observation of a γ -decaying millisecond isomeric state in 128 Cd 80

    Energy Technology Data Exchange (ETDEWEB)

    Jungclaus, A.; Grawe, H.; Nishimura, S.; Doornenbal, P.; Lorusso, G.; Simpson, G. S.; Söderström, P. -A.; Sumikama, T.; Taprogge, J.; Xu, Z. Y.; Baba, H.; Browne, F.; Fukuda, N.; Gernhäuser, R.; Gey, G.; Inabe, N.; Isobe, T.; Jung, H. S.; Kameda, D.; Kim, G. D.; Kim, Y. -K.; Kojouharov, I.; Kubo, T.; Kurz, N.; Kwon, Y. K.; Li, Z.; Sakurai, H.; Schaffner, H.; Shimizu, Y.; Steiger, K.; Suzuki, H.; Takeda, H.; Vajta, Zs.; Watanabe, H.; Wu, J.; Yagi, A.; Yoshinaga, K.; Benzoni, G.; Bönig, S.; Chae, K. Y.; Coraggio, L.; Daugas, J. -M.; Drouet, F.; Gadea, A.; Gargano, A.; Ilieva, S.; Itaco, N.; Kondev, F. G.; Kröll, T.; Lane, G. J.; Montaner-Pizá, A.; Moschner, K.; Mücher, D.; Naqvi, F.; Niikura, M.; Nishibata, H.; Odahara, A.; Orlandi, R.; Patel, Z.; Podolyák, Zs.; Wendt, A.

    2017-09-01

    A new high-spin isomer in the neutron-rich nucleus 128Cd was populated in the projectile fission of a 238U beam at the Radioactive Isotope Beam Factory at RIKEN. A half-life of T1/2 = 6.3(8) ms was measured for the new state which was tentatively assigned a spin/parity of (15-). The experimental results are compared to shell model calculations performed using state-of-the-art realistic effective interactions and to the neighbouring nucleus 129Cd. In the present experiment no evidence was found for the decay of a 18+ E6 spin-trap isomer, based on the complete alignment of the two-neutron and two-proton holes in the 0h11/2 and the 0g9/2 orbit, respectively, which is predicted to exist by the shell model.

  5. Isomeric states close to doubly magic $^{132}$Sn studied with JYFLTRAP

    CERN Document Server

    Kankainen, A; Eronen, T; Gorelov, D; Jokinen, A; Kolhinen, V S; Moore, I D; Penttilä, H; Rinta-Antila, S; Rissanen, J; Saastamoinen, A; Sonnenschein, V; Äystö, J

    2012-01-01

    The double Penning trap mass spectrometer JYFLTRAP has been employed to measure masses and excitation energies for $11/2^-$ isomers in $^{121}$Cd, $^{123}$Cd, $^{125}$Cd and $^{133}$Te, for $1/2^-$ isomers in $^{129}$In and $^{131}$In, and for $7^-$ isomers in $^{130}$Sn and $^{134}$Sb. These first direct mass measurements of the Cd and In isomers reveal deviations to the excitation energies based on results from beta-decay experiments and yield new information on neutron- and proton-hole states close to $^{132}$Sn. A new excitation energy of 144(4) keV has been determined for $^{123}$Cd$^m$. A good agreement with the precisely known excitation energies of $^{121}$Cd$^m$, $^{130}$Sn$^m$, and $^{134}$Sb$^m$ has been found.

  6. Theoretical study of deactivation and isomerization pathways of 1,2-dithiete in excited electronic states

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The potential energy surface crossings for 1,2-dithiete have been investigated using the complete active space self-consistent field(CASSCF) method and simple group theory.Using the full Pauli-Breit spin-orbit coupling(SOC) operator(■) SO) which consists of the one-electron(■) SO1) and two-electron(■) SO2) terms,we estimate the strengths of the SOC(198.37 cm-1 when symmetry is imposed,and 211.35 cm-1 with no symmetry constraints),which plays an essential role in the spin transitions between different spin states.The calculations show that the photolysis of 1,3-dithiol-2-one leads to the formation of trans-dithioglyoxal(trans-MinS0) as a primary product which subsequently gives a secondary product identified as thiolthioketene.Our calculated results are in close agreement with the experimental observations.

  7. On the spectroscopic constants, first electronic state, vibrational frequencies, and isomerization of hydroxymethylene (HCOH+)

    Science.gov (United States)

    Theis, Riley A.; Fortenberry, Ryan C.

    2017-09-01

    The hydroxymethylene cation (HCOH+) is believed to be chemically independent of the more stable formaldehyde cation isomer in interstellar chemistry and may likely be a precursor to methanol in chemical reaction networks. Previous work is corroborated here showing that the trans conformer of HCOH+ is 3.48 kcal/mol lower than the cis on the potential energy surface. The small energy difference between the conformers and the much larger dipole moment of cis-HCOH+ (2.73 D) make this conformer more likely to be observed than trans-HCOH+ via telescopic rotational spectroscopy. A strong adiabatic shift is also predicted in the first electronic excitation into the 1 2A‧‧/2 2A state out of either conformer into a C1 structure reducing the excitation wavelength from the near-ultraviolet all the way into the near-infrared. The full set of fundamental vibrational frequencies are also computed here at high-level. The 3306.0 cm-1 and 3225.3 cm-1 hydroxide stretches, respective of bare trans- and cis-HCOH+ , are in agreement with previous theory but are significantly higher than the frequencies determined from previous experiment utilizing argon tagging techniques. This shift is likely because the proton-bound complex created with the argon tag reduces the experimental frequencies. Lower-level computations including the argon tag bring the hydroxide stretches much closer to the experimental frequencies indicating that the predicted frequencies for bare HCOH+ are likely well-described.

  8. The potential surface in the ground electronic state of HCP with the isomerization process: the validity of calculating potential surface with DFT methods

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The density functional theory (DFT) provides us an effective way to calculate large cluster systems with moderate computational demands. We calculate potential energy surfaces (PES) with several different approaches of DFT. The PES in the ground electronic state are related to HCP's isomerization process. The calculated PES are compared with the “experimental” PES obtained by fitting from the experimental vibrational spectra and that given by the “accurate” quantum chemistry calculation with more expensive computations. The comparisons show that the potential surfaces calculated with DFT methods can reach the accuracy of less than 0.1 eV.

  9. Absolute E3 and M2 transition probabilities for the electromagnetic decay of the ensuremath I^{π=K^{π}=8-} isomeric state in 132Ce

    Science.gov (United States)

    Perkowski, J.; Andrzejewski, J.; Srebrny, J.; Bruce, A. M.; Droste, Ch.; Grodner, E.; Kisieliński, M.; Korman, A.; Kowalczyk, M.; Kownacki, J.; Król, A.; Marganiec, J.; Mierzejewski, J.; Morek, T.; Sobczak, K.; Trzaska, W. H.; Zielińska, M.

    2009-12-01

    The decay of the ensuremath I^{π}=K^{π}=8- isomeric state at 2340keV in 132Ce has been investigated in the 120Sn(16O, 4n)132Ce reaction. The measurements were carried out in e - γ and γ - γ coincidence modes using an electron spectrometer coupled to the OSIRIS II gamma-ray array at the Heavy Ion Laboratory of the University of Warsaw. Experimentally obtained internal conversion coefficients for the ensuremath 8- rightarrow 6+ and ensuremath 8- rightarrow 5+ transitions allowed the multipolarities, mixing ratios, reduced transition probabilities and hindrance factors to be determined.

  10. Isomerization of sugars

    Science.gov (United States)

    Moliner-Marin, Manuel; Roman-Leshkov, Yuriy; Davis, Mark E; Nikolla, Eranda

    2014-05-20

    Disclosed are processes for isomerizing saccharides. Also disclosed are processes for converting saccharides to furan derivatives. Also disclosed are processes for converting starch to furan derivatives.

  11. Evidence of shell effects in the excitation function of 0.136-MeV isomeric state populated in the 93Nb (n,2n) 92Nbm reaction

    Science.gov (United States)

    Gul, K.

    2004-09-01

    Calculation for the excitation function of 0.136-MeV ( 2+ ) isomeric state in 92Nb has been carried out using Hauser-Feshbach and pre-equilibrium nuclear reaction models in 10 20 MeV energy range. A satisfactory agreement between the calculation and measurements requires the suppression of contribution from the negative-parity doublet consisting of the 0.226-MeV ( 2- ) and 0.390-MeV ( 3- ) states in 92Nb . This can be explained on the basis of highly retarded gamma transitions of higher energy states to the negative-parity doublet on account of its different shell model configuration compared to the shell model configuration of positive-parity states.

  12. Variations of structures and solid-state conductivity of isomeric silver(I) coordination polymers having linear and V-shaped thiophene-centered ditriazole ligands

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Bin [State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); School of Environmental and Chemical Engineering, Nanchang Hangkong University, Nanchang, 330063 (China); Geng, Jiao; Zhang, Lie [State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China); Huang, Wei, E-mail: whuang@nju.edu.cn [State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 (China)

    2014-07-01

    A pair of new linear and V-shaped acceptor–donor–acceptor (A−D−A) thiophene-centered ditriazole structural isomers, i.e., 2,5-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 1}) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 2}), has been synthesized and characterized. They are used as μ{sub 2}-bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L{sup 1})(NO{sub 3})]{sub n} (1) and [Ag(L{sup 2})(NO{sub 3})]{sub n} (2), which are also structural isomers at the supramolecular level. X-ray single-crystal diffraction analyses for 1 and 2 reveal that they exhibit the same one-dimensional (1D) coordination polymers but different structural architectures because of the distinguishable shape and configuration of isomeric ligands (L{sup 1} and L{sup 2}) and the alterations of the coordination numbers. More interestingly, compared with the free ligands, 1D silver(I) polymeric isomers 1 and 2 show significant enhancement of solid-state conductivity to different extents (1.42×10{sup 4} and 2.17×10{sup 3} times), where 6.96 times' enhancement of solid-state conductivity from 1 to 2 has been observed. The formation of Ag–N coordinative bonds and the configurational discrepancy of L{sup 1} and L{sup 2} are believed to play important roles in facilitating the electron transport between molecules, which can also be supported by Density Function Theory calculations of their band gaps. - Graphical abstract: A pair of linear and V-shaped isomeric thiophene-centered ditriazole ligands (L{sup 1}) and L{sup 2} are used to prepare a pair of silver(I) polymeric isomers (1 and 2), where significant enhancement of solid-state conductivity to different extents are observed originating from the distinguishable shape and configuration of isomeric ligands. - Highlights: • A pair of linear and V-shaped thiophene-centered ditriazole structural isomers is prepared. • They are used as µ{sub 2}-bridging ligands to prepare a pair of silver

  13. Analysis of isomeric ratios for medium-mass nuclei

    Science.gov (United States)

    Danagulyan, A. S.; Hovhannisyan, G. H.; Bakhshiyan, T. M.; Kerobyan, I. A.

    2016-09-01

    Values of the isomeric ratios for product nuclei originating from simple charge-exchange reactions were analyzed. The cross sections for the formation of product nuclei in ground and isomeric states were calculated with the aid of the TALYS 1.4 and EMPIRE 3.2 codes. The calculated values of the isomeric ratios were compared with their experimental counterparts taken from the EXFOR database. For the 86,87Y, 94,95,96,99Tc, and 44Sc nuclei, the experimental values of the isomeric ratios exceed the respective calculated values. The nuclei in question feature weak deformations and have high-spin yrast lines and rotational bands. The possible reason behind the discrepancy between theoretical and experimental isomeric ratios is that the decay of yrast states leads with a high probability to the formation of isomeric states of detected product nuclei.

  14. Multi-structural variational transition state theory: kinetics of the 1,5-hydrogen shift isomerization of the 1-butoxyl radical including all structures and torsional anharmonicity.

    Science.gov (United States)

    Xu, Xuefei; Papajak, Ewa; Zheng, Jingjing; Truhlar, Donald G

    2012-03-28

    We investigate the statistical thermodynamics and kinetics of the 1,5-hydrogen shift isomerization reaction of the 1-butoxyl radical and its reverse isomerization. The partition functions and thermodynamic functions (entropy, enthalpy, heat capacity, and Gibbs free energy) are calculated using the multi-structural torsional (MS-T) anharmonicity method including all structures for three species (reactant, product, and transition state) involved in the reaction. The calculated thermodynamic quantities have been compared to those estimated by the empirical group additivity (GA) method. The kinetics of the unimolecular isomerization reaction was investigated using multi-structural canonical variational transition state theory (MS-CVT) including both multiple-structure and torsional (MS-T) anharmonicity effects. In these calculations, multidimensional tunneling (MT) probabilities were evaluated by the small-curvature tunneling (SCT) approximation and compared to results obtained with the zero-curvature tunneling (ZCT) approximation. The high-pressure-limit rate constants for both the forward and reverse reactions are reported as calculated by MS-CVT/MT, where MT can be ZCT or SCT. Comparison with the rate constants obtained by the single-structural harmonic oscillator (SS-HO) approximation shows the importance of anharmonicity in the rate constants of these reactions, and the effect of multi-structural anharmonicity is found to be very large. Whereas the tunneling effect increases the rate constants, the MS-T anharmonicity decreases them at all temperatures. The two effects counteract each other at temperatures 385 K and 264 K for forward and reverse reactions, respectively, and tunneling dominates at lower temperatures while MS-T anharmonicity has a larger effect at higher temperatures. The multi-structural torsional anharmonicity effect reduces the final reverse reaction rate constants by a much larger factor than it does to the forward ones as a result of the

  15. Three novel photoisomeric compounds of the 4-acyl pyrazolone derivants: Crystal structures and substituent effects on photo-isomerism in solid state

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Three new photoisomeric compounds: 1,3-diphenyl-4-benzal-5-pyrazolone 4-methylthiosemicarbazone (DPBP-MTSC), 1,3-diphenyl-4-(4′-methylbenzal)-5-pyrazolone 4-methylthiosemicarbazone (DP4MBP- MTSC), and 1,3-diphenyl-4-(4′-bromobenzal)-5-pyrazolone 4-methylthiosemicarbazone (DP4BrBP-MTSC) were synthesized by direct condensation of pyrazolones and 4-methylthiosemicarbazone. Their struc- tures were confirmed using 1H NMR, IR, elemental analyses, and X-ray crystallographic analyses. The photoisomeric properties in the solid state were studied under UV light irradiation and the photo- isomerization phenomena were interpreted by the double proton-transfer mechanism. Moreover, the effects of different substituent groups at the 4-position of the benzal in the three compounds on the photoisomeric properties were discussed.

  16. Three novel photoisomeric compounds of the 4-acyl pyrazolone derivants: Crystal structures and substituent effects on photo-isomerism in solid state

    Institute of Scientific and Technical Information of China (English)

    WANG JunHua; LIU Lang; LIU GuangFei; GUO JiXi; JIA DianZeng

    2008-01-01

    Three new photoisomeric compounds: 1,3-diphenyl-4-benzal-5-pyrazolone 4-methylthiosemicarbazone (DPBP-MTSC), 1,3-diphenyl-4-(4'-methylbenzal)-5-pyrazolone 4-methylthiosemicarbazone (DP4MBP-MTSC), and 1,3-diphenyl-4-(4'-bromobenzal)-5-pyrazolone 4-methylthiosemicarbazone (DP4BrBP-MTSC) were synthesized by direct condensation of pyrazolones and 4-methylthiosemicarbazone. Their struc-tures were confirmed using 1H NMR, IR, elemental analyses, and X-ray crystallographic analyses. The photoisomeric properties in the solid state were studied under UV light irradiation and the photo-isomerization phenomena were interpreted by the double proton-transfer mechanism. Moreover, the effects of different substituent groups at the 4-position of the benzal in the three compounds on the photoisomeric properties were discussed.

  17. Structural dynamics of nitrosylruthenium isomeric complexes studied with steady-state and transient pump-probe infrared spectroscopies

    Science.gov (United States)

    Zhao, Yan; Yang, Fan; Wang, Jianru; Yu, Pengyun; Pan, Huifen; Wang, Hongfei; Wang, Jianping

    2016-09-01

    The characteristic nitrosyl stretching (NO) in the region of 1800-1900 cm- 1 was used to study the geometric and ligand effect on two nitrosylruthenium complexes, namely [Ru(OAc)(2QN)2NO] (QN = 2-chloro-8-quinolinol (H2cqn) or QN = 2-methyl-8-quinolinol (H2mqn)). The NO stretching frequency (νNO) was found in the following order: νcis-1 (2cqn) > νcis-2 (2cqn) > νcis-1 (2mqn) > νtrans (2mqn). The results exhibited a spectral sensitivity of the NO mode to both charge distribution and ligand arrangement, which was supported by ab initio computations and natural bond orbital (NBO) analyses. Further, the vibrational population of the vibrationally excited NO stretching mode was found to relax on the order of 7-10 ps, showing less than 30% variation from one isomer to another, which were explained on the basis of NO local structures and solute-solvent interactions in these isomeric nitrosylruthenium complexes.

  18. 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)

  19. 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)

  20. Photobehavior of copper(I) compounds. 4. Role of the triplet state of (arylphosphine)copper(I) complexes in the photosensitized isomerization dienes

    Energy Technology Data Exchange (ETDEWEB)

    Liaw, B.; Orchard, S.W.; Kutal, C.

    1988-04-20

    Photoisomerization of cis- and trans-piperylene can be sensitized with high quantum efficiency by Cu(diphos)BH/sub 4/ (diphos is 1,2-bis(diphenylphosphino)ethane) and Cu(prophos)BH/sub 4/ (prophos is 1,3-bis(diphenylphosphino)propane). Sensitization is accompanied by quenching of the emissive /sup 3/(/sigma/-a/sub /pi//) excited state in each copper(I) complex, and the two processes occur with identical Stern-Volmer kinetics. Measurements of the trans/cis diene ratio at the photostationary state can be used to estimate the triplet-state energy as 60-61 kcal for Cu(diphos)BH/sub 4/ and > 61 kcal for Cu(prophos)BH/sub 4/; additional evidence suggests that 66-67 kcal is a reasonable value for the latter complex. Collectively, the results support the assignment of triplet-triplet energy transfer as the primary mechanism for sensitization and quenching in these systems. This mechanism also can accommodate earlier reports that Cu(diphos)BH/sub 4/ and Cu(prophos)BH/sub 4/ sensitize the valence isomerization of norbornadiene to quadricyclene with markedly different quantum efficiencies. 17 refs., 6 figs., 2 tabs.

  1. Cranked Skyrme-Hartree-Fock calculation for superdeformed and hyperdeformed rotational bands in N=Z nuclei from {sup 32}S to {sup 48}Cr

    Energy Technology Data Exchange (ETDEWEB)

    Inakura, T.; Mizutori, S.; Yamagami, M.; Matsuyanagi, K. E-mail: ken@ruby.scphys.kyoto-u.ac.jp

    2002-11-18

    With the use of the symmetry-unrestricted cranked Skyrme-Hartree-Fock method in the three-dimensional coordinate-mesh representation, we have carried out a systematic theoretical search for the superdeformed and hyperdeformed rotational bands in the mass A=30-50 region. Along the N=Z line, we have found superdeformed solutions in {sup 32}S, {sup 36}Ar, {sup 40}Ca, {sup 44}Ti, and hyperdeformed solutions in {sup 36}Ar, {sup 40}Ca, {sup 44}Ti, {sup 48}Cr. The superdeformed band in {sup 40}Ca is found to be extremely soft against both the axially symmetric (Y{sub 30}) and asymmetric (Y{sub 31}) octupole deformations. An interesting role of symmetry breaking in the mean field is pointed out.

  2. Cranked Skyrme-Hartree-Fock calculation for superdeformed and hyperdeformed rotational bands in N=Z nuclei from {sup 32}S to {sup 48}Cr

    Energy Technology Data Exchange (ETDEWEB)

    Inakura, T.; Yamagami, M.; Matsuyanagi, K. [Kyoto Univ., Dept. of Physics, Kyoto (Japan); Mizutori, S. [Kansai Women' s College, Dept. of Human Science, Kashiwara, Osaka (Japan)

    2003-02-01

    With the use of the symmetry-unrestricted cranked Skyrme-Hartree-Fock method in the three-dimensional coordinate-mesh representation, we have carried out a systematic theoretical search for the superdeformed and hyperdeformed rotational bands in the mass A=30-50 region. Along the N=Z line, we have found superdeformed solutions in {sup 32}S, {sup 36}Ar, {sup 40}Ca, {sup 44}Ti, and hyperdeformed solutions in {sup 36}Ar, {sup 40}Ca, {sup 44}Ti, {sup 48}Cr. The superdeformed band in {sup 40}Ca is found to be extremely soft against both the axially symmetric (Y{sub 30}) and asymmetric (Y{sub 31}) octupole deformations. An interesting role of symmetry breaking in the mean field is pointed out. (author)

  3. Cranked Skyrme-Hartree-Fock calculation for superdeformed and hyperdeformed rotational bands in /N=Z nuclei from 32S to 48Cr

    Science.gov (United States)

    Inakura, T.; Mizutori, S.; Yamagami, M.; Matsuyanagi, K.

    2002-11-01

    With the use of the symmetry-unrestricted cranked Skyrme-Hartree-Fock method in the three-dimensional coordinate-mesh representation, we have carried out a systematic theoretical search for the superdeformed and hyperdeformed rotational bands in the mass A=30-50 region. Along the N= Z line, we have found superdeformed solutions in 32S, 36Ar, 40Ca, 44Ti, and hyperdeformed solutions in 36Ar, 40Ca, 44Ti, 48Cr. The superdeformed band in 40Ca is found to be extremely soft against both the axially symmetric ( Y30) and asymmetric ( Y31) octupole deformations. An interesting role of symmetry breaking in the mean field is pointed out.

  4. Low-lying isomeric state in {sup 80}Ga from the {beta}{sup -} decay of {sup 80}Zn

    Energy Technology Data Exchange (ETDEWEB)

    LicA, R.; Marginean, N.; Ghita, D.G. [Horia Hulubei National Institute for Physics and Nuclear Engineering, Bucharest (Romania); and others

    2012-10-20

    A new level scheme was constructed for {sup 80}Ga which is significantly different from the one previously reported. The excitation energy of a new low-lying state recently reported in [2] was identified at 22.4 keV. Properties of the level scheme suggest that the ground state has spin J = 6 and the first excited state has spin J = 3. The spin assignments are in agreement with laser spectroscopy values previously measured. Our work provides the first evidence for the J = 6 being the ground state.

  5. Systematic study of favored \\alpha-decay half-lives of closed shell odd-A and doubly-odd nuclei related to ground and isomeric states

    CERN Document Server

    Sun, Xiao-Dong; Li, Xiao-Hua

    2016-01-01

    In this work, we systematically investigate the favored $\\alpha$-decay half-lives and $\\alpha$ preformation probabilities of both odd-$A$ and doubly-odd nuclei related to ground and isomeric states around the doubly magic cores at $Z=82$, $N=82$ and at $Z=82$, $N=126$, respectively, within a two-potential approach from the view of the valence nucleon (or hole). The results show that the $\\alpha$ preformation probability is linear related to $N_\\text{p}N_\\text{n}$ or $N_\\text{p}N_\\text{n}I$, where $N_\\text{p}$, $N_\\text{n}$, and $I$ are the number of valence protons (or holes), the number of valence neutrons (or holes), and the isospin of the parent nucleus, respectively. Fitting the $\\alpha$ preformation probabilities data extracted from the differences between experimental data and calculated half-lives without a shell correction, we give two analytic formulas of the $\\alpha$ preformation probabilities and the values of corresponding parameters. Using those formulas and the parameters, we calculate the $\\alp...

  6. Symmetry control of radiative decay in linear polyenes: low barriers for isomerization in the S1 state of hexadecaheptaene.

    Science.gov (United States)

    Christensen, Ronald L; Galinato, Mary Grace I; Chu, Emily F; Fujii, Ritsuko; Hashimoto, Hideki; Frank, Harry A

    2007-02-14

    The room temperature absorption and emission spectra of the 4-cis and all-trans isomers of 2,4,6,8,10,12,14-hexadecaheptaene are almost identical, exhibiting the characteristic dual emissions S1-->S0 (21Ag- --> 11Ag-) and S2-->S0 (11Bu+ --> 11Ag-) noted in previous studies of intermediate length polyenes and carotenoids. The ratio of the S1-->S0 and S2-->S0 emission yields for the cis isomer increases by a factor of approximately 15 upon cooling to 77 K in n-pentadecane. In contrast, for the trans isomer this ratio shows a 2-fold decrease with decreasing temperature. These results suggest a low barrier for conversion between the 4-cis and all-trans isomers in the S1 state. At 77 K, the cis isomer cannot convert to the more stable all-trans isomer in the 21Ag- state, resulting in the striking increase in its S1-->S0 fluorescence. These experiments imply that the S1 states of longer polyenes have local energy minima, corresponding to a range of conformations and isomers, separated by relatively low (2-4 kcal) barriers. Steady state and time-resolved optical measurements on the S1 states in solution thus may sample a distribution of conformers and geometric isomers, even for samples represented by a single, dominant ground state structure. Complex S1 potential energy surfaces may help explain the complicated S2-->S1 relaxation kinetics of many carotenoids. The finding that fluorescence from linear polyenes is so strongly dependent on molecular symmetry requires a reevaluation of the literature on the radiative properties of all-trans polyenes and carotenoids.

  7. Neutron single-particle strengths at N =40 , 42: Neutron knockout from Ni,7068 ground and isomeric states

    Science.gov (United States)

    Recchia, F.; Weisshaar, D.; Gade, A.; Tostevin, J. A.; Janssens, R. V. F.; Albers, M.; Bader, V. M.; Baugher, T.; Bazin, D.; Berryman, J. S.; Brown, B. A.; Campbell, C. M.; Carpenter, M. P.; Chen, J.; Chiara, C. J.; Crawford, H. L.; Hoffman, C. R.; Kondev, F. G.; Korichi, A.; Langer, C.; Lauritsen, T.; Liddick, S. N.; Lunderberg, E.; Noji, S.; Prokop, C.; Stroberg, S. R.; Suchyta, S.; Wimmer, K.; Zhu, S.

    2016-11-01

    The distribution of single-particle strength in Ni,6967 was characterized with one-neutron knockout reactions from intermediate-energy Ni,7068 secondary beams, selectively populating neutron-hole configurations at N =39 and 41, respectively. The spectroscopic strengths deduced from the measured partial cross sections to the individual final states, as tagged by their γ -ray decays, are used to identify and quantify neutron configurations in the wave functions. While 69Ni compares well with shell-model predictions, the results for 67Ni challenge the validity of current effective shell-model Hamiltonians by revealing discrepancies that cannot be explained so far. These results suggest that our understanding of the low-lying states in the neutron-rich, semimagic Ni isotopes may be incomplete and requires further investigation on both the experimental and theoretical sides.

  8. Molecular Switch for Sub-Diffraction Laser Lithography by Photoenol Intermediate-State Cis-Trans Isomerization.

    Science.gov (United States)

    Mueller, Patrick; Zieger, Markus M; Richter, Benjamin; Quick, Alexander S; Fischer, Joachim; Mueller, Jonathan B; Zhou, Lu; Nienhaus, Gerd Ulrich; Bastmeyer, Martin; Barner-Kowollik, Christopher; Wegener, Martin

    2017-06-27

    Recent developments in stimulated-emission depletion (STED) microscopy have led to a step change in the achievable resolution and allowed breaking the diffraction limit by large factors. The core principle is based on a reversible molecular switch, allowing for light-triggered activation and deactivation in combination with a laser focus that incorporates a point or line of zero intensity. In the past years, the concept has been transferred from microscopy to maskless laser lithography, namely direct laser writing (DLW), in order to overcome the diffraction limit for optical lithography. Herein, we propose and experimentally introduce a system that realizes such a molecular switch for lithography. Specifically, the population of intermediate-state photoenol isomers of α-methyl benzaldehydes generated by two-photon absorption at 700 nm fundamental wavelength can be reversibly depleted by simultaneous irradiation at 440 nm, suppressing the subsequent Diels-Alder cycloaddition reaction which constitutes the chemical core of the writing process. We demonstrate the potential of the proposed mechanism for STED-inspired DLW by covalently functionalizing the surface of glass substrates via the photoenol-driven STED-inspired process exploiting reversible photoenol activation with a polymerization initiator. Subsequently, macromolecules are grown from the functionalized areas and the spatially coded glass slides are characterized by atomic-force microscopy. Our approach allows lines with a full-width-at-half-maximum of down to 60 nm and line gratings with a lateral resolution of 100 nm to be written, both surpassing the diffraction limit.

  9. Effect of isomeric structures of branched cyclic hydrocarbons on densities and equation of state predictions at elevated temperatures and pressures.

    Science.gov (United States)

    Wu, Yue; Bamgbade, Babatunde A; Burgess, Ward A; Tapriyal, Deepak; Baled, Hseen O; Enick, Robert M; McHugh, Mark A

    2013-07-25

    The cis and trans conformation of a branched cyclic hydrocarbon affects the packing and, hence, the density, exhibited by that compound. Reported here are density data for branched cyclohexane (C6) compounds including methylcyclohexane, ethylcyclohexane (ethylcC6), cis-1,2-dimethylcyclohexane (cis-1,2), cis-1,4-dimethylcyclohexane (cis-1,4), and trans-1,4-dimethylcyclohexane (trans-1,4) determined at temperatures up to 525 K and pressures up to 275 MPa. Of the four branched C6 isomers, cis-1,2 exhibits the largest densities and the smallest densities are exhibited by trans-1,4. The densities are modeled with the Peng-Robinson (PR) equation of state (EoS), the high-temperature, high-pressure, volume-translated (HTHP VT) PREoS, and the perturbed chain, statistical associating fluid theory (PC-SAFT) EoS. Model calculations highlight the capability of these equations to account for the different densities observed for the four isomers investigated in this study. The HTHP VT-PREoS provides modest improvements over the PREoS, but neither cubic EoS is capable of accounting for the effect of isomer structural differences on the observed densities. The PC-SAFT EoS, with pure component parameters from the literature or from a group contribution method, provides improved density predictions relative to those obtained with the PREoS or HTHP VT-PREoS. However, the PC-SAFT EoS, with either set of parameters, also cannot fully account for the effect of the C6 isomer structure on the resultant density.

  10. Effect of Isomeric Structures of Branched Cyclic Hydrocarbons on Densities and Equation of State Predictions at Elevated Temperatures and Pressures

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yue; Bamgbade, Babatunde A; Burgess, Ward A; Tapriyal, Deepak; Baled, Hseen O; Enick, Robert M; McHugh, Mark

    2013-07-25

    The cis and trans conformation of a branched cyclic hydrocarbon affects the packing and, hence, the density, exhibited by that compound. Reported here are density data for branched cyclohexane (C6) compounds including methylcyclohexane, ethylcyclohexane (ethylcC6), cis-1,2-dimethylcyclohexane (cis-1,2), cis-1,4-dimethylcyclohexane (cis-1,4), and trans-1,4-dimethylcyclohexane (trans-1,4) determined at temperatures up to 525 K and pressures up to 275 MPa. Of the four branched C6 isomers, cis-1,2 exhibits the largest densities and the smallest densities are exhibited by trans-1,4. The densities are modeled with the Peng–Robinson (PR) equation of state (EoS), the high-temperature, high-pressure, volume-translated (HTHP VT) PREoS, and the perturbed chain, statistical associating fluid theory (PC-SAFT) EoS. Model calculations highlight the capability of these equations to account for the different densities observed for the four isomers investigated in this study. The HTHP VT-PREoS provides modest improvements over the PREoS, but neither cubic EoS is capable of accounting for the effect of isomer structural differences on the observed densities. The PC-SAFT EoS, with pure component parameters from the literature or from a group contribution method, provides improved density predictions relative to those obtained with the PREoS or HTHP VT-PREoS. However, the PC-SAFT EoS, with either set of parameters, also cannot fully account for the effect of the C6 isomer structure on the resultant density.

  11. Theoretical and Experimental Evidence of Hydrogen Migration rather than Isomerization in the Acetylene Dication

    Science.gov (United States)

    Liekhus-Schmaltz, Chelsea; Li, Zheng; Petrovic, Vladimir; Martinez, Todd; Bucksbaum, Phil; AMO75113 Collaboration

    2016-05-01

    Theoretical calculations and experimental results in the acetylene dication have long agreed that isomerization after x-ray excitation occurs in the first singlet state, where the carbon-carbon bond lives long enough for isomerization to complete. These same calculations predict that a large barrier to isomerization exists that would cause isomerization to occur in about a picosecond, while there is some evidence for ultrafast isomerization in under 100 fs. However, new ab initio calculations of the acetylene dication reveal that ultrafast isomerization after x-ray excitation is unlikely. In this talk, we present evidence that signatures of hydrogen migration observed in recent time resolved LCLS data are mostly due to hydrogen migration in an excited state which dissociates too quickly for isomerization to complete. This material is based upon work supported by the National Science Foundation under Grant No. PHY-0649578.

  12. -Phenoxo--pseudohalide and -pseudohalide dinuclear, tetranuclear and one-dimensional complexes: magneto-structural correlation and interesting type of solid state isomerism

    Indian Academy of Sciences (India)

    Sujit Sasmal; Sasankasekhar Mohanta

    2012-11-01

    Five Schiff base ligands have been utilized to explore metallo-pseudohalide (azide or cyanate) systems. These ligands are the 1:1 condensation products of 3-methoxysalicylaldehyde with ethanolamine (H2L1)/1-(2-aminoethyl)-piperidine (HL2)/ 4-(2-aminoethyl)-morpholine (HL3) or salicylaldehyde with 1-(2-aminoethyl)-piperidine (HL4)/4-(2-aminoethyl)-morpholine (HL5). The derived complexes are as follows: Four heterobridged -phenoxo-1,1-azide/cyanate dinickel(II) compounds of composition [Ni$^{\\text{II}}_{2}$ (HL1)3(1,1-N3)]$\\cdot$3H2O (1), [Ni$^{\\text{II}}_{2}$ (L2)2(1,1-N3)(N3)(H2O)]·CH3CH2OH (2), [Ni$^{\\text{II}}_{2}$ (L3)2-(1,1-N3)(CH3CN)(H2O)](ClO4)·H2O·CH3CN (3) and [Ni$^{\\text{II}}_{2}$ (HL1)3(1,1-NCO)]·2H2O (4); Two 1,3-azide bridged tetranickel(II) compounds [{NiII(L4)(1,3-N3)(H2O)}4] (5) and [{NiII(L5)(1,3-N3)(H2O)}4] (6); Two 1,3-azide/cyanate one-dimensional compounds [CuIIL5(1,3-NCO)]·2H2O (7) and [CuIIL5(1,3-N3)]·2H2O (8). Except compound 5 which shows overall antiferromagnetic coupling, other compounds exhibit overall ferromagnetic interaction. Syntheses, crystal structures, magnetic properties, density functional theoretical (DFT) calculations and experimental/theoretical magneto-structural correlations have been carried out which have revealed some interesting observations on composition/topology, magneto-structural correlations and solid state isomerism. The results have been already published. The present report deals with a review of the salient and interesting features of these works.

  13. Probing cis-trans isomerization in the S{sub 1} state of C{sub 2}H{sub 2} via H-atom action and hot band-pumped IR-UV double resonance spectroscopies

    Energy Technology Data Exchange (ETDEWEB)

    Changala, P. Bryan; Baraban, Joshua H.; Field, Robert W., E-mail: rwfield@mit.edu [Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Merer, Anthony J. [Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan (China); Department of Chemistry, University of British Columbia, Vancouver, British Columbia V6T 1Z1 (Canada)

    2015-08-28

    We report novel experimental strategies that should prove instrumental in extending the vibrational and rotational assignments of the S{sub 1} state of acetylene, C{sub 2}H{sub 2}, in the region of the cis-trans isomerization barrier. At present, the assignments are essentially complete up to ∼500 cm{sup −1} below the barrier. Two difficulties arise when the assignments are continued to higher energies. One is that predissociation into C{sub 2}H + H sets in roughly 1100 cm{sup −1} below the barrier; the resulting quenching of laser-induced fluorescence (LIF) reduces its value for recording spectra in this region. The other difficulty is that tunneling through the barrier causes a staggering in the K-rotational structure of isomerizing vibrational levels. The assignment of these levels requires data for K values up to at least 3. Given the rotational selection rule K′ − ℓ{sup ′′} = ± 1, such data must be obtained via excited vibrational levels of the ground state with ℓ{sup ′′} > 0. In this paper, high resolution H-atom resonance-enhanced multiphoton ionization spectra are demonstrated to contain predissociated bands which are almost invisible in LIF spectra, while preliminary data using a hyperthermal pulsed nozzle show that ℓ{sup ′′} = 2 states can be selectively populated in a jet, giving access to K′ = 3 states in IR-UV double resonance.

  14. Isomeric ratio measurements with the ILL LOHENGRIN spectrometer

    OpenAIRE

    Chebboubi A.; Kessedjian G.; Litaize O.; Serot O.; Faust H.; Bernard D.; Blanc A.; Köster U.; Méplan O.; Mutti P.; Sage C.

    2016-01-01

    The modelling of γ heating and neutron damage inside a nuclear reactor is essential to design the next generation of nuclear reactors. The determination of the fission fragment momentum is a key element to perform accurate calculations of the γ heating. One way to assess this information is to look at the isomeric ratio of different nuclei. According to the lifetime of the isomeric state, different experimental techniques were developed at the LOHENGRIN spectrometer. A focus on the measuremen...

  15. Isomerization dynamics of a buckled nanobeam.

    Science.gov (United States)

    Collins, Peter; Ezra, Gregory S; Wiggins, Stephen

    2012-11-01

    We analyze the dynamics of a model of a nanobeam under compression. The model is a two-mode truncation of the Euler-Bernoulli beam equation subject to compressive stress applied at both ends. We consider parameter regimes where the first mode is unstable and the second mode can be either stable or unstable, and the remaining modes (neglected) are always stable. Material parameters used correspond to a silicon nanobeam. The two-mode model Hamiltonian is the sum of a (diagonal) kinetic energy term and a potential energy term. The form of the potential energy function suggests an analogy with isomerization reactions in chemistry, where "isomerization" here corresponds to a transition between two stable beam configurations. We therefore study the dynamics of the buckled beam using the conceptual framework established for the theory of isomerization reactions. When the second mode is stable the potential energy surface has an index one saddle, and when the second mode is unstable the potential energy surface has an index two saddle and two index one saddles. Symmetry of the system allows us to readily construct a phase space dividing surface between the two "isomers" (buckled states); we rigorously prove that, in a specific energy range, it is a normally hyperbolic invariant manifold. The energy range is sufficiently wide that we can treat the effects of the index one and index two saddles on the isomerization dynamics in a unified fashion. We have computed reactive fluxes, mean gap times, and reactant phase space volumes for three stress values at several different energies. In all cases the phase space volume swept out by isomerizing trajectories is considerably less than the reactant density of states, proving that the dynamics is highly nonergodic. The associated gap time distributions consist of one or more "pulses" of trajectories. Computation of the reactive flux correlation function shows no sign of a plateau region; rather, the flux exhibits oscillatory decay

  16. Isomeric ratio measurements with the ILL LOHENGRIN spectrometer

    Directory of Open Access Journals (Sweden)

    Chebboubi A.

    2016-01-01

    Full Text Available The modelling of γ heating and neutron damage inside a nuclear reactor is essential to design the next generation of nuclear reactors. The determination of the fission fragment momentum is a key element to perform accurate calculations of the γ heating. One way to assess this information is to look at the isomeric ratio of different nuclei. According to the lifetime of the isomeric state, different experimental techniques were developed at the LOHENGRIN spectrometer. A focus on the measurement of isomeric ratios of 136I in neutron induced fission of 241Pu is presented. A discussion with the current assumptions used in the evaluation process for isomeric ratio is also shown.

  17. Exercises in anatomy: cardiac isomerism.

    Science.gov (United States)

    Anderson, Robert H; Sarwark, Anne E; Spicer, Diane E; Backer, Carl L

    2014-01-01

    It is well recognized that the patients with the most complex cardiac malformations are those with so-called visceral heterotaxy. At present, it remains a fact that most investigators segregate these patients on the basis of their splenic anatomy, describing syndromes of so-called asplenia and polysplenia. It has also been known for quite some time, nonetheless, that the morphology of the tracheobronchial tree is usually isomeric in the setting of heterotaxy. And it has been shown that the isomerism found in terms of bronchial arrangement correlates in a better fashion with the cardiac anatomy than does the presence of multiple spleens, or the absence of any splenic tissue. In this exercise in anatomy, we use hearts from the Idriss archive of Lurie Children's Hospital in Chicago to demonstrate the isomeric features found in the hearts obtained from patients known to have had heterotaxy. We first demonstrate the normal arrangements, showing how it is the extent of the pectinate muscles in the atrial appendages relative to the atrioventricular junctions that distinguishes between morphologically right and left atrial chambers. We also show the asymmetry of the normal bronchial tree, and the relationships of the first bronchial branches to the pulmonary arteries supplying the lower lobes of the lungs. We then demonstrate that diagnosis of multiple spleens requires the finding of splenic tissue on either side of the dorsal mesogastrium. Turning to hearts obtained from patients with heterotaxy, we illustrate isomeric right and left atrial appendages. We emphasize that it is only the appendages that are universally isomeric, but point out that other features support the notion of cardiac isomerism. We then show that description also requires a full account of veno-atrial connections, since these can seemingly be mirror-imaged when the arrangement within the heart is one of isomerism of the atrial appendages. We show how failure to recognize the presence of such isomeric

  18. 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.

  19. A Comparative Account of the Kinetics of Light-Induced E-Z Isomerization of an Anthracene-Based Organogelator in Sol, Gel, Xerogel, and Powder States: Fiber to Crystal Transformation.

    Science.gov (United States)

    Mondal, Sanjoy; Chakraborty, Priyadarshi; Das, Sujoy; Bairi, Partha; Nandi, Arun K

    2016-05-31

    The organogel of (E)-N'-(anthracene-10-ylmethylene)-3,4,5-tris(dodecyloxy)benzohydrazide (I) in methyl cyclohexane having a fibrillar network structure exhibits excellent fluorescence, which decreases sharply with time upon photoirradiation at λ = 365 nm. It has been attributed to the transformation of the E isomer of I to the Z isomer, and the kinetics of E-Z isomerization are compared for the sol, gel, xerogel, and powder states. The rate constants at different temperatures are measured from Avrami plots and its increase with an increase in temperature, indicating temperature acts as a promoter for photoirradiated E-Z isomeization along the imine (C═N) bond. In the powder form, the rate constant values are the lowest compared to those of other states for all temperatures and the xerogels exhibit the highest rate of E-Z isomerization. The rate constants of sol and gel states mostly lie between the two. The wide-angle X-ray scattering pattern changes after ultraviolet (UV) irradiation with the generation of new sharp peaks whose intensities increase with an increase in irradiation time. A polarized optical microscopic study indicates formation of small crystalline dots on the fibers in the gels, dendritic morphology on the xerogel fibers, and large needlelike morphology at the surface boundary of the solid. The dried I gel exhibits a melting peak at 96.7 °C, but upon irradiation, two peaks are observed at 98.5 and 152.7 °C; the latter has been attributed to the melting of crystals of Z isomers. Similar higher melting peaks are observed both for the xerogel and for powders after UV irradiation; the powders exhibit the highest meting peak at 159.4 °C. Possible reasons for the variation of rate constant values in the four different states and the difference in morphology and melting points of crystals of Z isomers of I are discussed.

  20. Isomeric Ratios For Nuclei With Z=62-67 And A=142-152 Produced In The Relativistic Fragmentation Of Pb-208

    OpenAIRE

    Myalski, S.; Maj, A.; Podolyak, Zs; Becker, F.; Bednarczyk, P.(The Niewodniczanski Institute of Nuclear Physics, Krakow, Poland); Benzoni, G.; Blank, B.; Brandau, C; Bruce, A.M.; Caceres, L.; Camera, F.; Catford, W.N.; Cullen, I. J.; Dombradi, Zs.; Doornenbal, P.

    2009-01-01

    Isomeric states in nuclei with Z = 62-67 and A = 142-152 produced in the fragmentation of the relativistic (1 GeV/nucleon) Pb-208 beam were investigated. Isomeric ratios were determined for 10 isomeric states. Significant differences between theoretical and experimental values were observed.

  1. Roaming dynamics in Ketene isomerization

    CERN Document Server

    Mauguière, Frédéric A L; Ezra, Gregory S; Farantos, Stavros C; Wiggins, Stephen

    2014-01-01

    A reduced two dimensional model is used to study Ketene isomerization reaction. In light of recent results by Ulusoy \\textit{et al.} [J.\\ Phys.\\ Chem.\\ A {\\bf 117}, 7553 (2013)], the present work focuses on the generalization of the roaming mechanism to the Ketene isomerization reaction by applying our phase space approach previously used to elucidate the roaming phenomenon in ion-molecule reactions. Roaming is again found be associated with the trapping of trajectories in a phase space region between two dividing surfaces; trajectories are classified as reactive or nonreactive, and are further naturally classified as direct or non-direct (roaming). The latter long-lived trajectories are trapped in the region of non-linear mechanical resonances, which in turn define alternative reaction pathways in phase space. It is demonstrated that resonances associated with periodic orbits provide a dynamical explanation of the quantum mechanical resonances found in the isomerization rate constant calculations by Gezelter...

  2. Syntheses, structures, and magnetic properties of three one-dimensional end-to-end azide/cyanate-bridged copper(II) compounds exhibiting ferromagnetic interaction: new type of solid state isomerism.

    Science.gov (United States)

    Sasmal, Sujit; Sarkar, Sohini; Aliaga-Alcalde, Núria; Mohanta, Sasankasekhar

    2011-06-20

    The work in this paper presents the syntheses, structures, and magnetic properties of three end-to-end (EE) azide/cyanate-bridged copper(II) compounds [Cu(II)L(1)(μ(1,3)-NCO)](n)·2nH(2)O (1), [Cu(II)L(1)(μ(1,3)-N(3))](n)·2nH(2)O (2), and [Cu(II)L(2)(μ(1,3)-N(3))](n) (3), where the ligands used to achieve these species, HL(1) and HL(2), are the tridentate Schiff base ligands obtained from [1 + 1] condensations of salicylaldehyde with 4-(2-aminoethyl)-morpholine and 3-methoxy salicylaldehyde with 1-(2-aminoethyl)-piperidine, respectively. Compounds 1 and 2 crystallize in the monoclinic P2(1)/c space group, while compound 3 crystallizes in the orthorhombic Pbca space group. The metal center in 1-3 is in all cases pentacoordinated. Three coordination positions of the metal center in 1, 2, or 3 are satisfied by the phenoxo oxygen atom, imine nitrogen atom, and morpholine (for 1 and 2) or piperidine (for 3) nitrogen atom of one deprotonated ligand, [L(1)](-) or [L(2)](-). The remaining two coordination positions are satisfied by two nitrogen atoms of two end-to-end bridging azide ligands for 2 and 3 and one nitrogen atom and one oxygen atom of two end-to-end bridging cyanate ligands for 1. The coordination geometry of the metal ion is distorted square pyramidal in which one EE azide/cyanate occupies the apical position. Variable-temperature (2-300 K) magnetic susceptibilities of 1-3 have been measured under magnetic fields of 0.05 (from 2 to 30 K) and 1.0 T (from 30 to 300 K). The simulation reveals a ferromagnetic interaction in all three compounds with J values of +0.19 ± 0.01, +0.79 ± 0.01, and +1.25 ± 0.007 cm(-1) for 1, 2, and 3, respectively. Compound 1 is the sole example of a ferromagnetically coupled EE cyanate-bridged 1-D copper(II) system. In addition, a rare example of supramolecular isomerism and a nice example of magnetic isomerism have been observed and most interestingly a new type of solid state isomerism has emerged as a result of the comparison

  3. Simple, chemoselective, catalytic olefin isomerization.

    Science.gov (United States)

    Crossley, Steven W M; Barabé, Francis; Shenvi, Ryan A

    2014-12-01

    Catalytic amounts of Co(Sal(tBu,tBu))Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.

  4. Cranked Skyrme-Hartree-Fock calculation for superdeformed and hyperdeformed rotational bands in N=Z nuclei from sup 3 sup 2 S to sup 4 sup 8 Cr

    CERN Document Server

    Inakura, T; Yamagami, M; Matsuyanagi, K

    2002-01-01

    With the use of the symmetry-unrestricted cranked Skyrme-Hartree-Fock method in the three-dimensional coordinate-mesh representation, we have carried out a systematic theoretical search for the superdeformed and hyperdeformed rotational bands in the mass A=30-50 region. Along the N=Z line, we have found superdeformed solutions in sup 3 sup 2 S, sup 3 sup 6 Ar, sup 4 sup 0 Ca, sup 4 sup 4 Ti, and hyperdeformed solutions in sup 3 sup 6 Ar, sup 4 sup 0 Ca, sup 4 sup 4 Ti, sup 4 sup 8 Cr. The superdeformed band in sup 4 sup 0 Ca is found to be extremely soft against both the axially symmetric (Y sub 3 sub 0) and asymmetric (Y sub 3 sub 1) octupole deformations. An interesting role of symmetry breaking in the mean field is pointed out.

  5. The experimental isomeric cross-section ratio in the nuclear activation technique

    Science.gov (United States)

    Vänskä, R.; Rieppo, R.

    1981-02-01

    First, the experimental isomeric cross-section ratio is discussed considering a single metastable state induced. The experimental ratio is given in a straightforward and exact formula, which is generally applicable to any incident particle activation and to any isomeric pair of an exclusive, fractional or non-existing isomeric transition decay. Second, the derived experimental isomeric yield ration is adapted for the present work where neutron induced reactions are considered and gamma-ray spectrometry is utilized in the determination of the 14-15 MeV neutron activation cross-sections and isomeric cross-section ratios for the germanium reactions, 74Ge(n, α) 71m,gZn and 76Ge(n, 2n) 75m,gGe, leading to single metastable and ground states in the product.

  6. γ-ray Intensity Calculation for Isomeric Transition Decay

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In an isomeric transition (it is called simply IT) decay, electromagnetic radiation of gamma-ray isemitted in the transitions of nucleus from a high exciting state to a lower states and ground state, and anatomic radiation can be emitted as an alternative to gamma-ray emission in the transition of nucleusthrough internal conversion electron (it is called simply Ce) process. In general, the IT decay gamma-rays

  7. Direct observation of an isomeric state in {sup 98}Rb and nuclear properties of exotic rubidium isotopes measured by laser spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Procter, T.J.; Garnsworthy, A.B.; Levy, C.D.P.; Pearson, M.R. [TRIUMF, Vancouver, British Columbia (Canada); Behr, J.A.; Dilling, J. [TRIUMF, Vancouver, British Columbia (Canada); University of British Columbia, Department of Physics, Vancouver, British Columbia (Canada); Billowes, J. [The University of Manchester, School of Physics and Astronomy, Manchester (United Kingdom); Buchinger, F.; Crawford, J.E.; Leary, A.; Shelbaya, O.; Al Tamimi, W. [McGill University, Physics Department, Montreal, Quebec (Canada); Cheal, B. [University of Liverpool, Department of Physics, Liverpool (United Kingdom); Mane, E. [TRIUMF, Vancouver, British Columbia (Canada); Ministry of External Relations, Rio Bianco Institute, Brasilia (Brazil); Stolz, M. [Technische Universitaet Berlin, Berlin (Germany); Voss, A. [TRIUMF, Vancouver, British Columbia (Canada); University of Jyvaeskylae, Department of Physics, Jyvaeskylae (Finland)

    2015-02-01

    Fast-beam collinear laser spectroscopy experiments on rubidium have been performed at the ISAC radioactive ion beam facility at TRIUMF. Most recently, the neutron-rich {sup 98}Rb isotope has been studied for the investigation of shape coexistence. Two long-lived nuclear states in {sup 98}Rb have been clearly observed for the first time: a low-spin state, assigned a spin of I = 0, and a high-spin state. The high-spin state is tentatively assigned a spin of I = 3 based on this analysis in combination with gamma decay results. The measured nuclear properties of the two states are presented, alongside unpublished values of the neutron-deficient isotopes investigated previously. The mean-square charge radii of both states in {sup 98}Rb are observed to continue along the isodeformation line present after the N = 60 onset of deformation. (orig.)

  8. A case study of proline isomerization in cell signaling.

    Science.gov (United States)

    Min, Lie; Fulton, D Bruce; Andreotti, Amy H

    2005-01-01

    Protein-mediated interactions and enzymatic function provide the foundation upon which cellular signaling cascades control all of the activities of a cell. Post-translational modifications such as phosphorylation or ubiquitiation are well known means for modulating protein activity within the cell. These chemical modifications create new recognition motifs on proteins or shift conformational preferences such that protein catalytic and binding functions are altered in response to external stimuli. Moreover, detection of such modifications is often straightforward by conventional biochemical methods leading investigators toward mechanistic models of cell signaling involving post-translational modifications such as phosphorylation/dephosphorylation. While there is little doubt that such modifications play a significant role in transmission of information throughout the cell, there are certainly other mechanisms at work that are not as well understood at this time. Of particular interest in the context of this review is the intrinsic conformational switch afforded to a polypeptide by peptidyl prolyl cis/trans isomerization. Proline isomerization is emerging as a critical component of certain cell signaling cascades. In addition to serving as a conformational switch that enables a protein to adopt functionally distinct states, proline isomerization may serve as a recognition element for the ubiquitous peptidyl prolyl isomerases. This overview takes a close look at one particular signaling protein, the T cell specific tyrosine kinase Itk, and examines the role of proline isomerization and the peptidyl prolyl isomerase cyclophilin A in mediating Itk function following T cell receptor engagement.

  9. Catalysis of Protein Disulfide Bond Isomerization in a Homogeneous Substrate†

    Science.gov (United States)

    Kersteen, Elizabeth A.; Barrows, Seth R.; Raines, Ronald T.

    2008-01-01

    Protein disulfide isomerase (PDI) catalyzes the rearrangement of nonnative disulfide bonds in the endoplasmic reticulum of eukaryotic cells, a process that often limits the rate at which polypeptide chains fold into a native protein conformation. The mechanism of the reaction catalyzed by PDI is unclear. In assays involving protein substrates, the reaction appears to involve the complete reduction of some or all of its nonnative disulfide bonds followed by oxidation of the resulting dithiols. The substrates in these assays are, however, heterogeneous, which complicates mechanistic analyses. Here, we report the first analysis of disulfide bond isomerization in a homogeneous substrate. Our substrate is based on tachyplesin I, a 17-mer peptide that folds into a _-hairpin stabilized by two disulfide bonds. We describe the chemical synthesis of a variant of tachyplesin I in which its two disulfide bonds are in a nonnative state and side chains near its N-and C-terminus contain a fluorescence donor (tryptophan) and acceptor (N_-dansyllysine). Fluorescence resonance energy transfer from 280 to 465 nm increases by 28-fold upon isomerization of the disulfide bonds into their native state (which has a lower E°_ = -0.313 V than does PDI). We use this continuous assay to analyze catalysis by wild-type human PDI and a variant in which the C-terminal cysteine residue within each Cys—Gly—His—Cys active site is replaced with alanine. We find that wild-type PDI catalyzes the isomerization of the substrate with kcat/KM = 1.7 _ 105 M–1M s–1, which is the largest value yet reported for catalysis of disulfide bond isomerization. The variant, which is a poor catalyst of disulfide bond reduction and dithiol oxidation, retains virtually all of the activity of wild-type PDI in catalysis of disulfide bond isomerization. Thus, the C-terminal cysteine residues play an insignificant role in the isomerization of the disulfide bonds in nonnative tachyplesin I. We conclude that

  10. Catalysis of protein disulfide bond isomerization in a homogeneous substrate.

    Science.gov (United States)

    Kersteen, Elizabeth A; Barrows, Seth R; Raines, Ronald T

    2005-09-13

    Protein disulfide isomerase (PDI) catalyzes the rearrangement of nonnative disulfide bonds in the endoplasmic reticulum of eukaryotic cells, a process that often limits the rate at which polypeptide chains fold into a native protein conformation. The mechanism of the reaction catalyzed by PDI is unclear. In assays involving protein substrates, the reaction appears to involve the complete reduction of some or all of its nonnative disulfide bonds followed by oxidation of the resulting dithiols. The substrates in these assays are, however, heterogeneous, which complicates mechanistic analyses. Here, we report the first analysis of disulfide bond isomerization in a homogeneous substrate. Our substrate is based on tachyplesin I, a 17-mer peptide that folds into a beta hairpin stabilized by two disulfide bonds. We describe the chemical synthesis of a variant of tachyplesin I in which its two disulfide bonds are in a nonnative state and side chains near its N and C terminus contain a fluorescence donor (tryptophan) and acceptor (N(epsilon)-dansyllysine). Fluorescence resonance energy transfer from 280 to 465 nm increases by 28-fold upon isomerization of the disulfide bonds into their native state (which has a lower E(o') = -0.313 V than does PDI). We use this continuous assay to analyze catalysis by wild-type human PDI and a variant in which the C-terminal cysteine residue within each Cys-Gly-His-Cys active site is replaced with alanine. We find that wild-type PDI catalyzes the isomerization of the substrate with kcat/K(M) = 1.7 x 10(5) M(-1) s(-1), which is the largest value yet reported for catalysis of disulfide bond isomerization. The variant, which is a poor catalyst of disulfide bond reduction and dithiol oxidation, retains virtually all of the activity of wild-type PDI in catalysis of disulfide bond isomerization. Thus, the C-terminal cysteine residues play an insignificant role in the isomerization of the disulfide bonds in nonnative tachyplesin I. We conclude

  11. A proposed experimental method to determine $\\alpha$-sensitivity of splitting between ground and 7.6 eV isomeric states in Th-229

    OpenAIRE

    Berengut, J. C.; Dzuba, V. A.; Flambaum, V. V.; Porsev, S. G.

    2009-01-01

    The 7.6 eV electromagnetic transition between the nearly degenerate ground state and first excited state in the Th-229 nucleus may be very sensitive to potential changes in the fine-structure constant, $\\alpha = e^2/\\hbar c$. However, the sensitivity is not known, and nuclear calculations are currently unable to determine it. We propose measurements of the differences of atomic transition frequencies between thorium atoms (or ions) with the nucleus in the ground state and in the first excited...

  12. Band structure and decay channels of thorium-229 low-lying isomeric state for ensemble of thorium atoms adsorbed on calcium fluoride

    Energy Technology Data Exchange (ETDEWEB)

    Borisyuk, Petr V.; Vasilyev, Oleg S.; Krasavin, Andrey V.; Troyan, Victor I. [National Research Nuclear University ' ' MEPhI' ' (Moscow Engineering Physics Institute), Kashirskoye shosse 31, 115409 Moscow (Russian Federation); Lebedinskii, Yury Yu. [National Research Nuclear University ' ' MEPhI' ' (Moscow Engineering Physics Institute), Kashirskoye shosse 31, 115409 Moscow (Russian Federation); Moscow Institute of Physics and Technology (State University), Institutskiy per. 9, 141700 Dolgoprudny, Moscow region (Russian Federation); Tkalya, Eugene V. [Skobeltsyn Institute of Nuclear Physics, Lomonosov Moscow State University, Leninskie gory, 119991 Moscow (Russian Federation); Nuclear Safety Institute of Russian Academy of Science, Bol' shaya Tulskaya 52, 115191 Moscow (Russian Federation)

    2015-12-15

    The results are presented on the study of the electronic structure of thorium atoms adsorbed by the liquid atomic layer deposition from aqueous solution of thorium nitrate on the surface of CaF{sub 2}. The chemical state of the atoms and the change of the band structure in the surface layers of Th/CaF{sub 2} system on CaF{sub 2} substrate were investigated by XPS and REELS techniques. It was found that REELS spectra for Th/CaF{sub 2} system include peaks in the region of low energy losses (3-7 eV) which are missing in the similar spectra for pure CaF{sub 2}. It is concluded that the presence of the observed features in the REELS spectra is associated with the chemical state of thorium atoms and is caused by the presence of uncompensated chemical bonds at the Th/CaF{sub 2} interface, and, therefore, by the presence of unbound 6d- and 7s-electrons of thorium atoms. Assuming the equivalence of the electronic configuration of thorium-229 and thorium-232 atoms, an estimate was made on the time decay of the excited state of thorium-229 nuclei through the channel of the electron conversion. It was found that the relaxation time is about 40 μs for 6d-electrons, and about 1 μs for 7s-electrons. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Band structure and decay channels of thorium-229 low-lying isomeric state for ensemble of thorium atoms adsorbed on calcium fluoride

    OpenAIRE

    Borisyuk, P. V.; Vasilyev, O S; Krasavin, A.V.; Lebedinskii, Yu Yu; V. I. Troyan; Tkalya, E. V.

    2015-01-01

    The results are presented on the study of the electronic structure of thorium atoms adsorbed by the liquid atomic layer deposition from aqueous solution of thorium nitrate on the surface of CaF2. The chemical state of the atoms and the change of the band structure in the surface layers of Th/CaF2 system on CaF2 substrate were investigated by XPS and REELS techniques. It was found that REELS spectra for Th/CaF2 system include peaks in the region of low energy losses (3-7 eV) which are missing ...

  14. g-factor and quadrupole moment of the 212− isomeric state in 131La: Signature for a weakly-deformed magnetic rotational band head

    Directory of Open Access Journals (Sweden)

    Jasmeet Kaur

    2017-02-01

    Full Text Available The g-factor and the static quadrupole moment of a magnetic rotational band head 212− at 2121 keV in 131La have been determined by means of the time-differential perturbed angular distribution technique. The measured value of the g-factor, +1.060(4, is in agreement with the theoretical value for a three quasi-proton, π3{112−[505]⊗52+[422]⊗52+[413]} Nilsson configuration assignment. The observed spectroscopic quadrupole moment ratio, Qs(212−,131LaQs(192−,137La=0.457(4, supports the collective oblate shape (γ∼−60° with quadrupole deformation β2<0.07. The half-life of the 212− state, 37.2(1 ns, is re-measured with better accuracy.

  15. g-factor and quadrupole moment of the 21/2- isomeric state in 131La: Signature for a weakly-deformed magnetic rotational band head

    Science.gov (United States)

    Kaur, Jasmeet; Bansal, Neeraj; Bhati, A. K.; Kumar, R.; Sharma, Vijay R.; Kapoor, K.; Kumar, V.; Kaur, Navneet

    2017-02-01

    The g-factor and the static quadrupole moment of a magnetic rotational band head 21/2- at 2121 keV in 131La have been determined by means of the time-differential perturbed angular distribution technique. The measured value of the g-factor, + 1.060 (4), is in agreement with the theoretical value for a three quasi-proton, π3 {11/2- [ 505 ] ⊗5/2+ [ 422 ] ⊗5/2+ [ 413 ] } Nilsson configuration assignment. The observed spectroscopic quadrupole moment ratio, Qs (21/2- ,131 La)/Qs (19/2- ,137 La) = 0.457 (4), supports the collective oblate shape (γ ∼ - 60 °) with quadrupole deformation β2 < 0.07. The half-life of the 21/2- state, 37.2(1) ns, is re-measured with better accuracy.

  16. Molecular movie for the isomerization of acetylene dication made by time resolved Coulomb imaging

    CERN Document Server

    Li, Zheng; Curchod, Basile; Liekhus-Schmaltz, Chelsea; Vendrell, Oriol; Medvedev, Nikita; Pabst, Stefan; Cryan, James; Osipov, Timur; Bucksbaum, Phil; Martinez, Todd

    2016-01-01

    Experimental evidence has pointed toward the existence of ultrafast proton migration and isomerization as a key process for acetylene and its ions, however the actual mechanism for ultrafast isomerization of the acetylene [HCCH]2+ to vinylidene [H2CC]2+ dication remains nebulous. Theoretical studies show a high potential barrier of over 2 eV [J. Chem. Phys. 123, 134320 (2005)] for the isomerization pathways on the low lying dicationic states, the corresponding isomerization should take picoseconds. However a recent experiment with femtosecond X-ray free electron laser (XFEL) [Nature Commun. 6, 8199 (2015)] suggests signature of isomerization proceeding on a sub-100 femtosecond time scale. We present here a complete theoretical study of the dynamics of acetylene dication from Auger decay induced by X-ray photoionizing the carbon K shell. We find a pathway from high lying dissociative dicationic states, which can lead to the sub-100fs isomerization with assistance of the non-Born-Oppenheimer effect. Moreover, o...

  17. Theoretical Studies on the Isomerizations of CH3NO2

    Institute of Scientific and Technical Information of China (English)

    YANG Lijuan; LI Xiaoyan; ZENG Yanli; MENG Lingpeng; ZHENG Shijun

    2009-01-01

    The isomerizations of CH3NO2 (NM) have been investigated by density function theory (DFT) and electron density topological analysis methods. Nine isomers and eight isomerization channels were found. The connection relationship between the transition state (TS) and the isomers was confirmed by intrinsic reaction coordinate (IRC) tracing calculation. The calculation results show that in the CH3NO2→CH3ONOt process, the TS is a tight one (CH3NO2 does not break into CH3 and NO2 throughout the reaction), which is consistent with Arenass' results. A long structure transition region, which contains a four-numbered ring → a five-numbered ring → a four-numbered ring → a five-numbered ring structure, exists in CH3NOOc→CH2NOOH process. And it is the first time that a five-numbered ring TS was found in reaction.

  18. Isomerically Pure Tetramethylrhodamine Voltage Reporters.

    Science.gov (United States)

    Deal, Parker E; Kulkarni, Rishikesh U; Al-Abdullatif, Sarah H; Miller, Evan W

    2016-07-27

    We present the design, synthesis, and application of a new family of fluorescent voltage indicators based on isomerically pure tetramethylrhodamines. These new Rhodamine Voltage Reporters, or RhoVRs, use photoinduced electron transfer (PeT) as a trigger for voltage sensing, display excitation and emission profiles in the green to orange region of the visible spectrum, demonstrate high sensitivity to membrane potential changes (up to 47% ΔF/F per 100 mV), and employ a tertiary amide derived from sarcosine, which aids in membrane localization and simultaneously simplifies the synthetic route to the voltage sensors. The most sensitive of the RhoVR dyes, RhoVR 1, features a methoxy-substituted diethylaniline donor and phenylenevinylene molecular wire at the 5'-position of the rhodamine aryl ring, exhibits the highest voltage sensitivity to date for red-shifted PeT-based voltage sensors, and is compatible with simultaneous imaging alongside green fluorescent protein-based indicators. The discoveries that sarcosine-based tertiary amides in the context of molecular-wire voltage indicators prevent dye internalization and 5'-substituted voltage indicators exhibit improved voltage sensitivity should be broadly applicable to other types of PeT-based voltage-sensitive fluorophores.

  19. Ultrafast structural dynamics and isomerization in Rydberg-exited Quadricyclane

    Energy Technology Data Exchange (ETDEWEB)

    Rudakov, Fedor M [ORNL

    2012-01-01

    The quadricyclane - norbornadiene system is an important model for the isomerization dynamics between highly strained molecules. In a breakthrough observation for a polyatomic molecular system of that complexity, we follow the photoionization from Rydberg states in the time-domain to derive a measure for the time-dependent structural dynamics and the time-evolving structural dispersion even while the molecule is crossing electronic surfaces. The photoexcitation to the 3s and 3p Rydberg states deposits significant amounts of energy into vibrational motions. We observe the formation and evolution of the vibrational wavepacket on the Rydberg surface and the internal conversion from the 3p Rydberg states to the 3s state. In that state, quadricyclane isomerizes to norbornadiene with a time constant of {tau}{sub 2} = 136(45) fs. The lifetime of the 3p Rydberg state in quadricyclane is {tau}{sub 1} = 320(31) and the lifetime of the 3s Rydberg state in norbornadiene is {tau}{sub 3} = 394(32).

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

    Science.gov (United States)

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

    2016-03-21

    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.

  1. Isomerization mechanism in hydrazone-based rotary switches: lateral shift, rotation, or tautomerization?

    Science.gov (United States)

    Landge, Shainaz M; Tkatchouk, Ekatarina; Benítez, Diego; Lanfranchi, Don Antoine; Elhabiri, Mourad; Goddard, William A; Aprahamian, Ivan

    2011-06-29

    Two intramolecularly hydrogen-bonded arylhydrazone (aryl = phenyl or naphthyl) molecular switches have been synthesized, and their full and reversible switching between the E and Z configurations have been demonstrated. These chemically controlled configurational rotary switches exist primarily as the E isomer at equilibrium and can be switched to the protonated Z configuration (Z-H(+)) by the addition of trifluoroacetic acid. The protonation of the pyridine moiety in the switch induces a rotation around the hydrazone C=N double bond, leading to isomerization. Treating Z-H(+) with base (K(2)CO(3)) yields a mixture of E and "metastable" Z isomers. The latter thermally equilibrates to reinstate the initial isomer ratio. The rate of the Z → E isomerization process showed small changes as a function of solvent polarity, indicating that the isomerization might be going through the inversion mechanism (nonpolar transition state). However, the plot of the logarithm of the rate constant k vs the Dimroth parameter (E(T)) gave a linear fit, demonstrating the involvement of a polar transition state (rotation mechanism). These two seemingly contradicting kinetic data were not enough to determine whether the isomerization mechanism goes through the rotation or inversion pathways. The highly negative entropy values obtained for both the forward (E → Z-H(+)) and backward (Z → E) processes strongly suggest that the isomerization involves a polarized transition state that is highly organized (possibly involving a high degree of solvent organization), and hence it proceeds via a rotation mechanism as opposed to inversion. Computations of the Z ↔ E isomerization using density functional theory (DFT) at the M06/cc-pVTZ level and natural bond orbital (NBO) wave function analyses have shown that the favorable isomerization mechanism in these hydrogen-bonded systems is hydrazone-azo tautomerization followed by rotation around a C-N single bond, as opposed to the more common

  2. Effects of Pressure, Solvent, and Substituenton the Thermal Isomerization of 2-Oxo-spiro[diazirine-3,3-indoline]

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The kinetic effects of pressure, solvent, and substituent on the thermal isomerization from 2-oxospiro[diazirine-3,3-indoline] to 3-diazo-2-oxo-indoline have been examined. The rate constants of the thermal isomerization increased with increasing external pressure and were related to the σ+P substituent constant of Hammett correlation. The results suggest that the thermal isomerization proceeds via a dipolar transition state involving heterolytic bond fission. However, the kinetic solvent effects on the thermal isomerization were not observed. The special solvent effects were discussed on the basis of the linear free energy relationship.

  3. Isomerization of Asp residues plays an important role in αA-crystallin dissociation.

    Science.gov (United States)

    Takata, Takumi; Fujii, Noriko

    2016-03-01

    Aged cataract formation is caused by the accumulative precipitation of lens proteins incorporating diverse post-translational modifications. α-Crystallin, a major structural and functional lens protein, consists of a large polymeric structure that is dissociated and insolubilized with accumulative post-translational modifications. One such modification, isomerization of Asp, was recently identified in αB-crystallin monomers derived from aged lens. However, the distributions of Asp isomers in each lens fraction remain unknown. Here, α-crystallin fractions from aged lens were separated into heteropolymeric and monomeric forms to determine the Asp isomerization ratios in each fraction. Lens of four different ages were homogenized and centrifuged, and the soluble fraction was applied to size-exclusion chromatography. The heteropolymeric α-crystallin and monomeric crystallin fractions were obtained and concentrated. After trypsin digestion, each fraction was independently applied to liquid chromatography equipped with mass spectrometry to extract α-crystallin-derived peptides containing Asp isomers. The results showed that Asp58, Asp84 and Asp151 of αA-crystallin were highly isomerized in the monomeric fraction, but not isomerized to the same level in the heteropolymeric fraction. Each type of Asp isomerization increased in an age-dependent manner, was site-specific and was similar to previous results from lens water-insoluble fractions. These results imply that isomerization of Asp residues leads to dissociation of αA-crystallin from the heteropolymeric state and induces insolubilization in aged lens. Taken together, our findings suggest that isomerization of Asp might disrupt the higher order polymeric state of α-crystallin, resulting in decreased solubility and function, ultimately contributing to lens protein impairment and cataract formation with aging. © 2015 Federation of European Biochemical Societies.

  4. Low-lying isomeric levels in 75Cu

    Energy Technology Data Exchange (ETDEWEB)

    Daugas, J. M. [Grand Accelerateur National d' Ions Lourds (GANIL); Faul, T. [CEA, France; Grawe, H. [GSI-Hemholtzzentrum fur Schwerionenforschung, Darmstadt, Germany; Pfutzner, M. [University of Warsaw; Grzywacz, R. [University of Tennessee, Knoxville (UTK); Lewitowicz, M. [Grand Accelerateur National d' Ions Lourds (GANIL); Achouri, N. L. [CNRS/IN2P3, Caen, France; Angelique, J. C. [CNRS/IN2P3, Caen, France; Baiborodin, D. [Nuclear Physic Institute, Czech Republic; Bentida, R. [Universite de Lyon, France; Beraud, R. [Universite de Lyon, France; Borcea, C. [IFIN, Bucharest-Magurele, Romania; Bingham, C. R. [University of Tennessee, Knoxville (UTK); Catford, W. [University of Surrey, UK; Emsallem, A. [Universite de Lyon, France; De France, G. [Grand Accelerateur National d' Ions Lourds (GANIL); Grzywacz, K. L. [University of Tennessee, Knoxville (UTK); Lemmon, R. [Daresbury Laboratory, UK; Lopez Jimenez, M. J. [Grand Accelerateur National d' Ions Lourds (GANIL); de Oliveira Santos, F. [Grand Accelerateur National d' Ions Lourds (GANIL); Regan, P. H. [University of Surrey, UK; Rykaczewski, Krzysztof Piotr [ORNL; Sauvestre, J. E. [CEA, France; Sawicka, M. [University of Warsaw; Stanoiu, M. [Grand Accelerateur National d' Ions Lourds (GANIL); Sieja, K. [Technische Universitat Darmstadt, Germany; Nowacki, F. [Institut Pluridisciplinaire Hubert Curien, Strasbourg, France

    2010-01-01

    Isomeric low-lying states were identified and investigated in the 75Cu 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 75m1Cu and 75m2Cu, 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 g9/2. 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.

  5. Novel endo- to exo-isomerization of dicyclopentadiene

    Institute of Scientific and Technical Information of China (English)

    Xiang Wen Zhang; Kai Jiang; Qiang Jiang; Ji Jun Zou; Li Wang; Zhen Tao Mi

    2007-01-01

    Endo-dicyclopentadiene was isomerized to exo-isomer by thermal treatment at evaluated temperature and pressure.The reaction temperature and pressure are key factors for this novel isomerization.This result may have great potential for practical application.

  6. 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.

  7. Study on mechanism of isomerization between ammonium thiocyanate and thiourea

    Science.gov (United States)

    Zhang, Chao-Zhi; Niu, Meng-Xiao

    2016-12-01

    Application of ammonium thiocyanate that can be separated from wastewater in coking plant is limited. It may isomerize to thiourea which has widely applied in industry. However, the isomerization yield is low. Moreover, the isomerization temperature is more than 145 °C. In this paper, the isomerization was investigated. The mechanism of the isomerization was supposed based on quantum chemistry calculations. Ammonia was employed as a catalyst to lower isomerization temperature and improved the yield of thiourea in the isomerization reaction. Results of quantum chemical calculation and experiments support the supposed mechanism. The mechanism can be applied in production of thiourea from isomerization of ammonium thiocyanate. The paper suggests a useful way of resourcizing ammonium thiocyanate in wastewater.

  8. 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.

  9. Isomeric Yields Ratios in 120Te(γ,n)119m,gTe Reaction in the E1-GIANT Resonance Region

    Science.gov (United States)

    Mazur, V. M.; Symochko, D. M.; Bigan, Z. M.; Poltorzhytska, T. V.

    Isomeric state excitation in the 120Te(γ,n)119m,gTe reaction within the 10-20 MeV energy range has been studied with bremsstrahlung beams. Energy dependences of experimental isomeric yields ratios and reaction cross-sections have been obtained. Experimental results are compared with TALYS-1.2 calculations.

  10. Photo-isomerization of Aromatic α-Hydroxy Hydrazone

    Institute of Scientific and Technical Information of China (English)

    JIN Jing-yi; PAN Yan; LI Xiu-hua; HOU Jun; WU Xue; SU Zhong-min

    2012-01-01

    Photo-isomerization of aromatic α-hydroxy hydrazone was reported.We investigated the structures of salicylaldehyde phenylhydrozone(SP) in the ground state using density functional theory(DFT) with the B3LYP functional and the 6-31 l+G(d) basis set.All nine possible isomers of SP in the ground state consist of seven phenol forms and two ketone forms.Intrisic reaction coordinate(IRC) analysis discloses the existence of a cycle driven by the two proton transfer processes in the ground and excited states of SP,which suggests that no ketonic form could exist in the ground state.Further theoretical studies of the potential energy surfaces support a trans-cis conversion followed by a relaxation to the stable form of SP in the excited states.

  11. 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.

  12. Measurement of the isomeric yield ratios of fission products with JYFLTRAP

    CERN Document Server

    Gorelov, D; Hakala, J; Jokinen, A; Kolhinen, V S; Koponen, J; Lantz, M; Matteram, A; Moore, I; Penttilä, H; Pohjalainen, I; Pomp, S; Rakopoulos, V; Reponen, M; Rinta-Antilav, S; Schonnenschein, V; Simutkin, V; Solders, A; Voss, A; Äystö, J

    2014-01-01

    Several isomeric yield ratios of fission products in 25 MeV pr oton-induced fis- sion of 238 U were measured recently at the JYFLTRAP facility. The ion-g uide separator on-line method was utilized to produce radioacti ve ions. The dou- ble Penning-trap mass spectrometer was used to separate iso meric and ground states by their masses. To verify the new experimental techn ique γ -spectro- scopy method was used to obtain the same isomeric ratios.

  13. Theoretical exploration of the potential energy surface of the HOI → HIO isomerization reaction

    Science.gov (United States)

    Sun, Q.; Mackie, J. C.; Dlugogorski, B. Z.; Kennedy, E. M.

    2007-02-01

    The isomerization reaction HOI → HIO has been investigated using quantum mechanical techniques. The activation energy of the reaction at the CCSD(T) level of theory is 77.0 kcal/mol. Molecular parameters and relative energies of HOI, HIO, five HOI-H 2O complexes, three HIO-H 2O complexes and four transition states have been calculated by the B3LYP method. For isomerization assisted by a single water molecule, the activation energy whereby the water molecule directly facilitates proton transfer during isomerization, reduces to 48.4 kcal/mol. Where the water molecule interacts with the HOI/HIO system by forming hydrogen-bond and/or van der Waals complexes, the activation energy is not significantly reduced.

  14. CRIS: A new method in isomeric beam production

    Directory of Open Access Journals (Sweden)

    Lynch K.M.

    2013-12-01

    Full Text Available The Collinear Resonance Ionization Spectroscopy (CRIS experiment at ISOLDE, CERN, uses laser radiation to stepwise excite and ionize an atomic beam for the purpose of ultra-sensitive detection of rare isotopes, and hyperfine-structure measurements. The technique also offers the ability to purify an ion beam that is heavily contaminated with radioactive isobars, including the ground state of an isotope from its isomer, allowing decay spectroscopy on nuclear isomeric states to be performed. The isomeric ion beam is selected by resonantly exciting one of its hyperfine structure levels, and subsequently ionizing it. This selectively ionized beam is deflected to a decay spectroscopy station (DSS. This consists of a rotating wheel implantation system for alpha- and beta-decay spectroscopy, and up to three germanium detectors around the implantation site for gamma-ray detection. Resonance ionization spectroscopy and the new technique of laser assisted nuclear decay spectroscopy have recently been performed at the CRIS beam line on the neutron-deficient francium isotopes. Here an overview of the two techniques will be presented, alongside a description of the CRIS beam line and DSS.

  15. Isomerism of the atrial appendages in the fetus.

    Science.gov (United States)

    Ho, S Y; Cook, A; Anderson, R H; Allan, L D; Fagg, N

    1991-01-01

    Thirty hearts from fetuses with visceral heterotaxy were examined to determine the range of cardiac malformations. By examining the morphology of the atrial appendages, 20 hearts were identified as having left isomerism (67%) and 10 hearts right isomerism (33%). Fifteen of the hearts with left isomerism had biventricular atrioventricular connections and five had univentricular atrioventricular connections. All 10 hearts with right isomerism had biventricular atrioventricular connections. Flow to the pulmonary arteries was obstructed or occluded in 6 hearts with left isomerism (30%) and 7 hearts with right isomerism (70%). Obstruction to aortic flow was present in 4 hearts with left isomerism (20%). Anomalies of the systemic and pulmonary veins were common in both groups. The suprarenal portion of the inferior caval vein was interrupted in 11 hearts with left isomerism (55%) and 1 heart with right isomerism (10%). Atrioventricular septal defect was present in 13 hearts with left isomerism (65%) and 9 hearts with right isomerism (90%). The arrangement of the liver or stomach in each group was not consistent, nor was the status of the spleen. The constellations of cardiac malformations in both groups corresponded to those known in postnatal life and similar guidelines for their identification were applicable.

  16. Slower processes of the ultrafast photo-isomerization of an azobenzene observed by IR spectroscopy

    NARCIS (Netherlands)

    Koller, F.O.; Sobotta, C.; Schrader, T.E.; Cordes, T.; Schreier, W.J.; Sieg, A.; Gilch, P.

    2007-01-01

    The photo-induced trans–cis isomerization of the azobenzene derivative 4-nitro-4'-(dimethylamino)azobenzene in polar solution was studied by femtosecond UV/Vis and IR spectroscopy. The UV/Vis experiment reveals two excited state processes; the slower one (1 ps) is the internal conversion to the grou

  17. Slower processes of the ultrafast photo-isomerization of an azobenzene observed by IR spectroscopy

    NARCIS (Netherlands)

    Koller, F.O.; Sobotta, C.; Schrader, T.E.; Cordes, T.; Schreier, W.J.; Sieg, A.; Gilch, P.

    2007-01-01

    The photo-induced trans–cis isomerization of the azobenzene derivative 4-nitro-4'-(dimethylamino)azobenzene in polar solution was studied by femtosecond UV/Vis and IR spectroscopy. The UV/Vis experiment reveals two excited state processes; the slower one (1 ps) is the internal conversion to the

  18. 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.

  19. A review of drug isomerism and its significance

    OpenAIRE

    Chhabra, Naveen; Aseri, Madan L; Padmanabhan, Deepak

    2013-01-01

    Isomerism finds its importance in the field of clinical pharmacology and pharmacotherapeutics, as isomers differ in their pharmacokinetic and pharmacodyanmic properties. Drug isomerism has opened a new era of drug development. Currently, knowledge of isomerism has helped us in introducing safer and more effective drug alternatives of the newer as well as existing drugs. Many existing drugs have gone chiral switch i.e., switching from racemic mixture to one of its isomers. Cetrizine to levocet...

  20. Methods for suppressing isomerization of olefin metathesis products

    Energy Technology Data Exchange (ETDEWEB)

    Firth, Bruce E.; Kirk, Sharon E.; Gavaskar, Vasudeo S.

    2015-09-22

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. The isomerization suppression agent is phosphorous acid, a phosphorous acid ester, phosphinic acid, a phosphinic acid ester or combinations thereof. Methods of refining natural oils are described.

  1. Amine-Catalyzed Isomerization of Diethylmaleate to Diethylfumarate.

    Science.gov (United States)

    Glover, Irving T.; And Others

    1978-01-01

    This reaction is used in an introductory organic chemistry course to illustrate principles of gas-liquid chromatography, geometrical isomerism, homogeneous catalysis, and activation energy determinations. (BB)

  2. A Theoretical Study on the Isomerization of HSOF System

    Institute of Scientific and Technical Information of China (English)

    CHEN Wen-Kai; CAO Mei-Juan; LIU Shu-Hong; LI Yi; LI Jun-Qian; YANG Ying-Chun

    2005-01-01

    Ab initio Hartree-Fock theory at the aug-cc-pvtz level is used to investigate the equilibrium structures and isomerization of HSOF system. All of the transition states have been calculated and confirmed by the intrinsic reaction coordinate (IRC). Four equilibrium structures, HSOF, HOSF, SO(H)F and OS(H)F, are predicted in this paper. Though OSF2 has been observed experimentally, the present calculated results suggest that the linear form isomer, HOSF, is more stable than OS(H)F by 35.2 kJ/mol. The linear form HSOF and the branched SO(H)F isomer are more unstable and the computed relative energies are 318.3 and 510.0 kJ/mol, respectively with respect to HOSF isomer corrected with zero point vibrational energy.

  3. Lycopene degradation and isomerization kinetics during thermal processing of an olive oil/tomato emulsion.

    Science.gov (United States)

    Colle, Ines J P; Lemmens, Lien; Tolesa, Getachew N; Van Buggenhout, Sandy; De Vleeschouwer, Kristel; Van Loey, Ann M; Hendrickx, Marc E

    2010-12-22

    The stability of lycopene in an olive oil/tomato emulsion during thermal processing (80-140 °C) was studied. Initially, the degradation of total lycopene (all-E plus Z-forms) occurred quickly at temperatures above 100 °C. However, a nonzero plateau value, depending on the processing temperature, was attained after longer treatment times. Besides degradation, the isomerization of total-Z-lycopene as well as the individual isomerization of all-E-, 5-Z-, 9-Z-, and 13-Z-lycopene was studied in detail. After prolonged heating, the isomer conversion reached a temperature-dependent equilibrium state. The degradation of total lycopene and the isomerization could be described by a fractional conversion model. The temperature dependency of the corresponding reaction rate constants was quantified by the Arrhenius equation. The activation energy of degradation was estimated to be 28 kJ/mol, and the activation energy of overall (all-E and total-Z) isomerization was estimated to be 52 kJ/mol.

  4. A convenient method for experimental determination of yields and isomeric ratios in photonuclear reactions measured by the activation technique

    Science.gov (United States)

    Kolev, D.; Dobreva, E.; Nenov, N.; Todorov, V.

    1995-02-01

    A generalized exact formula is derived for a determination of the experimental isomeric ratio in any incident particle activation. For the particular case, when the activity of the ground state results from the simultaneous decay of both states and can be conveniently measured, the appropriate modification of this formula is evaluated and applied to six photonuclear reactions induced by 43 MeV bremsstrahlung. The experimental isomeric yield ratios of (γ, 3n) 110m,gIn; (γ, p) (γ, pn), (γ, 2n2p) 117m,gIn; (γ, n) 164m,gHo and (γ, 3n) 162m,gHo are deduced.

  5. Zeolite-catalyzed isomerization of tetroses in aqueous medium

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Riisager, Anders

    2014-01-01

    The isomerization of erythrose (ERO) was studied in water over commercially available large-pore zeolites such as, e.g. H-Y, H-USY and H-beta. Among the employed zeolites, H-USY(6) was found to efficiently isomerize the sugar yielding 45 % erythrulose (ERU), 42 % ERO and 3 % of the epimer threose...

  6. Enzymatic isomerization of glucose and xylose in ionic liquids

    DEFF Research Database (Denmark)

    Ståhlberg, Tim Johannes Bjarki; Woodley, John; Riisager, Anders

    2012-01-01

    Glucose isomerase has been found for the first time to catalyze the isomerization of glucose to fructose in the ionic liquid N, N-dibutylethanolammonium octanoate (DBAO). Isomerization was achieved at temperatures of 60-80 degrees C although a substantial amount of mannose was formed at elevated...

  7. Isomerizing olefin metathesis as a strategy to access defined distributions of unsaturated compounds from fatty acids.

    Science.gov (United States)

    Ohlmann, Dominik M; Tschauder, Nicole; Stockis, Jean-Pierre; Goossen, Käthe; Dierker, Markus; Goossen, Lukas J

    2012-08-22

    The dimeric palladium(I) complex [Pd(μ-Br)(t)Bu(3)P](2) was found to possess unique activity for the catalytic double-bond migration within unsaturated compounds. This isomerization catalyst is fully compatible with state-of-the-art olefin metathesis catalysts. In the presence of bifunctional catalyst systems consisting of [Pd(μ-Br)(t)Bu(3)P](2) and NHC-indylidene ruthenium complexes, unsaturated compounds are continuously converted into equilibrium mixtures of double-bond isomers, which concurrently undergo catalytic olefin metathesis. Using such highly active catalyst systems, the isomerizing olefin metathesis becomes an efficient way to access defined distributions of unsaturated compounds from olefinic substrates. Computational models were designed to predict the outcome of such reactions. The synthetic utility of isomerizing metatheses is demonstrated by various new applications. Thus, the isomerizing self-metathesis of oleic and other fatty acids and esters provides olefins along with unsaturated mono- and dicarboxylates in distributions with adjustable widths. The cross-metathesis of two olefins with different chain lengths leads to regular distributions with a mean chain length that depends on the chain length of both starting materials and their ratio. The cross-metathesis of oleic acid with ethylene serves to access olefin blends with mean chain lengths below 18 carbons, while its analogous reaction with hex-3-enedioic acid gives unsaturated dicarboxylic acids with adjustable mean chain lengths as major products. Overall, the concept of isomerizing metatheses promises to open up new synthetic opportunities for the incorporation of oleochemicals as renewable feedstocks into the chemical value chain.

  8. Ultrafast isomerization in a difluoroboryl-coordinated molecular switch

    Science.gov (United States)

    Consani, Cristina; Berberich, Martin; Würthner, Frank; Brixner, Tobias

    2017-09-01

    Molecular switches based on light-induced isomerization cycles are promising materials for sensors and biomedical applications. Understanding the details of the isomerization photocycle and identifying the nuclear coordinates involved in the photoreaction are relevant topics. Here we characterize the cis → trans and trans → cis isomerization of a new type of BF2-coordinated azo-dye molecular switch by pump-probe spectroscopy. While cis → trans isomerization is ultrafast and proceeds via a conical intersection, the trans → cis photocycle is more complex and involves at least three reaction channels. Finally, we employ the vibrational wavepackets accompanying isomerization to infer information on the nuclear degrees of freedom involved in the photoreaction.

  9. The mechanism for iron-catalyzed alkene isomerization in solution

    Energy Technology Data Exchange (ETDEWEB)

    Sawyer, Karma R.; Glascoe, Elizabeth A.; Cahoon, James F.; Schlegel, Jacob P.; Harris, Charles B.

    2008-05-27

    Here we report nano- through microsecond time-resolved IR experiments of iron-catalyzed alkene isomerization in room-temperature solution. We have monitored the photochemistry of a model system, Fe(CO){sub 4}({eta}{sup 2}-1-hexene), in neat 1-hexene solution. UV-photolysis of the starting material leads to the dissociation of a single CO to form Fe(CO){sub 3}({eta}{sup 2}-1-hexene), in a singlet spin state. This CO loss complex shows a dramatic selectivity to form an allyl hydride, HFe(CO){sub 3}({eta}{sup 3}-C{sub 6}H{sub 11}), via an internal C-H bond-cleavage reaction in 5-25 ns. We find no evidence for the coordination of an alkene molecule from the bath to the CO loss complex, but do observe coordination to the allyl hydride, indicating that it is the key intermediate in the isomerization mechanism. Coordination of the alkene ligand to the allyl hydride leads to the formation of the bis-alkene isomers, Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) and Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2}. Because of the thermodynamic stability of Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) over Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2} (ca. 12 kcal/mol), nearly 100% of the alkene population will be 2-alkene. The results presented herein provide the first direct evidence for this mechanism in solution and suggest modifications to the currently accepted mechanism.

  10. Electrochemically Promoted Organic Isomerization Reactions at Polymer Electrolyte Fuel Cell Cathodes

    Science.gov (United States)

    2011-01-04

    through the grant. Figure 3: (a): ATR-FTIR of hydrated Nafion 117. (b) Deconvolution of 1100-1300 cm -1 region. (c) Deconvolution of 920-1020 cm...transmission infrared spectroscopy of hydrated and dehydrated Nafion. In Abstracts of Papers, 240th ACS National Meeting, Boston, MA, United States, August...Chemical Society, 1997. 119(47): p. 11550-11551. 2. Ploense, L., et al., Spectroscopic study of NEMCA promoted alkene isomerizations at PEM fuel

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

    CERN Document Server

    Lin, Zheng-Zhe

    2013-01-01

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

  12. Two-Photon-Induced Isomerization of Spiropyran/Merocyanine at the Air/Water Interface Probed by Second Harmonic Generation.

    Science.gov (United States)

    Lin, Lu; Zhang, Zhen; Lu, Zhou; Guo, Yuan; Liu, Minghua

    2016-10-13

    Photochromic molecules often exhibit switchable hyperpolarizabilities upon photoisomerization between two molecular states and can be widely applied in nonlinear optical materials. Photoisomerization can occur through either one-photon or two-photon processes. Two-photon-induced isomerization has several advantages over one-photon process but has not been fully explored. In the present study, we have used second harmonic generation to investigate the two-photon-induced isomerization between spiropyran and merocyanine at the air/water interface. We show that spiropyran and merocyanine can be converted into each other reversibly with 780-nm laser-beam irradiation through two-photon processes. We also investigated the isomerization rates under various incident laser powers. Quantitative analysis revealed that the isomerization rates of spiropyran and merocyanine depend differently on the laser power. We attribute the difference to the distinct molecular structures of spiropyran and merocyanine. At the interface, nonplanar spiropyran molecules exist mainly as monomers, whereas planar merocyanine molecules form aggregates. Upon aggregation, steric hindrance effects and excitonic coupling efficiently arrest the photoisomerization of merocyanine. This work provides an in-depth understanding of two-photon-induced isomerization at the interface, which is beneficial for designing and controlling optical thin-film materials.

  13. Isomeric Detergent Comparison for Membrane Protein Stability

    DEFF Research Database (Denmark)

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

    2016-01-01

    Membrane proteins encapsulated by detergent micelles are widely used for structural study. Because of their amphipathic property, detergents have the ability to maintain protein solubility and stability in an aqueous medium. However, conventional detergents have serious limitations in their scope...... 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...

  14. Isomerization of -carotene by titanium tetrachloride catalyst

    Indian Academy of Sciences (India)

    V Rajendran; B H Chen

    2007-05-01

    Isomerization of all-trans--carotene occurs during shaking with 0.5% of titanium tetrachloride catalyst in methylene chloride at room temperature. In the present study we compared two types of columns C18 and C30 and various solvent systems for the separation of -carotene and its cis isomers by high performance liquid chromatography (HPLC). Results showed that -carotene isomers were resolved by employing a C30 column with a mobile phase of methanol (100%) (A) and methylene chloride (100%) (B) under a gradient elution condition. A total of eleven cis isomers and one all-trans--carotene isomer were resolved within 50 min at a flow rate of 1 ml/min and detection wave-length of 470 nm.

  15. Photosensitized cis/trans isomerization of 1-(1-propenyl)cycloalkenes

    Energy Technology Data Exchange (ETDEWEB)

    Inman, W.D.; Sanchez, K.A.J.; Chaidez, M.A.; Paulson, D.R. (California State Univ., Los Angeles (USA))

    1989-09-29

    The photosensitized cis/trans isomerization of a series of 1-(1-propenyl)cycloalkenes is reported. A plot of the photostationary state trans/cis ratio vs the sensitizer triplet energy for 1-(1-propenyl)cyclopentene shows a constant trans/cis ratio of {approx} 1.0 with high-energy sensitizers (E{sub T} > 61 kcal/mol). The plot shows one maxima at E{sub T} {approx} 55 kcal/mol with low-energy sensitizers (E{sub T} < 61 kcal/mol). This type of plot is very similar to those obtained with acyclic dienes such as piperylene. The 1-(1-propenyl)cyclohexene system shows a similar plot with high-energy sensitizers, but with low-energy sensitizers this system shows two maxima occurring at 56 and 47 kcal/mol, respectively. This double-maxima plot is rationalized by an unusually low trans/cis decay ratio for the s-cis relaxed triplet state of the 1-(1-propenyl)cyclohexene system. This double maxima is not observed in other diene systems due to a high trans/cis decay ratio for their s-cis relaxed triplet states. The photosensitized cis/trans isomerization of 2-ethylidene-10-methyl-1(9)-octalin was also studied as a model for a conformationally locked s-trans system. The 1-(1-propenyl)cycloheptene system undergoes photosensitized cis/trans isomerization, but photostationary cis/trans isomerization data could not be obtained due to a very efficient photosensitized dimerization of this diene system.

  16. 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.

  17. Energy dependence of the total reaction cross section of isomeric F-18(m) on silicon below 400 MeV

    NARCIS (Netherlands)

    Roberts, DA; Becchetti, FD; Janecke, J; Lee, MY; O'Donnell, TW; Pham, K; Warner, RE; Ronningen, RM; Wilschut, HW

    2002-01-01

    A 25 MeV/nucleon primary O-17 beam was used to produce an isomeric state F-18(m) beam via the single-nucleon transfer reaction O-17 (C-12, B-11)F-18(m). The total nuclear reaction cross section, sigma(R), of F-18(m) (metastable) on silicon was measured using a stack of silicon surface barrier detect

  18. Influence of the octupole mode on nuclear high-K isomeric properties

    Science.gov (United States)

    Minkov, Nikolay; Walker, Phil

    2014-05-01

    The influence of quadrupole-octupole deformations on the energy and magnetic properties of high-K isomeric states in even-even actinide (U, Pu, Cm, Fm, No), rare-earth (Nd, Sm and Gd), and superheavy (^{270}\\text{Ds}) nuclei is examined within a deformed shell model with pairing interaction. The neutron two-quasiparticle (2qp) isomeric energies and magnetic dipole moments are calculated over a wide range in the plane of quadrupole and octupole deformations. In most cases the magnetic moments exhibit a pronounced sensitivity to the octupole deformation. At the same time, the calculations outline three different groups of nuclei: with pronounced, shallow, and missing minima in the 2qp energy surfaces with respect to the octupole deformation. The result indicates regions of nuclei with octupole softness as well as with possible octupole deformation in the high-K isomeric states. These findings show the need for further theoretical analysis as well as of detailed experimental measurements of magnetic moments in heavy deformed nuclei.

  19. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Benjamin Joel [Univ. of California, Berkeley, CA (United States)

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in ~240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH2I2 and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a ~350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  20. Catalytic skeletal isomerization of linear butenes to isobutene

    CSIR Research Space (South Africa)

    Butler, AC

    1993-12-31

    Full Text Available since the late 1970s in implementing the catalytic skeletal isomerization reaction of these linear alkenes. Halogenated catalysts, especially those based on alumina, and prepared using a variety of compounds of fluorine, chlorine or bromine, have been...

  1. Methods for suppressing isomerization of olefin metathesis products

    Energy Technology Data Exchange (ETDEWEB)

    Firth, Bruce E.; Kirk, Sharon E.

    2015-10-27

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent that includes nitric acid to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. Methods of refining a natural oil are described.

  2. Sequential picosecond isomerizations in a photochromic ruthenium sulfoxide complex triggered by pump-repump-probe spectroscopy.

    Science.gov (United States)

    King, Albert W; Jin, Yuhuan; Engle, James T; Ziegler, Christopher J; Rack, Jeffrey J

    2013-02-18

    The complex [Ru(bpy)(2)(bpSO)](PF(6))(2), where bpy is 2,2'-bipydine and bpSO is 1,2-bis(phenylsulfinyl)ethane, exhibits three distinct isomers which are accessible upon metal-to-ligand charge-transfer (MLCT) irradiation. This complex and its parent, [Ru(bpy)(2)(bpte)](PF(6))(2), where bpte is 1,2-bis(phenylthio)ethane, have been synthesized and characterized by UV-visible spectroscopy, NMR, X-ray crystallography, and femtosecond transient absorption spectroscopy. A novel method of 2-color Pump-Repump-Probe spectroscopy has been employed to investigate all three isomers of the bis-sulfoxide complex. This method allows for observation of the isomerization dynamics of sequential isomerizations of each sulfoxide from MLCT irradiation of the S,S-bonded complex to ultimately form the O,O-bonded metastable complex. One-dimensional (1-D) and two-dimensional (2-D) (COSY, NOESY, and TOCSY) (1)H NMR data show the thioether and ground state S,S-bonded sulfoxide complexes to be rigorously C(2) symmetric and are consistent with the crystal structures. Transient absorption spectroscopy reveals that the S,S to S,O isomerization occurs with an observed time constant of 56.8 (±7.4) ps. The S,O to O,O isomerization time constant was found to be 59 (±4) ps by pump-repump-probe spectroscopy. The composite S,S- to O,O-isomer quantum yield is 0.42.

  3. Ground-state and isomeric-state cross sections for 181Ta( n,2n )180Ta between 8 and 15 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Bhatia, C. [Duke Univ., Durham, NC (United States); Triangle Univ. Nuclear Lab., Durham, NC (United States); Gooden, M. E. [Triangle Univ. Nuclear Lab., Durham, NC (United States); North Carolina State Univ., Raleigh, NC (United States); Tornow, W. [Duke Univ., Durham, NC (United States); Triangle Univ. Nuclear Lab., Durham, NC (United States); Tonchev, A. P. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2013-03-21

    Using the activation technique, the cross section for the reaction 181Ta(n,2n)180gTa was measured from 8 to 15 MeV in small energy steps to resolve inconsistencies in the existing database. The 93.4 keV γ ray from the decay of the 180gTa ground state was recorded with a high-purity germanium (HPGe) detector. The monitor reactions 27Al(n,α)24Na and 197Au(n,2n)196Au were used for neutron fluence determination. The ENDF VII.1 and TENDL 2011 evaluations are in considerable disagreement with the present data, which in turn agree very well with the majority of the existing data in the 14 MeV energy region. Furthermore, a detailed analysis using the code TALYS was performed to describe the present data and to predict the (n,2n) cross section to the isomeric state of 180Ta.

  4. Isomeric Island in the Vicinity of 66Fe

    Energy Technology Data Exchange (ETDEWEB)

    Daugas, J. M. [Grand Accelerateur National d' Ions Lourds (GANIL); Sawicka, M. [University of Warsaw; Pfutzner, M. [University of Warsaw; Matea, I. [Grand Accelerateur National d' Ions Lourds (GANIL); Grawe, H. [GSI-Hemholtzzentrum fur Schwerionenforschung, Darmstadt, Germany; Grzywacz, Robert Kazimierz [ORNL; Bingham, Carrol R [ORNL; Grzywacz-Jones, K. L. [Oak Ridge National Laboratory (ORNL); Rykaczewski, Krzysztof Piotr [ORNL

    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 g9/2 shell. Moreover, the excitation energy of the first 2+ and 4+ states in the 68Fe have been established by − 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.

  5. 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.

  6. Simulation of Photo-isomerization of Functionalized Azobenzene Derivatives

    Science.gov (United States)

    Tavazohi, Pedram; Herberger, Zachary; Lewis, James

    Photo-isomerization is the process of changing the isomer (cis , trans) of a molecule using light. In azobenzene this process can be utilized in a Metal Organic Framework (MOF) for adsorption of CO2. MOFs are created by two major components, metal ions, and organic molecules which are called linkers. The metal ions and linkers can be coordinated in a way that they form a porous material. In the cis isomer of azobenzene, the MOF's pore is available to be filled by CO2, but in the trans isomer the pore is filled with a benzene ring. The change from cis to trans will evacuate the pore if CO2 is present. The important considerations in using azobenzene photo-isomerization as a photo-switch in MOFs are, the quantum yield of the process, and the wavelength of the light which triggers photo-isomerization. By substitution of the functional groups of azobenzene and using the fewest switches surface-hopping algorithm in FIREBALL to simulate the photo-isomerization process we can tune the properties of the molecule as we desire and predict the best substitution sites for azobenzene functional groups. We studied the effects of functionalizing the molecule with OH, CH3, NH2, NO2 and COOH on isomerization quantum yield.

  7. Prolyl cis-trans isomerization as a molecular timer.

    Science.gov (United States)

    Lu, Kun Ping; Finn, Greg; Lee, Tae Ho; Nicholson, Linda K

    2007-10-01

    Proline is unique in the realm of amino acids in its ability to adopt completely distinct cis and trans conformations, which allows it to act as a backbone switch that is controlled by prolyl cis-trans isomerization. This intrinsically slow interconversion can be catalyzed by the evolutionarily conserved group of peptidyl prolyl cis-trans isomerase enzymes. These enzymes include cyclophilins and FK506-binding proteins, which are well known for their isomerization-independent role as cellular targets for immunosuppressive drugs. The significance of enzyme-catalyzed prolyl cis-trans isomerization as an important regulatory mechanism in human physiology and pathology was not recognized until the discovery of the phosphorylation-specific prolyl isomerase Pin1. Recent studies indicate that both phosphorylation-dependent and phosphorylation-independent prolyl cis-trans isomerization can act as a novel molecular timer to help control the amplitude and duration of a cellular process, and prolyl cis-trans isomerization might be a new target for therapeutic interventions.

  8. Phototriggered sulfoxide isomerization in [Ru(pic)2(dmso)2].

    Science.gov (United States)

    Rachford, Aaron A; Petersen, Jeffrey L; Rack, Jeffrey J

    2007-08-14

    We report the characterization and photochemistry of a simple ruthenium coordination complex containing only picolinate (pic) and dmso, which exhibits a large isomerization quantum yield (Phi(SS-->OO) = 0.50) in various solvents. The picolinate ligands of [Ru(pic)(2)(dmso)(2)] are in a cis arrangement so that the carboxylate oxygen of one pic ligand (O1) is trans to the pyridine of the second picolinate (N2). One dmso ligand (S1) is trans to a pyridine nitrogen (N1), while the second dmso (S2) is trans to a carboxylate oxygen (O3). The cyclic voltammetry, (1)H NMR, IR, and UV-vis spectroscopy data suggest that while both dmso ligands isomerize photochemically, only one dmso ligand isomerizes electrochemically. Isomerization quantum yields for each dmso ligand differ by an order of magnitude (Phi(SS-->SO) = 0.46 and Phi(SO-->OO) = 0.036). In agreement with previous results, the isomerization quantum yield for each dmso is dependent on the ligand that is trans to the dmso.

  9. Isomeric ratios for nuclei with Z=62-67 and A=142-152 produced in the relativistic fragmentation of 208Pb

    Energy Technology Data Exchange (ETDEWEB)

    Myalski, Szymon; Maj, Adam [IFJ PAN, Krakow (Poland); Podolyak, Zsolt [Dept. of Physics, Univ. of Surrey, Guildford (United Kingdom)

    2009-07-01

    We have investigated isomeric states in a number of nuclei with Z=62-67 and A=142-152, produced by the fragmentation of the relativistic(1 GeV/u) {sup 208}Pb beam from the SIS-18 synchrotron of the GSI facility on a {sup 9}Be target, and selected by the FRagment Separator(FRS). The selected nuclei of interest were implanted into the stopper, a block of plastic 7mm thick. The gamma-rays from the decay of isomeric states in the implanted nuclei were measured by the high purity germanium array, RISING. In total 22 nuclides were detected, isomeric states were observed in 9 of them:19{sup -} in {sup 152}Ho, 31/2{sup +} in {sup 153}Ho, 27{sup +} in {sup 148}Tb, 10{sup +}in {sup 144}Gd, 49/2{sup +}in {sup 147}Gd, 11/2{sup -} in {sup 143}Eu, 8{sup -} in {sup 144}Eu, 11/2{sup -} in {sup 145}Eu, 10{sup +} in {sup 142}Sm and 7{sup -} in {sup 142}Sm. Of special interest is the 27{sup +} state in {sup 148}Tb, the highest spin populated through the fragmentation reaction until present day. The aim of this work was the extraction of isomeric ratios(R) for these isomeric states. The R is the number of ions populated in a given isomeric state compared to the total number of ions populated for the selected nuclide. The R can provide information about the production reaction and nuclear structure. It was evaluated based on flight time, half-life, in-flight losses and by considering the finite measurement time. Results were compared with theoretical predictions, calculated using an abrasion-ablation approach.

  10. 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.

  11. Influence of Steam Treating on Deethylating Type Isomerization Catalyst

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    This article mainly worked on methods to reduce side reactions of the de-ethylating type catalyst for xylene isomerization. In laboratory the de-ethylating type catalyst for xylene isomerization was subjected to steam treatment at different temperatures and durations to achieve dealumination of the ZSM-5 zeolite to some extent, which could affect the change in Bronsted acid content to decrease xylene loss along with reduction of side reactions. Test results showed that the degree for reducing side reactions by steam treatment depended upon two important parameters-treating temperature and duration. The optimal condition required treating the catalyst at 500℃ for 8 hours.

  12. Excitation Localization/Delocalization Isomerism in a Strongly Coupled Covalent Dimer of 1,3-Diphenylisobenzofuran

    Energy Technology Data Exchange (ETDEWEB)

    Schrauben, Joel N.; Akdag, Akin; Wen, Jin; Havlas, Zdenek; Ryerson, Joseph L.; Smith, Millie B.; Michl, Josef; Johnson, Justin C.

    2016-05-26

    Two isomers of both the lowest excited singlet (S1) and triplet (T1) states of the directly para, para'-connected covalent dimer of the singlet-fission chromophore 1,3-diphenylisobenzofuran have been observed. In one isomer, excitation is delocalized over both halves of the dimer, and in the other, it is localized on one or the other half. For a covalent dimer in solution, such 'excitation isomerism' is extremely rare. The vibrationally relaxed isomers do not interconvert, and their photophysical properties, including singlet fission, differ significantly.

  13. Mediating states in 180Ta

    OpenAIRE

    Alexa, Petr

    2002-01-01

    Possible theoretical electromagnetic paths between the ground state and the isomeric state at 75.3 keV in 180Ta are discussed in the framework of the two-quasiparticle-plus-phonon model and the standard axially-symmetric rotor model including Coriolis mixing. Experimental transition rates from the isomeric state to the ground state via observed mediating states are compared to the theoretical ones.

  14. Investigation of Isomerization of 2-Seleno-1, 3, 2-diazaphospholidine Derivatives

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    For the first time the isomerization of 1, 3, 2-diazaphospholidine-2-selenide derivatives in refluxing benzene in the presence of trace water was observed. The structures of isomerized products were determined by IR, 1H NMR, 31P NMR, elemental analysis and X-ray crystallography. The mechanism of isomerization was also proposed.

  15. Isomeric and ground-state decay of $^{215}$Bi

    CERN Document Server

    Kurpeta, J; Andreyev, A N; Äystö, J; De Smet, A; De Witte, H; Evensen, A H; Fedosseev, V; Franchoo, S; Górska, M; Grawe, H; Huhta, M; Huyse, M; Janas, Z; Jokinen, A; Karny, M; Kugler, E; Kurcewicz, W; Köster, U; Lettry, Jacques; Nieminen, A; Partes, K; Ramdhane, M; Ravn, H L; Rykaczewski, K; Szerypo, J; Van de Vel, K; Van Duppen, P; Weissman, L; Walter, G; Wöhr, A

    2003-01-01

    A new high-spin isomer in /sup 215/Bi, with a half-life of 36.9(6) s, has been identified at the PSB-ISOLDE on-line mass separator using the pulsed-release technique combined with the element selective RILIS source. A decay scheme of /sup 215m/Bi was constructed and complemented with the low-spin structure observed in /sup 215g/Bi decay. The population of a cascade on top of the ( nu g/sub 9/2/)/sub 9/2+//sup 5/ level in /sup 215/Po provides evidence for Gamow-Teller beta -decay of the high-spin /sup 215/Bi isomer. (15 refs).

  16. A convenient method for experimental determination of yields and isomeric ratios in photonuclear reactions measured by the activation technique

    Energy Technology Data Exchange (ETDEWEB)

    Kolev, D. [Sofia Univ. (Bulgaria). Dept. of Physics; Dobreva, E. [Sofia Univ. (Bulgaria). Dept. of Physics; Nenov, N. [Sofia Univ. (Bulgaria). Dept. of Physics; Todorov, V. [A Higher Institute of Medicine, Sofia (Bulgaria)

    1995-03-15

    A generalized exact formula is derived for a determination of the experimental isomeric ratio in any incident particle activation. For the particular case, when the activity of the ground state results from the simultaneous decay of both states and can be conveniently measured, the appropriate modification of this formula is evaluated and applied to six photonuclear reactions induced by 43 MeV bremsstrahlung. The experimental isomeric yield ratios of ({gamma}, 3n) {sup 110m,g}In; ({gamma}, p) ({gamma}, pn), ({gamma}, 2n2p) {sup 117m,g}In; ({gamma}, n) {sup 164m,g}Ho and ({gamma}, 3n) {sup 162m,g}Ho are deduced. ((orig.)).

  17. cis- and trans-Stilbenes: Chromatographic Separation and Photochemical Isomerization.

    Science.gov (United States)

    Levine, Samuel G.; And Others

    1988-01-01

    Describes an experiment that is to be performed midway in the first semester of an undergraduate organic chemistry laboratory coinciding with the students' introduction to cis-trans isomerism in the study of alkenes. Discusses the apparatus, materials, experimental procedure, historical significance, and results. (CW)

  18. Separation of isomeric xylenes by pervaporation through cellulose ester membranes

    NARCIS (Netherlands)

    Mulder, M.H.V.; Kruitz, F.; Smolders, C.A.

    1982-01-01

    The interaction between the isomeric xylenes and different cellulose esters was investigated using solubility parameter considerations and through measurements of swelling values. p]Hansen's three-dimensional solubility parameters δd, δp, δh of all the components have been calculated. These values h

  19. Well-defined transition metal hydrides in catalytic isomerizations.

    Science.gov (United States)

    Larionov, Evgeny; Li, Houhua; Mazet, Clément

    2014-09-07

    This Feature Article intends to provide an overview of a variety of catalytic isomerization reactions that have been performed using well-defined transition metal hydride precatalysts. A particular emphasis is placed on the underlying mechanistic features of the transformations discussed. These have been categorized depending upon the nature of the substrate and in most cases discussed following a chronological order.

  20. Femtosecond Dynamics of Fundamental Reaction Processes in Liquids: Proton Transfer, Geminate Recombination, Isomerization and Vibrational Relaxation.

    Science.gov (United States)

    Schwartz, Benjamin Joel

    Femtosecond and picosecond transient absorption spectroscopy are used to probe several fundamental aspects of chemical reactivity in the condensed phase including proton transfer, germinate recombination, isomerization and vibrational relaxation. The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured for the first time, and the effects of external hydrogen-bonding interactions on the proton transfer are studied in detail. The proton transfer takes place in ~240 fsec in non-polar environments, but becomes faster than the instrumental resolution of 110 fsec in methanol solutions. A simple model is proposed to explain these results. The dynamics following photodissociation of CH _2I_2 and other small molecules provide the first direct observations of germinate recombination. The recombination of many different photodissociating species occurs on a ~350 fsec time scale. Results also show that recombination yields but not rates depend on the molecular details of the solvent environment and suggest that recombination kinetics are dominated by a single collision with the surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. The data show no simple correlation between the hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes. This strongly implies that the isomerization of these systems does not provide a suitable testing ground for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in the photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial

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

    Directory of Open Access Journals (Sweden)

    T. Dickel

    2015-05-01

    Full Text Available 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Dickel, T. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Plaß, W.R., E-mail: Wolfgang.R.Plass@exp2.physik.uni-giessen.de [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Ayet San Andres, S. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Ebert, J. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); Geissel, H.; Haettner, E. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Hornung, C. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); Miskun, I. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Pietri, S.; Purushothaman, S. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); and others

    2015-05-11

    {sup 211}Po ions in the ground and isomeric states were produced via {sup 238}U projectile fragmentation at 1000 MeV/u. The {sup 211}Po 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.

  3. 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.

  4. Nature of isomerism in exotic sulfur isotopes

    CERN Document Server

    Utsuno, Yutaka; Otsuka, Takaharu; Yoshida, Tooru; Tsunoda, Yusuke

    2014-01-01

    We clarify the origin of the anomalously hindered $E2$ decay from the $4^+_1$ level in $^{44}$S that has recently been observed, performing a novel many-body analysis in the shell model. Opposed to the normal yrast states, this level is dominated by a two-quasiparticle $K=4$ intrinsic state occupying $\

  5. 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.

  6. Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

    Science.gov (United States)

    Benjamin, Ilan; Pohorille, Andrew

    1993-01-01

    The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

  7. 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.

  8. Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

    Science.gov (United States)

    Benjamin, Ilan; Pohorille, Andrew

    1993-01-01

    The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

  9. Topological studies on IRC paths of the isomerization reaction of silicon methyl- nitrene

    Institute of Scientific and Technical Information of China (English)

    石彦波; 郑世钧; 孟令鹏

    1999-01-01

    On the basis of kinetic study of isomerization reaction of H3Si-N, ab initio (RHF, UHF/6-31G) calculations on some points of the singlet and triplet reaction paths were carried out. The breakage and formation of chemical bond in the reaction are discussed. The calculated results show that there is a transitional structure of three-membered ring on each of reaction paths. A ’structural transition region’ and a ’structural transition state’ in both of studied reaction are found. Our previous conclusion that the structure transition state (STS) always appears before the energy transition state (ETS) in endothermic reaction and after ETS in exothermic reaction is further confirmed. The relationship between the change of spin density distribution and the structural transition state are investigated.

  10. How Is cis-trans Isomerization Controlled in Dronpa Mutants? A Replica Exchange Molecular Dynamics Study.

    Science.gov (United States)

    Moors, Samuel L C; Michielssens, Servaas; Flors, Cristina; Dedecker, Peter; Hofkens, Johan; Ceulemans, Arnout

    2008-06-01

    The reversibly photoactivatable green fluorescent protein analog Dronpa holds great promise as a marker for various new cellular imaging applications. Using a replica exchange method which combines both Hamiltonian and temperature exchanges, the ground-state dynamics of Dronpa and two mutants with increased switching kinetics, Val157Gly and Met159Thr, were compared. The dominant chromophore state was found to be the cis isomer in all three proteins. The simulation data suggest that both mutations strongly increase the chromophore flexibility and cis-trans isomerization rate. We identify three key amino acids, Val157, Met159, and Phe173, which are able to impede the bottom hula-twist transition path, depending on their position and rotameric state. We believe our insights will help to understand the switching process and provide useful information for the design of new variants with improved fluorescence properties.

  11. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation. [Spiropyrans

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, B.J.

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in [approximately]240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH[sub 2]I[sub 2] and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a [approximately]350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  12. Studies of some isomeric yield ratios produced with bremsstrahlung

    Energy Technology Data Exchange (ETDEWEB)

    Kolev, Dimitar

    1998-05-11

    The experimental isomeric ratios for {sup 52m,g}Mn, {sup 86m,g}Y, {sup 87m,g}Y, {sup 89m,g}Zr, {sup 110m,g}In, {sup 111m,g}In, {sup 112m,g}In, {sup 152m1,g}Pm, {sup 152m2,m1}Eu, {sup 162m,g}Ho, {sup 164m,g}Ho and {sup 178m,g}Lu measured by the activation technique from different targets in ({gamma}, xnp) reactions (x{<=}3) at the bremsstrahlung end-point energy of 43 MeV are presented. The predictions of calculations performed by means of compound nucleus particle evaporation and final {gamma}-deexcitation were critically discussed. The importance of inclusion in the calculations of nonequilibrium particle emission and an adequate {gamma}-decay mode of isomeric nuclei was considered for some of the reactions investigated.

  13. Isomerization of propargyl cation to cyclopropenyl cation: Mechanistic elucidations and effects of lone pair donors

    Indian Academy of Sciences (India)

    Zodinpuia Pachuau; Kiew S Kharnaior; R H Duncan Lyngdoh

    2013-03-01

    This ab initio study examines two pathways (one concerted and the other two-step) for isomerization of the linear propargyl cation to the aromatic cyclopropenyl cation, also probing the phenomenon of solvation of this reaction by simple lone pair donors (NH3, H2O, H2S and HF) which bind to the substrate at two sites. Fully optimized geometries at the B3LYP/6-31G(d) level were used, along with single point QCISD(T)/6-311+G(d,p) and accurate G3 level calculations upon the DFT optimized geometries. For the unsolvated reaction, the two-step second pathway is energetically favoured over the one-step first pathway. Lone pair donor affinity for the various C3H$^{+}_{3}$ species follows the uniform order NH3 > H2S>H2O>HF. The activation barriers for the solvated isomerizations decrease in the order HF>H2O>H2S>NH3 for both pathways. The number of lone pairs on the donor heteroatom as well as the heteroatom electronegativity are factors related to both these trends. Compared to the unsolvated cases, the solvated reactions have transition states which are usually ‘later’ in position along the reaction coordinate, validating the Hammond postulate.

  14. Ultrafast spectroscopy and structural characterization of a photochromic isomerizing ruthenium bis-sulfoxide complex.

    Science.gov (United States)

    King, Albert W; Malizia, Jason P; Engle, James T; Ziegler, Christopher J; Rack, Jeffrey J

    2014-12-21

    Irradiation of [Ru(bpy)2(bpSOp)](PF6)2 (where bpy is 2,2'-bipyridine and bpSOp is 1,3-bis(phenylsulfinyl)propane) results in the formation of two new isomers, namely the S,O- and O,O-bonded species. The crystal structure of the bis-thioether and bis-sulfoxide complexes are reported. NMR spectroscopy of the bis-thioether complex in solution is consistent with the molecular structure determined by diffraction methods. Further, NMR spectroscopy of the bis-sulfoxide complex reveals two conformers in solution, one that is consistent with the solid state structure and a second conformer showing distortion in the aliphatic portion of the chelate ring. Time-resolved visible absorption spectroscopy reveals isomerization time constants of 91 ps in dichloroethane (DCE) and 229 ps in propylene carbonate (PC). Aggregate isomerization quantum yields of 0.57 and 0.42 have been determined in DCE and in PC, respectively. The kinetics of the thermal reversion from the O,O- to S,O-bonded isomer are strongly solvent dependent, occurring with rates of 2.41 × 10(-3) and 4.39 × 10(-5) s(-1) in DCE, and 4.68 × 10(-4) and 9.79 × 10(-6) s(-1) in PC. The two kinetic components are assigned to the two isomers identified in solution.

  15. 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.

  16. Isomerization of metastable amine radical cations by dissociation-recombination

    DEFF Research Database (Denmark)

    Pedersen, Anders Holmen; Nielsen, Christian Benedikt; Bojesen, Gustav;

    2015-01-01

    The metastable molecular ions of primary aliphatic amines branched at C2 can isomerize by cleavage-recombination, thereby facilitating fragmentation reactions that require less energy than simple cleavage of the initial molecular ion. This process complements the reactions described by Audier...... to account for the conspicuous absence of the conventional a-cleavage among the major fragmentation reactions of the metastable molecular ions of primary amines....

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

    Energy Technology Data Exchange (ETDEWEB)

    Royo, F.M. [Departamento de Quimica Organica-Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain); Villares, A. [Departamento de Quimica Organica-Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain); Martin, S. [Departamento de Quimica Organica-Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain); Giner, B. [Departamento de Quimica Organica-Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain); Lafuente, C. [Departamento de Quimica Organica-Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain)]. E-mail: celadi@unizar.es

    2007-05-15

    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.

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

    Science.gov (United States)

    Ishoey, Mette; Nielsen, Thomas E

    2014-07-14

    Metal-catalyzed isomerization of N- and O-allylic systems is emerging as an effective method to form synthetically useful iminium and oxocarbenium intermediates. In the presence of tethered nucleophiles, several recent examples illuminate this approach as a powerful strategy for the synthesis 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.

  19. [Ion mobility spectrometry for the isomeric volatile organic compounds].

    Science.gov (United States)

    Han, Hai-yan; Jia, Xian-de; Huang, Guo-dong; Wang, Hong-mei; Li, Jian-quan; Jin, Shun-ping; Jiang, Hai-he; Chu, Yan-nan; Zhou, Shi-kang

    2007-10-01

    Ion mobility spectrometry (IMS) is based on determining the drift velocities, which the ionized sample molecules attain in the weak electric field of a drift tube at atmospheric pressure. The drift behavior can be affected by structural differences of the analytes, so that ion mobility spectrometry has the ability to separated isomeric compounds. In the present article, an introduction to IMS is given, followed by a description of the instrument used for the experiments to differentiate isomeric compounds. Positive ion mobility spectras of three kinds of isomeric volatile organic compounds were studied in a homemade high-resolution IMS apparatus with a discharge ionization source. The study includes the differences in the structure of carbon chain, the style of function group, and the position of function group. The reduced mobility values were determined, which are in very good agreement with the previously reported theoretical values using neural network theory. The influence of the structural features of the substances and including the size and shape of the molecule has been investigated. The reduced mobility values increases in the order: alcohols ion mobility spectra of the constitutional isomers studied reflect the influence of structural features. In order to calibrate or determine the detection limits and the sensitivity of the ion mobility spectrometry, the exponential dilution flask (EDF) was used. Using this method, the detection limit of the analytes can reach the order of magnitude of ng x L(-1).

  20. Industrial Aplication of Catalytic Systems for n-Heptane Isomerization

    Directory of Open Access Journals (Sweden)

    Laura Olivia Alemán-Vázquez

    2011-07-01

    Full Text Available The ideal gasoline must have a high pump octane number, in the 86 to 94 range, and a low environmental impact. Alkanes, as a family, have much lower photochemical reactivities than aromatics or olefins, but only the highly branched alkanes have adequate octane numbers. The purpose of this work is to examine the possibilities of extending the technological alternative of paraffin isomerization to heavier feedstocks (i.e., n-heptane using non-conventional catalytic systems which have been previously proposed in the literature: a Pt/sulfated zirconia catalyst and a molybdenum sub-oxide catalyst. Under the experimental conditions at which these catalysts have been evaluated, the molybdenum sub-oxide catalyst maintains a good activity and selectivity to isomerization after 24 h, while the Pt/sulfated zirconia catalyst shows a higher dimethylpentanes/methylhexanes ratio, probably due to a lower operating temperature, but also a high formation of cracking products, and presents signs of deactivation after 8 h. Though much remains to be done, the performance of these catalysts indicates that there are good perspectives for their industrial application in the isomerization of n-heptane and heavier alkanes.

  1. Resolving Isomeric Glycopeptide Glycoforms with Hydrophilic Interaction Chromatography (HILIC).

    Science.gov (United States)

    Huang, Yining; Nie, Yongxin; Boyes, Barry; Orlando, Ron

    2016-09-01

    The ability to resolve glycans while attached to tryptic peptides would greatly facilitate glycoproteomics, as this would enable site-specific glycan characterization. Peptide/glycopeptide separations are typically performed using reversed-phase liquid chromatography (RPLC), where retention is driven by hydrophobic interaction. As the hydrophilic glycans do not interact significantly with the RPLC stationary phase, it is difficult to resolve glycopeptides that differ only in their glycan structure, even when these differences are large. Alternatively, glycans interact extensively with the stationary phases used in hydrophilic interaction chromatography (HILIC), and consequently, differences in glycan structure have profound chromatographic shifts in this chromatographic mode. Here, we evaluate HILIC for the separation of isomeric glycopeptide mixtures that have the same peptide backbone but isomeric glycans. Hydrophilic functional groups on both the peptide and the glycan interact with the HILIC stationary phase, and thus, changes to either of these moieties can alter the chromatographic behavior of a glycopeptide. The interactive processes permit glycopeptides to be resolved from each other based on differences in their amino acid sequences and/or their attached glycans. The separations of glycans in HILIC are sufficient to permit resolution of isomeric N-glycan structures, such as sialylated N-glycan isomers differing in α2-3 and α2-6 linkages, while these glycans remain attached to peptides.

  2. Tunneling in high-K isomeric decays

    CERN Document Server

    Shizuma, T; Shimizu, Y R

    2002-01-01

    We have systematically investigated highly-K-forbidden transitions observed in the Hf, W and Os region, using the gamma-tunneling model in which low-K and high-k states interact through a process of quantum tunneling. The measured hindrance factors are compared with the values calculated using the gamma-tunneling model. Isotope dependences of gamma-tunneling probabilities particularly for neutron-rich nuclei and the relation to stimulated decays of isomers are discussed. (author)

  3. 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)

  4. Pressure and temperature-dependent gauche-trans isomerization of 1-bromopropane: Raman measurement and statistical thermodynamic analysis

    Science.gov (United States)

    Hu, Min-Hom A.; de Souza, Luis E. S.; Lee, Meng-Rong; Ben-Amotz, Dor

    1999-02-01

    Raman measurements of the isomerization equilibrium in liquid 1-bromopropane are compared with perturbed hard-body fluid predictions. The integrated areas of the Raman bands arising from the C-Br stretch of the gauche and trans conformations are used to track the isomerization equilibrium as a function of pressure and temperature. Repulsive solvent-solute interactions are treated using the recently developed excluded-volume-anisotropy model (based on realistic molecular structures for the two isomers and the equation of state of liquid 1-bromopropane), and cohesive interactions are treated using the van der Waals mean field approximation. The results illustrate the delicate balance of attractive and repulsive solute-solvent interactions which underlie the effects of solvation on chemical equilibria. Comparison of the measured and predicted changes in ΔH with pressure, and ΔV with temperature, are used to determine parameters describing the attractive mean field and cavity formation energies of the two isomers, as well as the isomerization enthalpy and entropy of the isolated molecule.

  5. Light-induced geometric isomerization of 1,2-diphenylcyclopropanes included within Y zeolites: role of cation-guest binding.

    Science.gov (United States)

    Kaanumalle, Lakshmi S; Sivaguru, J; Sunoj, R B; Lakshminarasimhan, P H; Chandrasekhar, J; Ramamurthy, V

    2002-12-13

    Through a systematic study of several diphenylcyclopropane derivatives, we have inferred that the cations present within a zeolite control the excited-state chemistry of these systems. In the parent 1,2-diphenylcylopropane, the cation binds to the two phenyl rings in a sandwich-type arrangement, and such a mode of binding prevents cis-to-trans isomerization. Once an ester or amide group is introduced into the system (derivatives of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid), the cation binds to the carbonyl group present in these chromophores and such a binding has no influence on the cis-trans isomerization process. Cation-reactant structures computed at density functional theory level have been very valuable in rationalizing the observed photochemical behavior of diphenylcyclopropane derivatives included in zeolites. While the parent system, 1,2-diphenylcylopropane, has been extensively investigated in the context of chiral induction in solution, owing to its failure to isomerize from cis to trans, the same could not be investigated in zeolites. However, esters of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid could be studied within zeolites in the context of chiral induction. Chiral induction as high 20% ee and 55% de has been obtained with selected systems. These numbers, although low, are much higher than what has been obtained in solution with the same system or with the parent system by other investigators (maximum approximately 10% ee).

  6. Using torsional forces to explain the gradient temperature Raman spectra of endosulfan isomers and its irreversible isomerization

    Science.gov (United States)

    Schmidt, Walter F.; Hapeman, Cathleen J.; McConnell, Laura L.; Rice, Clifford P.; Broadhurst, C. Leigh; Nguyen, Julie K.; Qin, Jianwei; Chao, Kuanglin; Kim, Moon S.; Shelton, Daniel R.

    2017-07-01

    Since the 1950's, the broad-spectrum, organochlorine insecticide endosulfan (6,7,8, 9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) has been used on numerous crops. Due to its persistence, bioaccumulation, long-range transport, and adverse effects to human health and ecosystems, it was officially identified as a persistent organic pollutant (POP) in 2011. The last uses in the United States were phased out in 2016. Endosulfan consists of two diastereomers, α-endosulfan and β-endosulfan, and while the α-isomer exists as two asymmetrical, twist-chair enantiomers which interchange, the β-isomer is a symmetrical-chair conformation. In addition, the β-isomer was found to isomerize to the α-isomer. Gradient Temperature Raman Spectroscopy (GTRS) enables identification the molecular sites at which bending vibrational modes becomes twisting or wagging vibrational modes. Previous studies using GTRS and chemical calculations afforded evidence for specific bond movements and the irreversibility of the isomerization mechanism. However, not all of the vibrational modes observed in the spectra could be explained. Thus, new analyses of the GTRS data were conducted to examine the effects of torsional forces on the bond movement, which allowed for the identification of all the peaks. These newly-identified torsional forces provide further confirmation of the isomerization mechanism and its irreversibility. Finally, this isomerization explains why β-endosulfan is rarely detected in the atmosphere.

  7. Polarity controlled reaction path and kinetics of thermal cis-to-trans isomerization of 4-aminoazobenzene.

    Science.gov (United States)

    Joshi, Neeraj Kumar; Fuyuki, Masanori; Wada, Akihide

    2014-02-20

    Spectral and kinetic behavior of thermal cis-to-trans isomerization of 4-aminoazobenzene (AAB) is examined in various solvents of different polarities. In contrast to azobenzene (AB), it is found the rate of thermal isomerization of AAB is highly dependent on solvent polarity. Accelerated rates are observed in polar solvents as compared to nonpolar solvents. Moreover, a decrease in the barrier height with an increase in medium polarity is observed. Our observations suggest that inversion is the preferred pathway in cis-to-trans thermal isomerization in a nonpolar medium; however, in a polar medium, the isomerization path deviates from the inversion route and rotational behavior is incorporated. Differences in the kinetics and in mechanisms of isomerization in different media are rationalized in terms of modulation in barrier height by polarity of the medium and solute-solvent interaction. It is found that kinetics as well as the mechanism of thermal isomerization in AAB is controlled by the polarity of the medium.

  8. Chemical isomeric effects on propanol glassy structures

    CERN Document Server

    Cuello, G J; Bermejo, F J; Cabrillo, C

    2002-01-01

    We have studied the structure of both propanol isomers in their glassy and crystalline states by neutron diffraction. The glass-transition temperatures of 1- and 2-propanol are about 98 and 115 K, respectively and, surprisingly, even larger differences are observed for the melting temperatures of the stable crystals, which are 148 and 185 K, respectively. Their supercooled liquid phases show rather different relaxation spectra, 1-propanol manifesting strong deviations from Debye behavior, whereas 2-propanol shows a far weaker effect. We discuss the spectra obtained for the static structure factor and the static pair correlation function D(r). There is a noticeable difference in the position of the first sharp diffraction peak, which clearly indicates a density change, well correlated with the period of the intermolecular oscillations shown by D(r). (orig.)

  9. Substituent effect in the photochromism of two isomeric asymmetric diarylethenes having pyrrole and thiophene units

    Science.gov (United States)

    Wang, Renjie; Zhang, Xiaoxia; Pu, Shouzhi; Liu, Gang; Dai, Yanfeng

    2017-02-01

    Two new asymmetric isomeric diarylethenes having pyrrole and thiophene units have been synthesized by one-pot reaction and characterized by single crystal X-ray diffraction analysis. The two prepared diarylethenes had disparate crystal structures, and they exhibited distinctly different photochromic behavior, both in solution and in the solid state. Their photochromism, fatigue resistance, and fluorescence were investigated systematically. The methyl group at the reactive carbon atom could significantly enhance the quantum yield of cyclization step and decrease the quantum yield of cycloreversion step, whereas a cyano group at the same position could notably suppress the photocyclization reaction and promote the photocycloreversion reaction. The results indicated that the substituent at the reactive carbon atom could readily modulate the optoelectronic and physical properties for these diarylethenes.

  10. 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.

  11. Molecular Polymorphism: Microwave Spectra, Equilibrium Structures, and an Astronomical Investigation of the HNCS Isomeric Family

    CERN Document Server

    McGuire, Brett A; Thorwirth, Sven; Brünken, Sandra; Lattanzi, Valerio; Neill, Justin L; Spezzano, Silvia; Yu, Zhenhong; Zaleski, Daniel P; Remijan, Anthony J; Pate, Brooks H; McCarthy, Michael C

    2016-01-01

    The rotational spectra of thioisocyanic acid (HNCS), and its three energetic isomers (HSCN, HCNS, and HSNC) have been observed at high spectral resolution by a combination of chirped-pulse and Fabry-P\\'{e}rot Fourier-transform microwave spectroscopy between 6 and 40~GHz in a pulsed-jet discharge expansion. Two isomers, thiofulminic acid (HCNS) and isothiofulminic acid (HSNC), calculated here to be 35-37~kcal/mol less stable than the ground state isomer HNCS, have been detected for the first time. Precise rotational, centrifugal distortion, and nitrogen hyperfine coupling constants have been determined for the normal and rare isotopic species of both molecules; all are in good agreement with theoretical predictions obtained at the coupled cluster level of theory. On the basis of isotopic spectroscopy, precise molecular structures have been derived for all four isomers by correcting experimental rotational constants for the effects of rotation-vibration calculated theoretically. Formation and isomerization path...

  12. Kinetic barriers in the isomerization of substituted ureas: implications for computer-aided drug design

    Science.gov (United States)

    Loeffler, Johannes R.; Ehmki, Emanuel S. R.; Fuchs, Julian E.; Liedl, Klaus R.

    2016-05-01

    Urea derivatives are ubiquitously found in many chemical disciplines. N, N'-substituted ureas may show different conformational preferences depending on their substitution pattern. The high energetic barrier for isomerization of the cis and trans state poses additional challenges on computational simulation techniques aiming at a reproduction of the biological properties of urea derivatives. Herein, we investigate energetics of urea conformations and their interconversion using a broad spectrum of methodologies ranging from data mining, via quantum chemistry to molecular dynamics simulation and free energy calculations. We find that the inversion of urea conformations is inherently slow and beyond the time scale of typical simulation protocols. Therefore, extra care needs to be taken by computational chemists to work with appropriate model systems. We find that both knowledge-driven approaches as well as physics-based methods may guide molecular modelers towards accurate starting structures for expensive calculations to ensure that conformations of urea derivatives are modeled as adequately as possible.

  13. Direct two-photon excitation of isomeric transition in thorium-229 nucleus

    CERN Document Server

    Romanenko, V I; Yatsenko, L P; Romanenko, A V; Litvinov, A N; Kazakov, G A

    2012-01-01

    A possibility of the two-photon excitation of an isomeric state in a nucleus of thorium-229 has been discussed. The fluorescence intensity of the excitation is demonstrated to be identical for the irradiation of nuclei with either monochromatic light or polychromatic radiation consisting of a sequence of short light pulses of the same intensity. The two-photon excitation of Th^{3+} ion in an electromagnetic trap with a focused laser beam with a wavelength of about 320 nm and power of 100 mW can lead to the absorption saturation, at which the fluorescence emission with the frequency of the transition in a nucleus is maximal. In crystals doped with Th^{4+} to a concentration of about 10^{18} cm^{-3} and irradiated with a laser radiation 10 W in power, the emission of several photons per second with a wavelength of about 160 nm becomes possible.

  14. 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.

  15. Activation cross sections and isomeric ratios in reactions induced by 14. 5 MeV neutrons on [sup 152]Sm, [sup 154]Sm and [sup 178]Hf

    Energy Technology Data Exchange (ETDEWEB)

    Kirov, A. (Washington Univ., St. Louis, MO (United States). Dept. of Chemistry); Nenoff, N.; Georgieva, E.; Necheva, C. (Sofia Univ. (Bulgaria). Atomic Physics Dept.); Ephtimov, I. (IZR, Kostinbrod (Bulgaria))

    1993-05-01

    Cross sections for the reactions [sup 152]Sm(n, p)[sup 152g,m1,m2P]m, [sup 154]Sm(n, p)[sup 154g,m]Pm, [sup 178]Hf(n, p)[sup 178m,g]Lu, [sup 154]Sm(n, d)[sup 153]Pm and [sup 152]Sm(n, [alpha])[sup 149]Nd were measured at 14.5 meV neutron energy by the activation method. On the basis of these cross sections, the associated isomeric ratios in [sup 154]Pm, [sup 152]Pm, [sup 178]Lu and the comparison with the predictions of different compound and precompound models, conclusions are drawn about the role of the preequilibrium processes in 14.5 MeV neutron induced reactions. Calculations for equal angular momentum removal by equilibrium and preequilibrium emitted particles better reproduced the experimental isomeric ratios, than for higher angular momentum removal in the preequilibrium phase. The isomeric ratios may be used as a source of additional information about the spin of the isomeric states in [sup 152]Pm and [sup 154]Pm for which the spectroscopic information is uncertain. (orig.).

  16. Activation cross sections and isomeric ratios in reactions induced by 14.5 MeV neutrons on152Sm,154Sm and178Hf

    Science.gov (United States)

    Kirov, A.; Nenoff, N.; Georgieva, E.; Necheva, C.; Ephtimov, I.

    1993-09-01

    Cross sections for the reactions152Sm( n, p)152 g,m1, m2 Pm,154Sm( n, p)154 g,m Pm,178Hf( n, p)178 m,g Lu,154Sm( n, d)153Pm and152Sm( n, α)149Nd were measured at 14.5 MeV neutron energy by the activation method. On the basis of these cross sections, the associated isomeric ratios in154Pm,152Pm,178Lu and the comparison with the predictions of different compound and precompound models, conclusions are drawn about the role of the preequilibrium processes in 14.5 MeV neutron induced reactions. Calculations for equal angular momentum removal by equilibrium and preequilibrium emitted particles better reproduced the experimental isomeric ratios, than for higher angular momentum removal in the preequilibrium phase. The isomeric ratios may be used as a source of additional information about the spin of the isomeric states in152Pm and154Pm for which the spectroscopic information is uncertain.

  17. Isomerization and increase in the antioxidant properties of lycopene from Momordica cochinchinensis (gac) by moderate heat treatment with UV-Vis spectra as a marker.

    Science.gov (United States)

    Phan-Thi, Hanh; Waché, Yves

    2014-08-01

    Momordica cochinchinensis (gac) is a plant rich in lycopene. This pigment tends to solubilize in oil and get damaged during extraction. The impact of heating on cis-isomerization of oil-free lycopene in hexane was studied at 50 and 80°C during 240min with UV-Vis spectrometry, DAD-HPLC and TEAC test. The initial all-trans-form isomerized to the 13-cis isomer more rapidly at 80°C. After this treatment, 16% of the lycopene compounds were in the 9-cis-form. This isomer triggered an increase in the antioxidant properties which was detectable from concentrations above 9% and resulted in a change from 2.4 to 3.7μmol Trolox equivalent. It is thus possible to increase the bioactivity of lycopene samples by controlling heating. The evolution of ratios calculated from the global UV-Vis spectrum was representative of cis-isomerization and spectrometry can thus be a simple way to evaluate the state of isomerization of lycopene solutions. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    Metal-catalyzed isomerization of N- and O-allylic systems is emerging as an effective method to form synthetically useful iminium and oxocarbenium intermediates. In the presence of tethered nucleophiles, several recent examples illuminate this approach as a powerful strategy for the synthesis...... 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....

  19. Study on Isomerous CAD Model Exchange Based on Feature

    Institute of Scientific and Technical Information of China (English)

    SHAO Xiaodong; CHEN Feng; XU Chenguang

    2006-01-01

    A model-exchange method based on feature between isomerous CAD systems is put forward in this paper. In this method, CAD model information is accessed at both feature and geometry levels and converted according to standard feature operation. The feature information including feature tree, dimensions and constraints, which will be lost in traditional data conversion, as well as geometry are converted completely from source CAD system to destination one. So the transferred model can be edited through feature operation, which cannot be implemented by general model-exchange interface.

  20. 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...

  1. mer and fac isomerism in tris chelate diimine metal complexes.

    Science.gov (United States)

    Dabb, Serin L; Fletcher, Nicholas C

    2015-03-14

    In this perspective, we highlight the issue of meridional (mer) and facial (fac) orientation of asymmetrical diimines in tris-chelate transition metal complexes. Diimine ligands have long been the workhorse of coordination chemistry, and whilst there are now good strategies to isolate materials where the inherent metal centered chirality is under almost complete control, and systematic methodologies to isolate heteroleptic complexes, the conceptually simple geometrical isomerism has not been widely investigated. In systems where the two donor atoms are significantly different in terms of the σ-donor and π-accepting ability, the fac isomer is likely to be the thermodynamic product. For the diimine complexes with two trigonal planar nitrogen atoms there is much more subtlety to the system, and external factors such as the solvent, lattice packing and the various steric considerations play a delicate role in determining the observed and isolable product. In this article we discuss the possibilities to control the isomeric ratio in labile systems, consider the opportunities to separate inert complexes and discuss the observed differences in their spectroscopic properties. Finally we report on the ligand orientation in supramolecular systems where facial coordination leads to simple regular structures such as helicates and tetrahedra, but the ability of the ligand system to adopt a mer orientation enables self-assembled structures of considerable beauty and complexity.

  2. Isocyanurates with planar chirality: design, optical resolution, and isomerization.

    Science.gov (United States)

    Goto, Hidetoshi; Sudoh, Masanao; Kawamoto, Keiko; Sugimoto, Hiroshi; Inoue, Shohei

    2012-10-01

    Designs and syntheses of isocyanurates (1-3) are described on the basis of a novel concept that two enantiotopic faces of C(s) -symmetric, prochiral planar molecules are differentiated with a location of groups at the top or bottom of the planar skeleton using a rigid linker. Such isocyanurates are atropisomeric. The planar-chiral structures of 1 and 2(anti) (anti-conformer of 2) were confirmed by single-crystal X-ray analyses, and the space groups were P1 (for 1) and P2(1)/c (for 2(anti)), resulting that the crystals were racemates. Optical resolutions of 1-3 were successfully accomplished by using chiral high-performance liquid chromatography technique in combination with circular dichroism, absorption, and nuclear magnetic resonance spectroscopies and mass spectrometry. Furthermore, the rotational barriers (ΔG(‡)s) related to isomerizations of 1-3 were estimated to be 27.2 (for 1 at 50 °C), 27.6 (for 2(anti) at 50 °C), and 40.6 (for 3(syn) at 150 °C) kcal/mol. The ΔG(‡)s of 2 and 3 were higher than that of 1 and, in particular, that of 3 was highest among them. This result indicates that an introduction of bulky substituents and an intramolecular bridging are effective for inhibitions of the isomerizations.

  3. Studies of some isomeric yield ratios produced with bremsstrahlung

    CERN Document Server

    Kolev, D

    1998-01-01

    The experimental isomeric ratios for sup 5 sup 2 sup m sup , sup g Mn, sup 8 sup 6 sup m sup , sup g Y, sup 8 sup 7 sup m sup , sup g Y, sup 8 sup 9 sup m sup , sup g Zr, sup 1 sup 1 sup 0 sup m sup , sup g In, sup 1 sup 1 sup 1 sup m sup , sup g In, sup 1 sup 1 sup 2 sup m sup , sup g In, sup 1 sup 5 sup 2 sup m sup 1 sup , sup g Pm, sup 1 sup 5 sup 2 sup m sup 2 sup , sup m sup 1 Eu, sup 1 sup 6 sup 2 sup m sup , sup g Ho, sup 1 sup 6 sup 4 sup m sup , sup g Ho and sup 1 sup 7 sup 8 sup m sup , sup g Lu measured by the activation technique from different targets in (gamma, xnp) reactions (x<=3) at the bremsstrahlung end-point energy of 43 MeV are presented. The predictions of calculations performed by means of compound nucleus particle evaporation and final gamma-deexcitation were critically discussed. The importance of inclusion in the calculations of nonequilibrium particle emission and an adequate gamma-decay mode of isomeric nuclei was considered for some of the reactions investigated.

  4. Tandem Ring-Closing Metathesis/Isomerization Reactions for the Total Synthesis of Violacein

    DEFF Research Database (Denmark)

    Petersen, Mette T.; 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 prov...

  5. 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.

  6. Iridium complexes of new NCP pincer ligands: catalytic alkane dehydrogenation and alkene isomerization.

    Science.gov (United States)

    Jia, Xiangqing; Zhang, Lei; Qin, Chuan; Leng, Xuebing; Huang, Zheng

    2014-09-28

    Iridium complexes of novel NCP pincer ligands containing pyridine and phosphinite arms have been synthesized. One Ir complex shows good catalytic activity for alkane dehydrogenation, and all complexes are highly active for olefin isomerization. A combination of the Ir complex and a (PNN)Fe pincer complex catalyzes the formation of linear alkylboronates selectively from internal olefins via sequential olefin isomerization-hydroboration.

  7. 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.

  8. 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...

  9. 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.

  10. 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.

  11. RuCl3·3H2O Mediated Olefin Isomerizations in Ionic Liquids:A Highly Recyclable System for Olefin Isomerizations

    Institute of Scientific and Technical Information of China (English)

    SHAO Ming-bo; LIU Gui-yan; ZHAO Jing-jing; WANG Xiao-yu; WANG Jian-hui

    2012-01-01

    Herein lies a convenient and highly efficient method of olefin isomerization in the presence of RuCl3·3H2O in ionic liquid(IL).More importantly,RuCl3·3H2O is a robust and recyclable catalyst.Nine cycles of RuCl3·3H2O as the catalyst were performed for the isomerization reactions of the selected substrate in IL and MeOH.

  12. Identification of Asp isomerization in proteins by ¹⁸O labeling and tandem mass spectrometry.

    Science.gov (United States)

    Zhang, Jennifer; Katta, Viswanatham

    2012-01-01

    Isomerization of aspartic acid (Asp) to isoaspartic acid (isoAsp) via succinimide intermediate is a common route of degradation for proteins that can affect their structural integrity. As Asp/isoAsp is isobaric in mass, it is difficult to identify the site of modification by LC-MS/MS peptide mapping. Here, we describe an approach to label the Asp residue involved in isomerization at the protein level by hydrolyzing the succinimide intermediate in H₂¹⁸O. Tryptic digestion of this labeled protein will result in peptides containing the site of isomerization being 2 Da heavier than the ¹⁶O-containing counterparts, due to ¹⁸O incorporation during the hydrolysis process. Comparison of tandem mass spectra of isomerized peptides with and without ¹⁸O incorporation allows easy identification of the Asp residue involved. This method proved to be especially useful in identifying the sites when isomerization occurs in Asp-Asp motifs.

  13. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks

    Energy Technology Data Exchange (ETDEWEB)

    Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.; Beltran, Leslie V.; Kunz, Linda A.; Pals, Tessa M.; Quinn, Jordan R; Behrends, Jr., Raymond T.; Bernhardt, Randal J.

    2016-07-05

    Methods are provided for refining natural oil feedstocks and producing isomerized esters and acids. The methods comprise providing a C4-C18 unsaturated fatty ester or acid, and isomerizing the fatty acid ester or acid in the presence of heat or an isomerization catalyst to form an isomerized fatty ester or acid. In some embodiments, the methods comprise forming a dibasic ester or dibasic acid prior to the isomerizing step. In certain embodiments, the methods further comprise hydrolyzing the dibasic ester to form a dibasic acid. In certain embodiments, the olefin is formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having unsaturated esters.

  14. Candidates for Long Lived High-K Ground States in Superheavy Nuclei

    CERN Document Server

    Jachimowicz, P; Skalski, J

    2015-01-01

    On the basis of systematic calculations for 1364 heavy and superheavy nuclei, including odd-systems, we have found a few candidates for high-K ground states in superheavy nuclei. The macroscopic-microscopic model based on the deformed Woods-Saxon single particle potential which we use offers a reasonable description of SH systems, including known: nuclear masses, $Q_{\\alpha}$-values, fission barriers, ground state deformations, super- and hyper-deformed minima in the heaviest nuclei. %For odd and odd-odd systems, both ways of including pairing correlations, % blocking and the quasi-particle method, have been applied. Exceptionally untypical high-K intruder contents of the g.s. found for some nuclei accompanied by a sizable excitation of the parent configuration in daughter suggest a dramatic hindrance of the $\\alpha$-decay. Multidimensional hyper-cube configuration - constrained calculations of the Potential Energy Surfaces (PES's) for one especially promising candidate, $^{272}$ Mt, shows a $\\backsimeq$ 6 Me...

  15. Insights into the isomerization of photochromic oxazines from the excitation dynamics of BODIPY-oxazine dyads.

    Science.gov (United States)

    Deniz, Erhan; Battal, Mutlu; Cusido, Janet; Sortino, Salvatore; Raymo, Françisco M

    2012-08-07

    We synthesized five BODIPY-oxazine dyads in one to four synthetic steps from known precursors. They differ in the nature of the unsaturated spacer linking the oxazine photochrome to either the conjugated framework or the boron center of the BODIPY fluorophore. Despite the π-character of the linkers, the two functional components are electronically isolated in the ground state and the BODIPY fluorophore maintains its absorption and, with one exception, emission properties unaltered. Instead, the photochemical response of the photochromic component is completely suppressed within all dyads. Rather than the expected opening of the oxazine ring, the laser excitation of these molecular assemblies results in the effective population of the BODIPY triplet in four of the five dyads. Control experiments with appropriate model compounds indicate that the local excitation of the oxazine component results first in intersystem crossing and then energy transfer to the BODIPY component. In fact, the transfer of energy from the triplet state of the former to the triplet state of the latter competes successfully with the opening of the oxazine ring and prevents the isomerization of the photochromic component. These observations demonstrate, for the very first time, that the photoinduced opening of these photochromic oxazines occurs along the potential energy surface of their triplet state. Such valuable mechanistic insights into their excitation dynamics can guide the design of novel members of this family of photochromic compounds with improved photochemical properties.

  16. Effect of protonation on the isomerization properties of n-butylamine Schiff base of isomeric retinal as revealed by direct HPLC analyses: selection of isomerization pathways by retinal proteins.

    Science.gov (United States)

    Koyama, Y; Kubo, K; Komori, M; Yasuda, H; Mukai, Y

    1991-09-01

    Alumina adsorption chromatography and ion-pair reversed-phase chromatography were developed to analyze the isomers of unprotonated and protonated n-butylamine Schiff base of retinal (RSB and PRSB), respectively. Photoisomerization starting from the all-trans, 11-cis and 13-cis isomers was traced for RSB in n-hexane, acetonitrile, methanol and 1-butanol, and for PRSB in methanol, acetonitrile and 1-butanol. The quantum yields of photoisomerization for the all-trans, 9-cis, 11-cis and 13-cis isomers were determined for RSB and PRSB in the above solvents except 1-butanol. On the other hand, photoisomerization of isomeric retinal bound (through Schiff base linkage) to bovine serum albumin (RBSA) in aqueous solution (pH 3, 7 and 12) as well as thermal isomerization of RSB (in n-hexane), PRSB (in methanol) and RBSA (in aqueous solution, pH 7) were traced starting from the all-trans, 11-cis, and 13-cis isomers. Protonation of RSB drastically changes the pathway of photoisomerization and increases the quantum yields of isomeric RSB. The solvent polarity increases the quantum yields of RSB differently depending on the configuration. Protonation enhances thermal isomerization also. The results of the above model systems are compared with those of retinal proteins to rationalize their selection of the particular isomerization pathways.

  17. Molecular Choreography of Isomerization and Electron Transfer Using One and Two Dimensional Femtosecond Stimulated Raman Spectroscopy

    Science.gov (United States)

    Hoffman, David Paul

    Chemical reactions are defined by the change in the relative positions and bonding of nuclei in molecules. I have used femtosecond stimulated Raman spectroscopy (FSRS) to probe these transformations with structural specificity and high time precision revealing the mechanisms of two important classes of reactions; isomerization about an N=N bond and interfacial/intermolecular electron transfer. Isomerization about a double bond is one of the simplest, yet most important, photochemical reactions. In contrast to carbon double bonds, nitrogen double bonds can react via two possible mechanisms; rotation or inversion. To determine which pathway is predominant, I studied an azobenzene derivative using both FSRS and impulsive stimulated Raman spectroscopy (ISRS). The FSRS experiments demonstrated that the photochemical reaction occurs concomitantly with the 700 fs non-radiative decay of the excited state; because no major change in N=N stretching frequency was measured, I surmised that the reaction proceeds through an inversion pathway. My subsequent ISRS experiments confirmed this hypothesis; I observed a highly displaced, low frequency, inversion-like mode, indicating that initial movement out of the Franck-Condon region proceeds along an inversion coordinate. To probe which nuclear motions facilitate electron transfer and charge recombination, I used FSRS and the newly developed 2D-FSRS techniques to study two model systems, triphenylamine dyes bound to TiO2 nanoparticles and a molecular charge transfer (CT) dimer. In the dye-nanoparticle system I discovered that charge separation persists much longer (> 100 ps) than previously thought by using the juxtaposition of the FSRS and transient absorption data to separate the dynamics of the dye from that of the injected electron. Additionally, I discovered that dye constructs with an added vinyl group were susceptible to quenching via isomerization. The CT dimer offered an opportunity to study a system in which charge

  18. Cis-trans isomerizations of beta-carotene and lycopene: a theoretical study.

    Science.gov (United States)

    Guo, Wen-Hsin; Tu, Cheng-Yi; Hu, Ching-Han

    2008-09-25

    The all-trans to mono-cis isomerizations of polyenes and two C40H56 carotenes, beta-carotene and lycopene, at the ground singlet (S0) and triplet (T1) states are studied by means of quantum chemistry computations. At the S0 state of polyenes containing n acetylene units (Pn), we find that the energy barrier of the central C=C rotation decreases with n. In contrast, however, at the T 1 state, the rotational barrier increases with n. For the C40H56 carotenes, the rotational barriers of lycopene are lower than those of their beta-carotene counterparts. This difference renders the rotational rates of lycopene to be 1-2 orders of magnitude higher than those of beta-carotene at room temperature. For both these carotenes, the barrier is lowest for the rotation toward the 13-cis isomer. The relative abundances are in the following order: all-trans > 9-cis > 13-cis > 15-cis. Although the 5-cis isomer of lycopene has the lowest energy among the cis isomers, its formation from the all-trans form is restricted, owing to a very large rotational barrier. The possible physiological implications of this study are discussed.

  19. Surface electronic structure and isomerization reactions of alkanes on some transition metal oxides

    Science.gov (United States)

    Katrib, A.; Logie, V.; Saurel, N.; Wehrer, P.; Hilaire, L.; Maire, G.

    1997-04-01

    XP spectra of some reduced transition metal oxides are presented. Different number of free nd,( n + 1)s valence electrons in each case could be observed by the presence of a certain density of states (DOS) at the Fermi-level in the valence band (VB) energy region of the XP spectrum. Catalytic isomerization reactions of 2-methylpentane yielding 3-methylpentane and n-hexane at 350°C have been observed on these reduced valence surface states. The bifunctionel mechanism in terms of metallic and acidic sites required for such reactions is proposed by considering the metallic properties of the rutile deformed structure through the C-axis in the case of MoO 2 and WO 2, while the oxygen atom(s) in the lattice structure exhibit Brönsted acidic properties. On the other hand, highly reduced or clean surfaces of these transition metals yield hydrogenolysis catalytic reactions for the same reactant with methane as the major product. In all cases, the exposure of the lower valence oxidation states of bulk transition metal oxides to air results in the surface partial oxidation to the stable oxides such as MoO 3, WO 3, V 2O 5 and Nb 2O 5.

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

    DEFF Research Database (Denmark)

    Li, Hu; Yang, Song; Saravanamurugan, Shunmugavel

    2017-01-01

    /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........ Isomerization of glucose is also a central reaction for making renewable platform chemicals, such as lactic acid, 5-hydroxymethylfurfural (HMF), and levulinic acid. In these other applications, thermally stable catalysts are required, thus making use of enzymatic catalysis inadequate, since enzymes generally...

  1. Existence of long-lived isotopes of a superheavy element in natural Au

    CERN Document Server

    Marinov, A; Gentry, R V; Halicz, L; Kashiv, Y; Kolb, D; Miller, H W; Pape, A; Rodushkin, I; Segal, I

    2007-01-01

    Evidence for the existence of long-lived isotopes with atomic mass numbers 261 and 265 and abundance of (1-10)x10$^{-10}$ relative to Au has been found in a study of natural Au using an inductively coupled plasma - sector field mass spectrometer. The measured masses fit the predictions made for the masses of $^{261}$Rg and $^{265}$Rg (Z=111) and for some isotopes of nearby elements. The possibility that these isotopes belong to the recently discovered class of long-lived high spin super- and hyperdeformed isomeric states is discussed.

  2. 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

  3. Quantum chemical study of the isomerization of 24-methylenecycloartanol, a potential marker of olive oil refining.

    Science.gov (United States)

    Wedler, Henry B; Pemberton, Ryan P; Lounnas, Valère; Vriend, Gert; Tantillo, Dean J; Wang, Selina C

    2015-05-01

    Quantum chemical calculations on the isomerization of 24-methylenecycloartanol are described. An energetically viable mechanism, with a rate-determining protonation step, is proposed. This rearrangement may find applicability in tests for determining if an olive oil has been refined.

  4. Mixed Potential Energy Surfaces of the Ultrafast Isomerization of Retinal in Bacteriorhodopsin

    Directory of Open Access Journals (Sweden)

    Prokhorenko Valentyn I.

    2013-03-01

    Full Text Available We observe, using electronic two-dimensional photon echo spectroscopy, that the cis and trans potential energy surfaces of the ultrafast isomerization of retinal in bacteriorhodopsin are mixed via the hydrogen out of plane (HOOP mode.

  5. Communication: Effective spectroscopic Hamiltonian for multiple minima with above barrier motion: Isomerization in HO(2).

    Science.gov (United States)

    Barnes, George L; Kellman, Michael E

    2010-09-14

    We present a two-dimensional potential surface for the isomerization in the hydroperoxyl radical HO(2) and calculate the vibrational spectrum. We then show that a simple effective spectroscopic fitting Hamiltonian is capable of reproducing large scale vibrational spectral structure above the isomerization barrier. Polyad breaking with multiple resonances is necessary to adequately describe the spectral features of the system. Insight into the dynamical nature of isomerization related to the effective Hamiltonian is gained through classical trajectories on the model potential. Contrary to physical intuition, the bend mode is not a "reaction mode," but rather isomerization requires excitation in both stretch and bend. The dynamics reveals a Farey tree formed from the 2:1 and 3:1 resonances, corresponding to the resonance coupling terms in the effective Hamiltonian, with the prominent 5:2 (2:1+3:1) feature dividing the tree into parts that we call the 3:1 and 2:1 portions.

  6. Quantum chemical study of the isomerization of 24-methylenecycloartanol, a potential marker of olive oil refining

    NARCIS (Netherlands)

    Wedler, H.B.; Pemberton, R.P.; Lounnas, V.; Vriend, G.; Tantillo, D.J.; Wang, S.C.

    2015-01-01

    Quantum chemical calculations on the isomerization of 24-methylenecycloartanol are described. An energetically viable mechanism, with a rate-determining protonation step, is proposed. This rearrangement may find applicability in tests for determining if an olive oil has been refined.

  7. Isomerization and fluorescence depolarization of merocyanine 540 in polyacrylic acid. Effect of H

    Indian Academy of Sciences (India)

    Dipankar Sukul; Sobhan Sen; Partha Dutta; Kankan Bhattacharyya

    2002-10-01

    Dynamics of isomerization and fluorescence depolarization of merocyanine 540 (MC540) in an aqueous solution of polyacrylic acid (PAA) have been studied using picosecond time resolved fluorescence spectroscopy. It is observed that the dynamics of isomerization and depolarization are sensitive enough to monitor the uncoiling of PAA at high H (> 6). At low H (< 3), when the polymer remains in a hypercoiled form, polymer bound MC540 experiences very high microscopic friction and, hence, the isomerization and depolarization processes are very slow. At high H (> 6) a polyanion is formed and the polymer assumes an extended configuration due to electrostatic repulsion. At high H (> 6), the anionic probe MC540 is expelled from the polyanion to bulk water and the dynamics of isomerization and fluorescence depolarization become faster by 12 and 5 times respectively, compared to those at low H.

  8. β and Isomeric Decay of Nuclei in the 100Sn Region

    Science.gov (United States)

    Becerril, A. D.; Amthor, A. M.; Baumann, T.; Bazin, D.; Berryman, J. S.; Crawford, H.; Estrade, A.; Gade, A.; Ginter, T.; Guess, C. J.; Hausmann, M.; Hitt, G. W.; Lorusso, G.; Mantica, P. F.; Matos, M.; Meharchand, R.; Minamisono, K.; Montes, F.; Pereira, J.; Perdikakis, G.; Portillo, M.; Schatz, H.; Smith, K.; Stoker, J.; Zegers, R. T. G.

    2010-08-01

    The decay properties of rp-process nuclei in the vicinity of 100Sn have been studied at the National Superconducting Cyclotron Laboratory (NSCL). The measured β-decay half-life for 100Sn is 0.55-0.31+0.70 s, in agreement with a previous measurement. In 98In, the β-decay of the ground state plus that of a long lived isomer were observed with half-lives of 47(13) ms and 0.66(40) s respectively. The half-life of 96Cd, measured for the first time, is 1.03-0.21+0.24 s; however, the existence of a predicted isomeric state in this nucleus could not be confirmed. Additionally, a gamma cascade de-exciting a μ-isomer in the odd-odd nucleus 96Ag was observed. The implications of the measured half-life of 96Cd on the calculated rp-process final abundances are discussed.

  9. Spectrophotometric studies on alkaline isomerization of spinach ferredoxin.

    Science.gov (United States)

    Hasumi, H; Nagata, E; Nakamura, S

    1985-10-01

    The gross protein structure, the microenvironment of the iron-sulfur cluster, and the effect of neutral salts on the molecular structure of spinach ferredoxin were studied by CD and absorption spectroscopy in the alkaline pH range. In the pH range of 7-11, the existence of reversible isomerization which consisted of at least two proton dissociation processes was indicated by the statical CD and absorption spectra. The CD changes in the visible and far-UV regions were dramatic upon elevation of the pH from neutral to alkaline, indicating a significant alteration of the microenvironment of the cluster and a decrease in the ordered secondary structures. The absorption change in the visible region due to pH elevation was small but clearly observed with a high signal-to-noise ratio. The numbers of protons involved in the respective processes and the apparent pK values obtained from the pH-dependence of the CD changes were in good agreement with those obtained from the pH-dependence of the absorption changes in the visible region. In addition, the rate constants obtained from the time courses of the CD and absorption changes agreed with one another. By the addition of 1 M NaCl, the CD and absorption spectra at alkaline pH were reversed almost to those at neutral pH without significant pH change. On the other hand, above pH 11, ferredoxin was found to be irreversibly denatured. Based on analyses of the statical CD and absorption spectra and of the time courses of the CD changes, the probable mechanism of the isomerization was considered to be as follows: (Formula: see text) where H stands for a proton, N-form for native ferredoxin at neutral pH, N*-form for alkaline ferredoxin below pH 11 which still has the iron-sulfur cluster but with disordered secondary structures of the polypeptide chain, and D-form for completely denatured ferredoxin above pH 11. These results lead to the conclusions that (1) the interaction between the protein moiety and the iron-sulfur cluster is

  10. Effect of Ni Loading on the Catalytic Properties of Molybdenum Oxides for the Isomerization of Heptane

    Institute of Scientific and Technical Information of China (English)

    YingJunWANG; XinPingWANG; 等

    2002-01-01

    The catalytic properties of MoOx and incorporation Ni onto the MoOx for the isomerization of heptane have been investigated under atmospheric pressure at different conditions such as different flow rate of H2,different reaction temperature tec. Compared with MoOx, the Ni addition to the MoOx markedly improved the isomerization activity of heptane by improving the reducibility of MoO3 and activation of H2 in reaction.

  11. Effect of Ni Loading on the Catalytic Properties of Molybdenum Oxides for the Isomerization of Heptane

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The catalytic properties of MoOx and incorporation Ni onto the MoOx for the isomerization of heptane have been investigated under atmospheric pressure at different conditions such as different flow rate of H2, different reaction temperature etc.. Compared with MoOx, the Ni addition to the MoOx markedly improved the isomerization activity of heptane by improving the reducibility of MoO3 and activation of H2 in reaction.

  12. Influence of the steric effect of flexible isomeric phenylenediacetic acids on the resultant lead(II) coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yunlong; Zhao, Yanqing; Yang, Guo-Ping, E-mail: ygp@nwu.edu.cn; Guo, Yanjun; Wang, Yao-Yu, E-mail: wyaoyu@nwu.edu.cn; Shi, Qi-Zhen

    2015-03-15

    To study the steric effect of the flexible dicarboxylate ligands on the resultant formations of coordination polymers (CPs), four new Pb{sup II} CPs [Pb(1,2-pda)(H{sub 2}O)]{sub n} (1), [Pb(1,3-pda)]{sub n}·nH{sub 2}O (2), [Pb{sub 2}(1,4-pda){sub 2}(H{sub 2}O)]{sub n}·2nH{sub 2}O (3a and 3b) have been produced by the isomeric phenylenediacetic acids (H{sub 2}pda). The X-ray crystallography study reveals that CP 1 is a two-dimensional (2D) 4-connected sql (4{sup 4}.6{sup 2}) network via the weak Pb···O interactions built on 1D chain-like structure. CP 2 crystallizes in orthorhombic system with chiral space group P2{sub 1}2{sub 1}2{sub 1}, showing a 4-connected sra (4{sup 2}.6{sup 3}.8) framework where a left-handed helical motif is formed by Pb{sup II} ions and trans-1,3-pda ligands. More interestingly, CPs 3a and 3b are two true 3D polymorphs and have the different morphology. Topologically, the framework of 3a exhibits a 4-connected lon 6{sup 6} motif, while that of 3b is a (4,6)-connected fsh (4{sup 3}.6{sup 3}){sub 2}(4{sup 6}.6{sup 6}.8{sup 3}) net. It is found that the three isomeric pda anions display the various coordination fashions in four CPs. The different structural arrangements show that the steric effect of the isomeric H{sub 2}pda tectons has a positive role in directing the final products of Pb{sup II} CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature. - Graphical abstract: Four new Pb{sup II}-based CPs have been produced by the isomeric phenylenediacetic acids (H{sub 2}pda). The different structural arrangements show that the steric effect of the isomeric H{sub 2}pda tectons has a positive role in directing the final products of Pb{sup II} CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature. - Highlights: • Four Pb{sup II}-based coordination polymers were produced by phenylenediacetic acids. • The crystal and topological structures of the

  13. Cross sections for the formation of 69Znm,g and 71Znm,g in neutron induced reactions near their thresholds: Effect of reaction channel on the isomeric cross-section ratio

    Science.gov (United States)

    Nesaraja, C. D.; Sudár, S.; Qaim, S. M.

    2003-08-01

    Excitation functions were measured for the reactions 72Ge(n,α)69Znm,g, 69Ga(n,p)69Znm,g, 70Zn(n,2n)69Znm,g, 74Ge(n,α)71Znm,g, and 71Ga(n,p)71Znm,g over the neutron energy range of 6.3 12.4 MeV. Quasimonoenergetic neutrons in this energy range were produced via the 2H(d,n)3He reaction using a deuterium gas target at the Jülich variable energy compact cyclotron. Use was made of the activation technique in combination with high-resolution HPGe-detector γ-ray spectroscopy. In a few cases low-level β-counting was also applied. In order to decrease the interfering activities in those cases, either radiochemical separations were performed or isotopically enriched targets were used. For most of the reactions, the present measurements provide the first consistent sets of data near their thresholds. From the available experimental data, isomeric cross-section ratios were determined for the isomeric pair 69Znm,g in (n,α), (n,p), and (n,2n) reactions, and for the pair 71Znm,g in (n,α) and (n,p) reactions. Nuclear model calculations using the code STAPRE, which employs the Hauser-Feshbach (statistical model) and exciton model (precompound effects) formalisms, were undertaken to describe the formation of both isomeric and ground states of the products. The calculational results on the total (n,α), (n,p), and (n,2n) cross sections agree fairly well with the experimental data. The experimental isomeric cross-section ratios, however, are reproduced only approximately by the calculation. For both the isomeric pairs investigated, the isomeric cross-section ratio in the (n,p) reaction is higher than in other reactions.

  14. Photochemical Isomerization and Topochemical Polymerization of the Programmed Asymmetric Amphiphiles

    Science.gov (United States)

    Kim, Dae-Yoon; Lee, Sang-A.; Jung, Daseal; Jeong, Kwang-Un

    2016-06-01

    For the advancement in multi-stimuli responsive optical devices, we report the elaborate molecular engineering of the dual photo-functionalized amphiphile (abbreviated as AZ1DA) containing both a photo-isomerizable azobenzene and a photo-polymerizable diacetylene. To achieve the efficient photochemical reactions in thin solid films, the self-assembly of AZ1DA molecules into the ordered phases should be precisely controlled and efficiently utilized. First, the remote-controllable light shutter is successfully demonstrated based on the reversible trans-cis photo-isomerization of azobenzene group in the smectic A mesophase. Second, the self-organized monoclinic crystal phase allows us to validate the photo-polymerization of diacetylene moiety for the photo-patterned thin films and the thermo-responsible color switches. From the demonstrations of optically tunable thin films, it is realized that the construction of strong relationships between chemical structures, molecular packing structures and physical properties of the programmed molecules is the core research for the development of smart and multifunctional soft materials.

  15. Cyclophilin A catalyzes proline isomerization by an electrostatic handle mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Camilloni, Carlo; Sahakyan, Aleksander B.; Holliday, Michael; Isern, Nancy G.; Zhang, Fengli; Eisenmesser, Elan Z.; Vendruscolo, Michele

    2014-07-15

    Proline isomerization is a ubiquitous process that plays a key role in the folding of proteins and in the regulation of their functions1-3. Different families of enzymes, known as peptidyl-prolyl isomerases (PPIases), catalyse this reaction, which involves the interconversion between the cis and trans isomers of the Nterminal amide bond of the amino acid proline2,3. A complete description of the mechanisms by which these enzymes function, however, has remained elusive. Here, we show that cyclophilin A, one of the most common PPIases4, provides a catalytic environment that acts on the substrate through an electrostatic lever mechanism. In this mechanism, the electrostatic field in the catalytic site turns the electric dipole associated with the carboxylic group of the amino acid preceding the proline in the substrate, thus causing the rotation of the peptide bond between the two residues. This mechanism resulted from the analysis of an ensemble of conformations populated by cyclophilin A during the enzymatic reaction using a combination of NMR measurements, molecular dynamics simulations and density functional theory calculations. We anticipate that this approach will be helpful in elucidating whether the electrostatic lever mechanism that we describe is common to other PPIases, and more generally to characterise other enzymatic processes.

  16. Photochemical generation, isomerization, and oxygenation of stilbene cation radicals

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, F.D.; Bedell, A.M.; Dykstra, R.E.; Elbert, J.E. (Northwestern Univ., Evanston, IL (USA)); Gould, I.R.; Farid, S. (Eastman Kodak Co., Rochester, NY (USA))

    1990-10-24

    The cation radicals of cis- and trans-stilbene and several of their ring-substituted derivatives have been generated in solution directly by means of pulsed-laser-induced electron transfer to singlet cyanoanthracenes or indirectly via electron transfer from biphenyl to the singlet cyanoanthracene followed by secondary electron transfer from the stilbenes to the biphenyl cation radical. Transient absorption spectra of the cis- and trans-stilbene cation radicals generated by secondary electron transfer are similar to those previously obtained in 77 K matrices. Quantum yields for radical ion-pair cage escape have been measured for direct electron transfer from the stilbenes to three neutral and one charged singlet acceptor. These values increase as the ion-pair energy increases due to decreased rate constants for radical ion-pair return electron transfer, in accord with the predictions of Marcus theory for highly exergonic electron transfer. Cage-escape efficiencies are larger for trans- vs cis-stilbene cation radicals, possibly due to the greater extent of charge delocalization in the planar trans vs nonpolar cis cation radicals. Cage-escape stilbene cation radicals can initiate a concentration-dependent one way cis- {yields} trans-stilbene isomerization reaction.

  17. Isomerization and fragmentation pathways of 1,2-azaborine.

    Science.gov (United States)

    Edel, Klara; Fink, Reinhold F; Bettinger, Holger F

    2016-01-05

    The generation of 1,2-azaborine (4), the BN-analogue of ortho-benzyne, was recently achieved by elimination of tert-butyldimethylchlorosilane under the conditions of flash vacuum pyrolysis. The present investigation identifies by computational means pathways for the thermal isomerization and fragmentation of 1,2-azaborine. The computations were performed using single reference (hybrid/density functional, second order Møller-Plesset perturbation, and coupled cluster theories) as well as multiconfiguration methods (complete active space SCF based second order perturbation theory, multireference configuration interaction, and multiconfiguration coupled electron pair approximation) with basis sets up to polarized triple-ζ quality. The 1,2-azaborine is, despite the distortion of its molecular structure, the most stable C4H4BN isomer investigated. The formation of BN-endiyne isomers is highly unfavorable as the identified pathways involve barriers close to 80 kcal mol(-1). The concerted fragmentation to ethyne and 2-aza-3-bora-butadiyne even has a barrier close to 120 kcal mol(-1). The fragmentation of BN-enediynes has energetic requirements similar to enediynes. © 2015 Wiley Periodicals, Inc.

  18. An automated exploration of the isomerization and dissociation pathways of (E)-1,2-dichloroethene cations and anions

    Science.gov (United States)

    Kishimoto, Naoki; Nishi, Yuito

    2017-04-01

    Isomerization and dissociation pathways after the photoionization or electron attachment of (E)-1,2-dichloroethene were calculated with an automated exploration method utilizing a scaled hypersphere search of the anharmonic downward distortion following algorithm at the UB3LYP/6-311G(2d,d,p) level of theory. The potential energies of transition states and dissociation channels were calculated by a composite method ((RO)CBS-QB3) and compared with the breakdown diagrams and electron attachment spectra observed in previous spectroscopic studies. The results of single point calculations with several DFT and post-SCF methods are compared using the root mean square deviations from the (RO)CBS-QB3 energies for six states of anionic dichloroethene.

  19. Conformational preferences and prolyl cis-trans isomerization of phosphorylated Ser/Thr-Pro motifs.

    Science.gov (United States)

    Byun, Byung Jin; Kang, Young Kee

    2010-04-01

    The conformational study on Ac-pSer-Pro-NHMe and Ac-pThr-Pro-NHMe peptides has been carried out using hybrid density functional methods with the implicit solvation reaction field theory at the B3LYP/ 6-311++G(d,p)//B3LYP/6-31+G(d) level of theory in the gas phase and in solution (chloroform and water). For both pSer-Pro and pThr-Pro peptides in the gas phase and in chloroform, the most preferred conformation has the alpha-helical structure for the pSer/pThr residue, the down-puckered polyproline I structure for the Pro residue, and the cis prolyl peptide bond between the two residues, in which two hydrogen bonds between the phosphate oxygens with the backbone N--H groups seem to play a role. However, the trans conformations that have a single hydrogen bond of the phosphate oxygen with either of two backbone N--H groups become most preferred for both peptides in water. This is because the hydration free energy of the anionic oxygen of the phosphate group is expected to dramatically decrease for the cis conformation upon formation of the hydrogen bond with the backbone N--H groups. These calculated results are consistent with the observations by NMR and IR experiments, suggesting the existence of hydrogen bonds between the charged phosphoryl group and the backbone amide protons in solution. The calculated cis populations of 14.7 and 14.2% and rotational barriers of 19.87 and 20.57 kcal/mol to the cis-to-trans isomerization for pSer-Pro and pThr-Pro peptides in water, respectively, are consistent with the observed values for pSer-Pro and pThr-Pro containing peptides from NMR experiments. However, the hydrogen bond between the prolyl nitrogen and the following amide N--H group, which was suggested to be capable of catalyzing the prolyl isomerization, does not play a role in stabilizing the preferred transition state for the pSer/pThr-Pro peptides in water. Instead, the amide hydrogen of the NHMe group is involved in a bifurcated hydrogen bond with the anionic oxygen

  20. A bacterial tyrosine aminomutase proceeds through retention or inversion of stereochemistry to catalyze its isomerization reaction.

    Science.gov (United States)

    Wanninayake, Udayanga; Walker, Kevin D

    2013-07-31

    β-Amino acids are biologically active compounds of interest in medicinal chemistry. A class I lyase-like family of aminomutases isomerizes (S)-α-arylalanines to the corresponding β-amino acids by exchange of the NH2/H pair. This family uses a 3,5-dihydro-5-methylidene-4H-imidazol-4-one (MIO) group within the active site to initiate the reaction. The absolute stereochemistry of the product is known for an MIO-dependent tyrosine aminomutase from Chondromyces crocatus (CcTAM) that isomerizes (S)-α-tyrosine to (R)-β-tyrosine. To evaluate the cryptic stereochemistry of the CcTAM mechanism, (2S,3S)-[2,3-(2)H2]- and (2S,3R)-[3-(2)H]-α-tyrosine were stereoselectively synthesized from unlabeled (or [(2)H]-labeled) (4'-hydroxyphenyl)acrylic acids by reduction with D2 (or H2) gas and a chiral Rh-Prophos catalyst. GC/EIMS analysis of the [(2)H]-β-tyrosine biosynthesized by CcTAM revealed that the α-amino group was transferred to Cβ of the phenylpropanoid skeleton with retention of configuration. These labeled substrates also showed that the pro-(3S) proton exchanges with protons from the bulk media during its migration to Cα during catalysis. (1)H- and (2)H NMR analyses of the [(2)H]-β-tyrosine derived from (2S)-[3,3-(2)H2]-α-tyrosine by CcTAM catalysis showed that the migratory proton attached to Cα of the product also with retention of configuration. CcTAM is stereoselective for (R)-β-tyrosine (85%) yet also forms the (S)-β-tyrosine enantiomer (15%) through inversion of configuration at both migration termini, as described herein. The proportion of the (S)-β-isomer made by CcTAM during steady state interestingly increased with solvent pH, and this effect on the proposed reaction mechanism is also discussed.

  1. Computational studies of the isomerization and hydration reactions of acetaldehyde oxide and methyl vinyl carbonyl oxide.

    Science.gov (United States)

    Kuwata, Keith T; Hermes, Matthew R; Carlson, Matthew J; Zogg, Cheryl K

    2010-09-02

    Alkene ozonolysis is a major source of hydroxyl radical (*OH), the most important oxidant in the troposphere. Previous experimental and computational work suggests that for many alkenes the measured *OH yields should be attributed to the combined impact of both chemically activated and thermalized syn-alkyl Criegee intermediates (CIs), even though the thermalized CI should be susceptible to trapping by molecules such as water. We have used RRKM/master equation and variational transition state theory calculations to quantify the competition between unimolecular isomerization and bimolecular hydration reactions for the syn and anti acetaldehyde oxide formed in trans-2-butene ozonolysis and for the CIs formed in isoprene ozonolysis possessing syn-methyl groups. Statistical rate theory calculations were based on quantum chemical data provided by the B3LYP, QCISD, and multicoefficient G3 methods, and thermal rate constants were corrected for tunneling effects using the Eckart method. At tropospheric temperatures and pressures, all thermalized CIs with syn-methyl groups are predicted to undergo 1,4-hydrogen shifts from 2 to 8 orders of magnitude faster than they react with water monomer at its saturation number density. For thermalized anti acetaldehyde oxide, the rates of dioxirane formation and hydration should be comparable.

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

    Science.gov (United States)

    Skultety, Ludovit; Frycak, Petr; Qiu, Changling; Smuts, Jonathan; Shear-Laude, Lindsey; Lemr, Karel; Mao, James X; Kroll, Peter; Schug, Kevin A; Szewczak, Angelica; Vaught, Cory; Lurie, Ira; Havlicek, Vladimir

    2017-06-08

    Distinguishing isomeric representatives of "bath salts", "plant food", "spice", or "legal high" remains a challenge for analytical chemistry. In this work, we used vacuum ultraviolet spectroscopy combined with gas chromatography to address this issue on a set of forty-three designer drugs. All compounds, including many isomers, returned differentiable vacuum ultraviolet/ultraviolet spectra. The pair of 3- and 4-fluoromethcathinones (m/z 181.0903), as well as the methoxetamine/meperidine/ethylphenidate (m/z 247.1572) triad, provided very distinctive vacuum ultraviolet spectral features. On the contrary, spectra of 4-methylethcathinone, 4-ethylmethcathinone, 3,4-dimethylmethcathinone triad (m/z 191.1310) displayed much higher similarities. Their resolution was possible only if pure standards were probed. A similar situation occurred with the ethylone and butylone pair (m/z 221.1052). On the other hand, majority of forty-three drugs was successfully separated by gas chromatography. The detection limits for all the drug standards were in the 2-4 ng range (on-column amount), which is sufficient for determinations of seized drugs during forensics analysis. Further, state-of-the-art time-dependent density functional theory was evaluated for computation of theoretical absorption spectra in the 125-240 nm range as a complementary tool. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Intramolecular interactions, isomerization and vibrational frequencies of two paracetamol analogues: A spectroscopic and a computational approach

    Science.gov (United States)

    Viana, Rommel B.; Ribeiro, Gabriela L. O.; Santos, Sinara F. F.; Quintero, David E.; Viana, Anderson B.; da Silva, Albérico B. F.; Moreno-Fuquen, Rodolfo

    2016-06-01

    The aim of this investigation was to determine the molecular properties and provide an interpretation of the vibrational mode couplings of these two paracetamol analogues: 2-bromo-2-methyl-N-(4-nitrophenyl)-propanamide and 2-bromo-2-methyl-N-p-tolyl-propanamide. E/Z isomers, keto/enol unimolecular rearrangement and prediction of the transition state structures in each mechanism were also assessed using the Density Functional Theory (DFT). The DFT estimates a high energy gap between E and Z isomers (9-11 kcal·mol- 1), with barrier heights ranging from 16 to 19 kcal·mol- 1. In contrast, the barrier energies on the keto/enol isomerization are almost 10 kcal·mol- 1 higher than those estimated for the E/Z rearrangement. The kinetic rate constant was also determined for each reaction mechanism. Natural bond orbital analysis and the quantum theory of atoms in molecules were used to interpret the intramolecular hydrogen bonds and to understand the most important interactions that govern the stabilization of each isomer. Furthermore, an analysis of the atomic charge distribution using different population methodologies was also performed.

  4. Highly selective Lewis acid sites in desilicated MFI zeolites for dihydroxyacetone isomerization to lactic acid.

    Science.gov (United States)

    Dapsens, Pierre Y; Mondelli, Cecilia; Pérez-Ramírez, Javier

    2013-05-01

    Desilication of commercial MFI-type (ZSM-5) zeolites in solutions of alkali metal hydroxides is demonstrated to generate highly selective heterogeneous catalysts for the aqueous-phase isomerization of biobased dihydroxyacetone (DHA) to lactic acid (LA). The best hierarchical ZSM-5 sample attains a LA selectivity exceeding 90 %, which is comparable to that of the state-of-the-art catalyst (i.e., the Sn-beta zeolite); this optimized hierarchical catalyst is recyclable over three runs. The Lewis acid sites, which are created through desilication along with the introduction of mesoporosity, are shown to play a crucial role in the formation of the desired product; these cannot be achieved by using other post-synthetic methods, such as steaming or impregnation of aluminum species. Desilication of other metallosilicates, such as Ga-MFI, also leads to high LA selectivity. In the presence of a soluble aluminum source, such as aluminum nitrate, alkaline-assisted alumination can introduce these unique Lewis acid centers in all-silica MFI zeolites. These findings highlight the potential of zeolites in the field of biomass-to-chemical conversion, and expand the applicability of desilication for the generation of selective catalytic centers. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Modeling trans-cis chromophore isomerization for the asFP595 kindling protein

    Science.gov (United States)

    Grigorenko, Bella L.; Nemukhin, Alexander V.

    2007-02-01

    We present the results of modeling properties of the chromophore, 2-acetyl-4-(p-hydroxybenzylidene)-1-methyl-5- imidazolone (AHBMI), from the newly discovered fluorescent protein asFP595 inside the protein environment by using the combined quantum mechanical - molecular mechanical (QM/MM) method. In this approach, the chromophore unit and the side chains of the nearest amino acid residues are assigned to the quantum subsystem. The starting coordinates of heavy atoms were taken from the relevant crystal structures of the protein. Hydrogen atoms were added manually, and the structure of the model protein system was optimized by using QM/MM energy minimization for the trans-form of the chromophore. The Hartree-Fock/6-31G quantum chemical approximation and the AMBER force field parameters were employed in geometry optimization. The points on potential energy surfaces of the ground and first and second excited electronic states were computed with the complete active space self-consistent field approximation in the quantum subsystem under different choices of the QM/MM partitioning. Possible pathways for the trans-cis photo isomerization presumably responsible for the kindling properties of asFP595 as well as other mechanisms of photo excitation are discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

    Moliner, Manuel [California Inst. of Technology (CalTech), Pasadena, CA (United States); Roman-Leshkov, Yuriy [California Inst. of Technology (CalTech), Pasadena, CA (United States); Davis, Mark E. [California Inst. of Technology (CalTech), Pasadena, CA (United States)

    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 (1:50 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].

  7. Correlation between the molecular structure and trans←→ cis isomerization characteristics of azobenzenes

    Institute of Scientific and Technical Information of China (English)

    HAN Mina; HONDA Takumu

    2012-01-01

    Photochemical and thermal isomerization of various azobenzenes was systematically investigated to understand the correlation between the molecular structure and trans←→cis isomerization characteristics of azobenzenes.A blue shift in π-π* absorption band of ortho-alkylated azobenzenes (1o and 2o) was observed together with a reduction in molar extinction coefficient (ε) in comparison with both meta-alkylated azobenzenes (4m and 5m) and 7p lacking the meta and ortho substituents.For ortho-alkylated azobenzene,photochemical trans-to-cis isomerization and thermal back cis-to-trans isomerization in solution occurred slowly when compared with 4m,5m and 7p.The half-life time of the cis form of 2o was found to be 380 h,which is about 8-50 times longer than those of comparable 4m,5m (43-13 h) and 7p (7h).Furthermore,comparison of the molecular structure and isomerization characteristics of azobenzene thiol (2oand 5m) self-assembled monolayers on flat gold surfaces indicates that the trans-to-cis photoconversion in monolayer systems is influenced by steric hindrance and strong intermolecular interaction between azobenzene units.

  8. Formation and decay of fluorobenzene radical anions affected by their isomeric structures and the number of fluorine atoms.

    Science.gov (United States)

    Higashino, Saki; Saeki, Akinori; Okamoto, Kazumasa; Tagawa, Seiichi; Kozawa, Takahiro

    2010-08-12

    Aryl fluoride has attracted much attention as a resist component for extreme ultraviolet (EUV) lithography, because of the high absorption cross section of fluorine for EUV photons; however, less is known about electron attachment to fluorobenzene (FBz) and the stability of the reduced state. Picosecond and nanosecond pulse radiolysis of tetrahydrofuran solutions of FBz from mono-, di-, tri-, tetra-, penta-, and hexafluorobenzene was performed, and the effects of isomeric structure and number of fluorine atoms were examined. Scavenging of solvated electrons was found to correlate with the electron affinity obtained by density functional theory in the gas phase, whereas the decay of FBz radical anions was dominated by the activation energy of fluorine anion dissociation calculated using a polarized continuum model (PCM). A sharp contrast in the lifetimes of ortho-, meta-, and para-position difluorobenzene was observed, which could provide information on the molecular design of functional materials.

  9. Interplay between metal binding and cis/trans isomerization in legume lectins: structural and thermodynamic study of P. angolensis lectin.

    Science.gov (United States)

    Garcia-Pino, Abel; Buts, Lieven; Wyns, Lode; Loris, Remy

    2006-08-04

    The interplay between metal binding, carbohydrate binding activity, stability and structure of the lectin from Pterocarpus angolensis was investigated. Removal of the metals leads to a more flexible form of the protein with significantly less conformational stability. Crystal structures of this metal-free form show significant structural rearrangements, although some structural features that allow the binding of sugars are retained. We propose that substitution of an asparagine residue at the start of the C-terminal beta-strand of the legume lectin monomer hinders the trans-isomerization of the cis-peptide bond upon demetallization and constitutes an intramolecular switch governing the isomer state of the non-proline bond and ultimately the lectin phenotype.

  10. Molecular polymorphism: microwave spectra, equilibrium structures, and an astronomical investigation of the HNCS isomeric family.

    Science.gov (United States)

    McGuire, Brett A; Martin-Drumel, Marie-Aline; Thorwirth, Sven; Brünken, Sandra; Lattanzi, Valerio; Neill, Justin L; Spezzano, Silvia; Yu, Zhenhong; Zaleski, Daniel P; Remijan, Anthony J; Pate, Brooks H; McCarthy, Michael C

    2016-08-10

    The rotational spectra of thioisocyanic acid (HNCS), and its three energetic isomers (HSCN, HCNS, and HSNC) have been observed at high spectral resolution by a combination of chirped-pulse and Fabry-Pérot Fourier-transform microwave spectroscopy between 6 and 40 GHz in a pulsed-jet discharge expansion. Two isomers, thiofulminic acid (HCNS) and isothiofulminic acid (HSNC), calculated here to be 35-37 kcal mol(-1) less stable than the ground state isomer HNCS, have been detected for the first time. Precise rotational, centrifugal distortion, and nitrogen hyperfine coupling constants have been determined for the normal and rare isotopic species of both molecules; all are in good agreement with theoretical predictions obtained at the coupled cluster level of theory. On the basis of isotopic spectroscopy, precise molecular structures have been derived for all four isomers by correcting experimental rotational constants for the effects of rotation-vibration interaction calculated theoretically. Formation and isomerization pathways have also been investigated; the high abundance of HSCN relative to ground state HNCS, and the detection of strong lines of SH using CH3CN and H2S, suggest that HSCN is preferentially produced by the radical-radical reaction HS + CN. A radio astronomical search for HSCN and its isomers has been undertaken toward the high-mass star-forming region Sgr B2(N) in the Galactic Center with the 100 m Green Bank Telescope. While we find clear evidence for HSCN, only a tentative detection of HNCS is proposed, and there is no indication of HCNS or HSNC at the same rms noise level. HSCN, and tentatively HNCS, displays clear deviations from a single-excitation temperature model, suggesting weak masing may be occurring in some transitions in this source.

  11. 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

  12. Study of {sup 235}U excitation in plasma: Isomere experiment at Phebus; Etude de l'excitation de l'{sup 235}U dans un plasma: l'experience isomere sur Phebus

    Energy Technology Data Exchange (ETDEWEB)

    Meot, V.; Baudin, J.-C.; Musolino, N.; Camus, C

    2000-12-01

    We present an experimental study of the excitation of the first isomeric level of {sup 235}U, in plasma created by laser. Several responsible mechanisms for the population of this level are discussed, then an experimental overview is given. The ISOMERE experiment, performed with the PHEBUS laser is presented. Results are compared with theoretical prediction. (authors)

  13. Isomerization and optical bistability of DR1 doped organic-inorganic sol-gel thin film

    Science.gov (United States)

    Gao, Tianxi; Que, Wenxiu; Shao, Jinyou

    2015-10-01

    To investigate the isomerization process of the disperse red 1 (DR1) doped TiO2/ormosil thin film, both the photo-isomerization and the thermal isomerization of the thin films were observed as a change of the absorption spectrum. Under a real-time heat treatment, the change of the linear refractive index shows a thermal stable working temperature range below Tg. The optical bistability (OB) effect of the DR1 doped thin films based on different matrices was studied and measured at a wavelength of 532 nm. Results indicate that the TiO2/ormosils based thin film presents a better OB-gain than that of the poly (methyl methacrylate) (PMMA) based thin film due to its more rigid network structure. Moreover, it is also noted that higher titanium content is helpful for enhancing the OB-gain of the as-prepared hybrid thin films.

  14. Efficient isomerization of glucose to fructose over zeolites in consecutive reactions in alcohol and aqueous media.

    Science.gov (United States)

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

    2013-04-10

    Isomerization reactions of glucose were catalyzed by different types of commercial zeolites in methanol and water in two reaction steps. The most active catalyst was zeolite Y, which was found to be more active than the zeolites beta, ZSM-5, and mordenite. The novel reaction pathway involves 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 chemicals like alkyl levulinates is viable at higher temperatures.

  15. 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.

  16. Lycopene inhibits the isomerization of β-carotene during quenching of singlet oxygen and free radicals.

    Science.gov (United States)

    Heymann, Thomas; Heinz, Philipp; Glomb, Marcus A

    2015-04-01

    The present study aimed to investigate the influence of singlet oxygen and radical species on the isomerization of carotenoids. On the one hand, lycopene and β-carotene standards were incubated with 1,4-dimethylnaphthalene-1,4-endoperoxide that produced singlet oxygen in situ. (13Z)- and (15Z)-β-carotene were preferentially generated at low concentrations of singlet oxygen, while high concentrations resulted in formation of (9Z)-β-carotene. The addition of different concentrations of lycopene led to the same isomerization progress of β-carotene, but resulted in a decreased formation of (9Z)-β-carotene and retarded degradation of (all-E)-β-carotene. On the other hand, isomerization of β-carotene and lycopene was induced by ABTS-radicals, too. As expected from the literature, chemical quenching was observed especially for lycopene, while physical quenching was preferred for β-carotene. Mixtures of β-carotene and lycopene resulted in a different isomerization progress compared to the separate β-carotene model. As long as lycopene was present, almost no isomerization of β-carotene was triggered; after that, strong formation of (13Z)-, (9Z)-, and (15Z)-β-carotene was initiated. In summary, lycopene protected β-carotene against isomerization during reactions with singlet oxygen and radicals. These findings can explain the pattern of carotenoid isomers analyzed in fruits and vegetables, where lycopene containing samples showed higher (all-E)/(9Z)-β-carotene ratios, and also in in vivo samples such as human blood plasma.

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

    CERN Document Server

    Eronen, T; Hager, U; Hakala, J; Jokinen, A; Kankainen, A; Rahaman, S; Rissanen, J; Weber, C; Äystö, J

    2008-01-01

    A new procedure to prepare isomerically clean samples of ions with a mass resolving power of more than 100,000 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.

  18. The Chemical Isomerization of Whey Lactose to Lactulose by Using Column Reactor

    Directory of Open Access Journals (Sweden)

    *T. N. Musa

    2015-06-01

    Full Text Available The isomerization of whey lactose to lactulose was carried out using column reactors of 1, 2 and 3M sodium aluminates at 30 and 70o C. The effect of different sodium aluminates molarities, temperature and flow rates on the formation of lactulose and overall degradation have been studied. There was a proportional relationship between lactulose formation and sodium aluminates molarities, the same as with the isomerization temperature, 67 and 80% lactulose were respectively obtained at 30 and 70o C by using 3M sodium aluminates. A reverse relationship was found between lactulose formation and flow rates. The previous relationships were true with overall degradations.

  19. Engineered DsbC chimeras catalyze both protein oxidation and disulfide-bond isomerization in Escherichia coli: Reconciling two competing pathways

    OpenAIRE

    Segatori, Laura; Paukstelis, Paul J.; Gilbert, Hiram F.; Georgiou, George

    2004-01-01

    In the Escherichia coli periplasm, the formation of protein disulfide bonds is catalyzed by DsbA and DsbC. DsbA is a monomer that is maintained in a fully oxidized state by the membrane enzyme DsbB, whereas DsbC is a dimer that is kept reduced by a second membrane protein, DsbD. Although the catalytic regions of DsbA and DsbC are composed of structurally homologous thioredoxin motif domains, DsbA serves only as an oxidase in vivo, whereas DsbC catalyzes disulfide reduction and isomerization a...

  20. On possible shape isomers in the Pt-Ra region of nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Nerlo-Pomorska, B.; Pomorski, K. [UMCS, Lublin (Poland); Bartel, J. [IPHC, Strasbourg (France); Schmitt, C. [IPHC, Strasbourg (France); GANIL, Caen (France)

    2017-04-15

    A certain number of yet unknown super- and hyper-deformed shape isomeric states are predicted in even-even nuclei of the region between Pt and Ra, using the macroscopic-microscopic model based on the Lublin Strasbourg Drop for the macroscopic energy and shell plus pairing corrections evaluated through the Yukawa-folded mean-field potential for the microscopic part. A new, rapidly converging shape parametrization is used to describe the vast range of nuclear deformations between the ground and the fission isomeric states up to near the scission configuration. Quadrupole moments are evaluated in the local minima and turn out to be in good agreement with the experimental data wherever available. (orig.)

  1. Evidence for a long-lived superheavy nucleus with atomic mass number A=292 and atomic number Z=~122 in natural Th

    CERN Document Server

    Marinov, A; Kolb, D; Pape, A; Kashiv, Y; Brandt, R; Gentry, R V; Miller, H W

    2008-01-01

    Evidence for the existence of a superheavy nucleus with atomic mass number A=292 and abundance (1-10)x10^(-12) relative to 232Th has been found in a study of natural Th using inductively coupled plasma-sector field mass spectrometry. The measured mass matches the predictions [1,2] for the mass of an isotope with atomic number Z=122 or a nearby element. Its estimated half-life of t1/2 >= 10^8 y suggests that a long-lived isomeric state exists in this isotope. The possibility that it might belong to a new class of long-lived high spin super- and hyperdeformed isomeric states is discussed.[3-6

  2. Photophysical studies of the trans to cis isomerization of the push-pull molecule: 1-(pyridin-4-yl)-2-(N-methylpyrrol-2-yl)ethene (mepepy).

    Science.gov (United States)

    Mokdad, Audrey; Belof, Jonathan L; Yi, Sung Wook; Shuler, Stephen E; McLaughlin, Mark L; Space, Brian; Larsen, Randy W

    2008-09-11

    Organic molecules possessing intramolecular charge-transfer properties (D-pi-A type molecules) are of key interest particularly in the development of new optoelectronic materials as well as photoinduced magnetism. One such class of D-pi-A molecules that is of particular interest contains photoswitchable intramolecular charge-transfer states via a photoisomerizable pi-system linking the donor and acceptor groups. Here we report the photophysical and electronic properties of the trans to cis isomerization of 1-(pyridin-4-yl)-2-(N-methylpyrrol-2-yl)ethene ligand (mepepy) in aqueous solution using photoacoustic calorimetry (PAC) and theoretical methods. Density functional theory (DFT) calculations demonstrate a global energy difference between cis and trans isomers of mepepy to be 8 kcal mol(-1), while a slightly lower energy is observed between the local minima for the trans and cis isomers (7 kcal mol(-1)). Interestingly, the trans isomer appears to exhibit two ground-state minima separated by an energy barrier of approximately 9 kcal mol(-1). Results from the PAC studies indicate that the trans to cis isomerization results in a negligible volume change (0.9 +/- 0.4 mL mol(-1)) and an enthalpy change of 18 +/- 3 kcal mol(-1). The fact that the acoustic waves associated with the trans to cis transition of mepepy overlap in frequency with those of a calorimetric reference implies that the conformational transition occurs faster than the approximately 50 ns response time of the acoustic detector. Comparison of the experimental results with theoretical studies provide evidence for a mechanism in which the trans to cis isomerization of mepepy results in the loss of a hydrogen bond between a water molecule and the pyridine ring of mepepy.

  3. 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

  4. Spectroscopic and structural studies of quinoline derivatives—II. Forrier transform i.r. spectroscopy. 1. Rotational isomerism in 3-ethoxycarbonyl-4(1H)-quinolone and some of its substituted derivatives,

    Science.gov (United States)

    Mirek, Julian; Urbanek, Zbigniew H.

    Rotational isomerism associated with internal rotation about the ring carbon(3)-ester carbonyl carbon single bond in a series of 3-ethoxycarbonyl-4(1H)-quinolones have been investigated spectroscopically in the solid state using Fourier transform i.r. and laser Raman spectroscopy. Particular attention is given to the 1700, 1300 and 1100 cm -1 spectral regions related primarily to the vibrations of the CO 2C 2H 5 group. Within these regions rotational isomerism appeared in the compounds examined. The conformational changes are discussed and evidence is reported for occurrence of the unsubstituted compound 1 itself in the solid state at ambient temperature as an equilibrium mixture of both the s-trans ( 1a) and s-cis ( 1b) rotamers (this is in contrast to previous findings), and of its Bz-substituted derivatives.

  5. CBS-QB3 calculation of quantum chemical molecular descriptors of isomeric thiadiazoles.

    Science.gov (United States)

    Glossman-Mitnik, Daniel

    2006-12-01

    The results of the calculation of several molecular descriptors of isomeric thiadiazoles through the CBS-QB3 model chemistry are presented in this work. The results could be useful in quantitative structure-activity relationship (QSAR) or quantitative structure-property relationship (QSPR) studies of derivatives of the nitrogen-containing analogs of thiophene.

  6. 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

  7. Bio-olefins via tandem isomerization-decarboxylation catalysis upon fatty acids

    Science.gov (United States)

    A facile Ru-catalyzed route to bio-alkenes from alkenoic fatty acids will be discussed. A readily accessible pre-catalyst [Ru(CO)2RCO2]n. apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds in an aliphatic chain and, subsequently, decarboxylating specific i...

  8. 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.

  9. 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...

  10. 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

    -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...

  11. Synthesis of tetrahydro-β-carbolines via isomerization of N-allyltryptamines

    DEFF Research Database (Denmark)

    Ascic, Erhad; Hansen, Casper L.; Le Quement, Sebastian T.

    2012-01-01

    An efficient and broadly applicable alternative to the classical Pictet–Spengler synthesis of tetrahydro-β-carbolines is presented. The method relies on metal-catalyzed isomerization of allylic amines to form reactive iminium intermediates which can be trapped by a tethered indole nucleophile....

  12. Molecular Driving Forces for Z/E Isomerization Mediated by Heteroatoms : The Example Hemithioindigo

    NARCIS (Netherlands)

    Nenov, Artur; Cordes, Thorben; Herzog, Teja T.; Zinth, Wolfgang; Vivie-Riedle, Regina de

    2010-01-01

    A combined experimental and theoretical investigation of photoinduced Z/E isomerizations is presented. Unsubstituted Hemithioindigo is selected as a representative minimal model to unravel the reaction mechanism in the presence of heteroatoms on an atomic level. Time-resolved spectroscopy reveals mu

  13. Valence isomerization of cyclohepta-1,3,5-triene and its heteroelement analogues

    Directory of Open Access Journals (Sweden)

    Helen Jansen

    2011-12-01

    Full Text Available The valence isomerization of the all-carbon and heteroelement analogues of cyclohepta-1,3,5-triene into the corresponding bicyclo[4.1.0]hepta-2,4-dienes is reviewed to show the impact of the heteroatom on the stability of both valence isomers. The focus is on the parent systems and their synthetic applications.

  14. 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......V, which is significantly lower than that observed for the reaction within opsin proteins....

  15. Xylose isomerization with zeolites in a two-step alcohol-water process.

    Science.gov (United States)

    Paniagua, Marta; Saravanamurugan, Shunmugavel; Melian-Rodriguez, Mayra; Melero, Juan A; Riisager, Anders

    2015-03-01

    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 xyluloside (step 1) followed by hydrolysis after water addition to form additional xylulose (step 2). NMR spectroscopy studies performed with (13) C-labeled xylose confirmed the proposed reaction pathway. The most active catalyst examined was zeolite Y, which proved more active than zeolite beta, ZSM-5, and mordenite. The yield of xylulose obtained over H-USY (Si/Al=6) after 1 h of reaction at 100 °C was 39%. After water hydrolysis in the second reaction step, the yield increased to 47%. Results obtained from pyridine adsorption studies confirm that H-USY (6) is a catalyst that combines Brønsted and Lewis acid sites, and isomerizes xylose in alcohol media to form xylulose at low temperature. The applied zeolites are commercially available; do not contain any auxiliary tetravalent metals, for example, tin, titanium, or zirconium; isomerize xylose efficiently; are easy to regenerate; and are prone to recycling.

  16. Development and Commercial Application of Supported Palladium Catalyst for Isomerization of C5/C6 Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    Han Song; Hu Yaoliang; Xu Zhengge; Wu Zhengtai; Shi Li; Ding Yunlong

    2005-01-01

    @@ 1 Introduction China has enforced a new gasoline standard starting 2003 to limit the olefins, aromatics and benzene contents in gasoline.The isomerate is the cleanest gasoline component because it does not contain the above-mentioned components, and is also an excellent gasoline blending component because of its higher RON and MON ratings.

  17. New Hydrogen Bonded Supramolecular Hydrogels Formed through Gelating Two Isomeric Building Units Simultaneously

    Institute of Scientific and Technical Information of China (English)

    Ji Wei WU; Li Ming TANG; Kai CHEN; Liang YAN; Yu Jiang WANG

    2006-01-01

    New hydrogen bonded supramolecular hydrogels were formed through simultaneously gelating two isomeric building units, 4-oxo-4-(2-pyridinylamino)butanoic acid (G1) and 4-oxo-4-(3-pyridinylamino)butanoic acid (G2) at various molar ratios in water.

  18. Isomerization of cis-1,2-dimethylcyclohexane in single-pulse shock tube experiments.

    Science.gov (United States)

    Rosado-Reyes, Claudette M; Tsang, Wing

    2014-09-11

    Cyclic hydrocarbons are major constituents of jet fuels and reference compounds in jet fuel surrogates. The kinetic and thermal stability and reaction mechanisms of fuel molecules are essential input parameters in the models and simulations used in the design of novel fuels, renewable energy technologies, and devices. A detailed study and analysis of the pyrolytic chemistry of cis-1,2-dimethylcyclohexane has been performed in single-pulse shock tube experiments. The investigations are carried out over the temperature range of 1100 to 1200 K at about 2.5 atm pressure. The isomeric products are trans-1,2-dimethylcyclohexane, 1-octene, and (cis + trans)-2-octene. The three octene isomers can be attributed to internal disproportionation processes. Assuming a diradical mechanism and that cis-1,2-dimethylcyclohexane is formed in equal amount with respect to its trans isomer, the total rate expression for isomerization is kC-C = 10(15.5±0.8) exp(-38,644 ± 2061 K/T) s(-1). The rate constants are over an order of magnitude smaller than the equivalent noncyclic hydrocarbon system. The presence of the isomeric octenes suggests that internal disproportionation is an important component of the isomerization process.

  19. Kinetic studies of lycopene isomerization in a tributyrin model system at gastric pH.

    Science.gov (United States)

    Moraru, Catalin; Lee, Tung-Ching

    2005-11-16

    A semi-preparative HPLC method was developed in order to isolate and purify the 13-cis-lycopene isomer in tomato-based materials. The result was compared with the naturally predominant all-trans-lycopene isomer, in terms of stability to gastric pH at physiological temperature in a tributyrin model system. Kinetic experiments confirmed that lycopene isomerization is a reversible reaction, and under these conditions the all-trans isomer is more stable than the 13-cis isomer. In addition, it was found that at gastric pH 13-cis-lycopene would predominantly isomerize to the all-trans form rather than undergo oxidation/breakdown. A simulation based on the rate constants calculated in the kinetic study indicated that at gastric pH the lycopene isomeric distribution aimed toward an equilibrium characterized by approx 16% 13-cis-, 16% 9-cis-, and 68% all-trans-lycopene. This study suggests that pH-driven isomerization in the stomach is at least partially responsible for the relatively high cis-lycopene proportion found in vivo.

  20. Model mechanisms for the thermal cis—trans isomerization of cyanines

    Science.gov (United States)

    Schöffel, Klaus; Dietz, Fritz; Krossner, Thomas

    1990-08-01

    Quantum-chemical calculations have been performed for rotations around the different CC bonds of streptocyanine cations and of various ion pairs of TMC + and PMC + with Cl - as the gegenion (counterion) in order to explain the experimentally well known temperature dependence of the activation energy for the thermal isomerization.

  1. The Isomerization of Allylrhodium Intermediates in the Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines**

    Science.gov (United States)

    Hepburn, Hamish B; Lam, Hon Wai

    2014-01-01

    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. PMID:25205604

  2. 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…

  3. Roaming Isomerization of Photoexcited Halogenated Alkanes in the Gas and Liquid Phases

    Science.gov (United States)

    Borin, Veniamin A.; Matveev, Sergey M.; Budkina, Darya S.; Hicks, Christopher M.; Mereshchenko, Andrey S.; Butaeva, Evgeniia V.; Vorobyev, Vasily V.; Tarnovsky, Alexander N.

    2017-06-01

    Recent experimental and computational gas-phase studies have brought to light a new type of unimolecular decomposition called a "roaming mechanism. It has only been observed in the gas phase, and whether it also occurs in solution is an intriguing question. Using ultrafast transient absorption spectroscopy, we report direct isomerization of CHBr_{3}, BBr_{3}, and PBr_{3} geminal tribromides in solution within the first 100 fs after S_{1}-excitation. The gas-phase conditions do not affect the earliest course of similar isomerization of CHBr_{3}. High-level ab initio simulations on XBr_{3} (X = B, P, and CH) suggest that isomerization is governed by an energetically and dynamically accessible S_{1}/S_{0} conical intersection and can be best described as a roaming-mediated pathway. Following the initial relaxation from the Franck-Condon point, "wandering" of the central atoms and migration of Br atom starts on a planar region of the S_{1} surface, and in the vicinity of the conical intersection ( 40 fs) the XBr_{2} and Br fragments become separated to ≥ 3 Å. After passage through the conical intersection, the partially dissociated bromine atom slips off the XBr_{2} bisector plane, and forms the Br-Br bond of the BrXBr-Br isomer ( 60 fs). We give examples of similar roaming isomerization in several other di- and polyhalogenated alkanes. The authors gratefully acknowledges grants from the National Science Foundation (CHE-0847707, 0923360, and 1626420) which supported this work.

  4. Antenatal diagnosis of left atrial isomerism and heterotaxy syndrome in fetus with Meckel-Gruber syndrome.

    Science.gov (United States)

    Kurtulmuş, Seçil; Demirpençe, Savaş; Can Öztekin, Deniz; Koç, Altuğ; Tavlı, Vedide

    2014-03-01

    We aimed to present a fetus with Meckel-Gruber syndrome (MKS) who had left atrial isomerism, heterotaxy syndrome and complete heart block. A 26-year-old healthy female was referred to our clinic in the 23rd week of her pregnancy. The fetus had multiple systemic anomalies including fetal heart. Fetal echocardiography revealed a horizontal liver, left-sided stomach and vena cava interruption with azygos continuation. There was also an apical trabecular ventricular septal defect, aorta and pulmonary artery arising from the left ventricle, pulmonary artery hypoplasia, pulmonary valve stenosis and left atrial isomerism. The heart rate was 46/min, consistent with third-degree atrioventricular block. Multiple anomalies including occipital encephalocele, bilateral polycystic kidneys, cleft lip, cleft palate, and polydactyly were also detected in the obstetric ultrasonography. The pregnancy was terminated in the 23rd gestational week based on the consensus of perinatology council. The autopsy examination confirmed the diagnosis of MKS, left atrial isomerism and heterotaxy syndrome. Although some cardiac defects have been reported previously in MKS fetuses, here we expand the cardiac spectrum of anomalies associated with MKS to include left atrial isomerism and heterotaxy syndrome.

  5. DFT Studies on the Isomerization of Butene Double Bond Catalyzed by 1-Butyl-3-methyl-imidazolium in Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    LI Ying-Xia; PU Min; CHEN Biao-Hua; LI Hui-Ying; LIU Kun-Hui; WANG Wen-Xing

    2005-01-01

    The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels.The variations of the bond parameters in the course of reaction were analyzed.The zero point energy corrections were performed by vibrational analysis.The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry.The intrinsic reaction coordinates (IRC) were calculated from the transition state.The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction.The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJmol-1 and the reverse energy barrier about 209 kJmol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.

  6. A coupled cluster study of the structures, spectroscopic properties, and isomerization path of NCS - and CNS -

    Science.gov (United States)

    Pak, Youngshang; Woods, R. Claude; Peterson, Kirk A.

    1995-12-01

    Three-dimensional near-equilibrium potential energy surfaces and dipole moment functions have been calculated for the X 1Σ+ ground states of NCS- and CNS-, using the coupled cluster method with single and double substitutions augmented by a perturbative estimate of triple excitations [CCSD(T)] with a set of 154 contracted Gaussian-type orbitals. The corresponding equilibrium bond lengths at their linear geometries are re(NC)=1.1788 Å and re(CS)=1.6737 Å for NCS-, and re(CN)=1.1805 Å and re(NS)=1.6874 Å for CNS-. The predicted equilibrium rotational constants Be of NCS- and CNS- are 5918.2 and 6282.7 MHz, respectively. The former agrees very well with the known experimental value (5919.0 MHz). Full three-dimensional variational calculations have also been carried out using the CCSD(T) potential energy and dipole moment functions to determine the rovibrational energy levels and dipole moment matrix elements for both NCS- and CNS-. The corresponding fundamental band origins (cm-1) ν1, ν2, and ν3 and their absolute intensities (km/mol) at the CCSD(T) level are 2060.9/306.1, 451.5/2.2, and 707.5/12.8, respectively, for NCS- and 2011.4/6.6, 343.7/2.3, and 624.9/0.2 for CNS-. The calculated ν1 (CN stretching) value for NCS- is in very good agreement with the experimental result, 2065.9 cm-1. The calculated dipole moments of NCS- and CNS- in their ground vibrational states are 1.427 and 1.347 D, respectively. The transition state geometry (saddle point) for the isomerization of NCS-→CNS- is predicted at the CCSD(T) level to be r(NC)=1.2044 Å, R(CS)=1.9411 Å and θ(∠NCS)=86.8°. Its calculated energy is 62.6 and 26.5 kcal/mol above the minima of NCS- and CNS-, respectively, including zero-point energy corrections. The structure of the NCS radical was also optimized at the same level of theory, yielding ion to neutral bond length shifts in excellent agreement with those derived from recent photoelectron spectroscopy experiments.

  7. Isomeric yield ratio for the [sup 95]Mo (p,n) [sup 95m,g]Tc reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nagame, Y.; Baba, S. (Japan Atomic Energy Research Inst., Tokai-mura, Ibaraki (Japan). Dept. of Radioisotopes); Saito, T. (Osaka Univ., Toyonaka (Japan). Faculty of Science)

    1994-03-01

    Excitation functions and isomeric yield ratios for the [sup 95]Mo(p,n) (p,n) [sup 95m.g]Tc reactions up to E[sub p] = 28 MeV are analyzed with a statistical model. In the vicinity of the threshold energy E[sub p] [<=] 12 MeV, the experimental isomeric yield ratios are well reproduced by the calculations, while the calculation overestimates the experimental value beyond that energy. This suggests that the contribution of a pre-equilibrium process occurs above E[sub p] [approx] 12 MeV. The relationship between the isomeric yield ratio and compound nucleus spin distribution is discussed. (Author).

  8. Excitation functions and isomeric cross section ratios of the 63Cu(n,α)60Com,g, 65Cu(n,α)62Com,g, and 60Ni(n,p)60Com,g processes from 6 to 15 MeV

    Science.gov (United States)

    Cserpák, F.; Sudár, S.; Csikai, J.; Qaim, S. M.

    1994-03-01

    Excitation functions were measured for the 63Cu(n,α)60Com, 65Cu(n,α)62Com, and 65Cu(n,α)62Cog reactions over the neutron energy range of 6.3 to 14.8 MeV. Use was made of the activation technique in combination with high resolution γ-ray spectroscopy. The nuetrons were produced via the 2H(d,n)3He reaction using a deuterium gas target at a variable energy compact cyclotron (En=6.3-11.9 MeV) and via the 3H(d,n)4He reaction using a solid Ti-T target at a neutron generator (En=13.7-14.8 MeV). From the available experimental data isomeric cross section ratios were determined for the isomeric pair 60Com,g in 63Cu(n,α) and 60Ni(n,p) reactions, and for the pair 62Com,g in the 65Cu(n,α) reaction. Statistical model calculations taking into account precompound effects were performed for the formation of both the isomeric and ground states of the products. The calculational results on the total (n,p) and (n,α) cross sections agree well with the experimental data; in the case of isomeric states, however, some deviations occur. The experimental isomeric cross section ratios are reproduced only approximately by the calculation; at 15 MeV the spin distribution of the level density has a significant effect on the calculation. For low-lying levels the isomeric cross section ratio depends strongly on the spins of the levels involved and not on their excitation energies. At a given neutron energy the population of the higher spin isomer appears to be higher in the (n,α) process than in the (n,p) reaction.

  9. Fluorine for Hydrogen Exchange in the Hydrofluorobenzene Derivatives C6HxF(6-x), where x = 2, 3, 4 and 5 by Monomeric [1,2,4-(Me3C)3C5H2]2CeH; The Solid State Isomerization of [1,2,4-(Me3C)3C5H2]2Ce(2,3,4,5-C6HF4) to [1,2,4-(Me3C)3C5H2]2Ce(2,3,4,6-C6HF4)

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, Richard; Werkema, Evan L.; Andersen, Richard A.

    2008-04-21

    The reaction between monomeric bis(1,2,4-tri-t-butylcyclopentadienyl)cerium hydride, Cp'2CeH, and several hydrofluorobenzene derivatives is described. The aryl derivatives that are the primary products, Cp'2Ce(C6H5-xFx) where x = 1,2,3,4, are thermally stable enough to be isolated in only two cases, since all of them decompose at different rates to Cp'2CeF and a fluorobenzyne; the latter is trapped by either solvent when C6D6 is used or by a Cp'H ring when C6D12 is the solvent. The trapped products are identified by GCMS analysis after hydrolysis. The aryl derivatives are generated cleanly by reaction of the metallacycle, Cp'((Me3C)2C5H2C(Me2)CH2)Ce, with a hydrofluorobenzene and the resulting arylcerium products, in each case, are identified by their 1H and 19F NMR spectra at 20oC. The stereochemical principle that evolves from these studies is that the thermodynamic isomer is the one in which the CeC bond is flanked by two ortho-CF bonds. This orientation is suggested to arise from the negative charge that is localized on the ipso-carbon atom due to Co(delta+)-Fo(delta-) polarization. The preferred regioisomer is determined by thermodynamic rather than kinetic effects; this is illustrated by the quantitative, irreversible solid-state conversion at 25oC over two months of Cp'2Ce(2,3,4,5-C6HF4) to Cp'2Ce(2,3,4,6-C6HF4), an isomerization that involves a CeC(ipso) for C(ortho)F site exchange.

  10. Fluorine for Hydrogen Exchange in the Hydrofluorobenzene Derivatives C6HxF(6-x), where x = 2, 3, 4 and 5 by Monomeric [1,2,4-(Me3C)3C5H2]2CeH; The Solid State Isomerization of [1,2,4-(Me3C)3C5H2]2Ce(2,3,4,5-C6HF4) to [1,2,4-(Me3C)3C5H2]2Ce(2,3,4,6-C6HF4)

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, Richard; Werkema, Evan L.; Andersen, Richard A.

    2008-04-21

    The reaction between monomeric bis(1,2,4-tri-t-butylcyclopentadienyl)cerium hydride, Cp'2CeH, and several hydrofluorobenzene derivatives is described. The aryl derivatives that are the primary products, Cp'2Ce(C6H5-xFx) where x = 1,2,3,4, are thermally stable enough to be isolated in only two cases, since all of them decompose at different rates to Cp'2CeF and a fluorobenzyne; the latter is trapped by either solvent when C6D6 is used or by a Cp'H ring when C6D12 is the solvent. The trapped products are identified by GCMS analysis after hydrolysis. The aryl derivatives are generated cleanly by reaction of the metallacycle, Cp'((Me3C)2C5H2C(Me2)CH2)Ce, with a hydrofluorobenzene and the resulting arylcerium products, in each case, are identified by their 1H and 19F NMR spectra at 20oC. The stereochemical principle that evolves from these studies is that the thermodynamic isomer is the one in which the CeC bond is flanked by two ortho-CF bonds. This orientation is suggested to arise from the negative charge that is localized on the ipso-carbon atom due to Co(delta+)-Fo(delta-) polarization. The preferred regioisomer is determined by thermodynamic rather than kinetic effects; this is illustrated by the quantitative, irreversible solid-state conversion at 25oC over two months of Cp'2Ce(2,3,4,5-C6HF4) to Cp'2Ce(2,3,4,6-C6HF4), an isomerization that involves a CeC(ipso) for C(ortho)F site exchange.

  11. Isomeric ruthenium terpyridine complexes [Ru(trpy)(L)Cl]n+ containing the unsymmetrically bidentate acceptor L=3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine. Synthesis, structures, electrochemistry, spectroscopy and DFT calculations.

    Science.gov (United States)

    Patra, Srikanta; Sarkar, Biprajit; Ghumaan, Sandeep; Patil, Mahendra P; Mobin, Shaikh M; Sunoj, Raghavan B; Kaim, Wolfgang; Lahiri, Goutam Kumar

    2005-04-07

    The isomeric title complexes were obtained in almost equimolar ratio from the reaction of Ru(trpy)Cl3 and L. Crystal structure analyses of the perchlorate hemihydrates, electrochemical and spectroscopic (NMR, UV/VIS, EPR) studies, supported by DFT calculations, reveal distinct differences between the isomeric redox series [1]n+(tetrazine-Nt trans to Cl) and [2]n+(pyrazolyl-Np trans to Cl; n= 0, 1, 2). The latter system with the pi acceptors trpy and tetrazine in the equatorial plane and the pyrazolyl and chloride donors in the axial positions exhibits facilitated oxidation, lower energy MLCT transitions, more balanced chelate coordination, and a higher g anisotropy in the oxidised (RuIII) state. According to partially resolved EPR spectra of one-electron reduced neutral compounds and they have the unpaired electron predominantly in the tetrazine ring of L.

  12. Structure Analysis and Ion Abundance in CID- MS- MS Spectra of Isomeric Oligosaccharides Using Quadrupole Time-of- flight Mass Spectrometry: Distinguishing between Isomeric Oligosaccharides

    Institute of Scientific and Technical Information of China (English)

    Tohru YAMAGAKI; Kazuo TACHIBANA

    2001-01-01

    @@ N - Linked oligosaccharide were analyzed by using electrospray ionization (ESI) quadrupole time - of- fight mass spectrometry(Q - Tof MS).The isomers showed the same MS and collisioninduced desociation(CID) MS - MS spectra in the m/z values because the sequence of the sugar residues was the same.But the relative ion abundance of the specific fragment ion was greatly different between the isomers.So, the isomeric oligosacchariedes were distinguished by using the ion abundance in their CID -MS - MS spectra.Discussing the ion abundance in accurate level, quantitative analysis of the mixtures of isomers were also performed.

  13. 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...

  14. 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...

  15. Assessing computationally efficient isomerization dynamics: Delta-SCF density-functional theory study of azobenzene molecular switching

    CERN Document Server

    Maurer, Reinhard J; 10.1063/1.3664305

    2012-01-01

    We present a detailed comparison of the S0, S1 (n -> \\pi*) and S2 (\\pi -> \\pi*) potential energy surfaces (PESs) of the prototypical molecular switch azobenzene as obtained by Delta-self-consistent-field (Delta-SCF) Density-Functional Theory (DFT), time-dependent DFT (TD-DFT) and approximate Coupled Cluster Singles and Doubles (RI-CC2). All three methods unanimously agree in terms of the PES topologies, which are furthermore fully consistent with existing experimental data concerning the photo-isomerization mechanism. In particular, sum-method corrected Delta-SCF and TD-DFT yield very similar results for S1 and S2, when based on the same ground-state exchange-correlation (xc) functional. While these techniques yield the correct PES topology already on the level of semi-local xc functionals, reliable absolute excitation energies as compared to RI-CC2 or experiment require an xc treatment on the level of long-range corrected hybrids. Nevertheless, particularly the robustness of Delta-SCF with respect to state c...

  16. Theoretical studies on the structures and isomerization of the LiSiF3 system

    Institute of Scientific and Technical Information of China (English)

    冯大诚; 林启君; 冯圣玉; 吕文彩

    1999-01-01

    Various possible isomers of LiSiF3 system and isomerization between them have been studied at G2(MP2) level using ab initio calculations. The relative energies of four minimum points on the potential energy surface are -128.6, -194.3, -12.7 and -122.8 kJ/mol (taking the sum of the energies of LiF and SiF2 as zero) . The structural energy of the four-membered ring that contains three F-Si-F-Li four-membered rings with C3v symmetry is the lowest. The highest potential barrier for the isomerization of the remaining three-or four-membered structure is 12.5 kJ/mol.

  17. The Chemical Isomerization of Lactose to Lactulose by Using Sodium Hydroxide as Batch Reaction

    Directory of Open Access Journals (Sweden)

    *Nahla T. K

    2016-06-01

    Full Text Available Lactulose is a synthetic and non-absorbable disaccharide sugar containing glucose and fructose units. It is used for the treatment of constipation and hepatic encephalopathy. The purpose of this experiment was to synthesized lactulose in the presence of sodium hydroxide as a catalyst. The evaluation of lactulose synthesis was carried out at different concentration of sodium hydroxide (1, 2 and 3M and the study was also conducted at different temperatures (30, 50, 70, and 90 °C. In addition, the kinetics of lactose isomerization with respect to the time also studied. Finally, it was concluded that the lactulose formation was determined by spectrophotometric method. The lactulose isomerization increased about more than 30.9% at 90 °C in the presence of 1M sodium hydroxide and 20 % lactose concentration.

  18. Femtosecond structural dynamics drives the trans/cis isomerization in photoactive yellow protein.

    Science.gov (United States)

    Pande, Kanupriya; Hutchison, Christopher D M; Groenhof, Gerrit; Aquila, Andy; Robinson, Josef S; Tenboer, Jason; Basu, Shibom; Boutet, Sébastien; DePonte, Daniel P; Liang, Mengning; White, Thomas A; Zatsepin, Nadia A; Yefanov, Oleksandr; Morozov, Dmitry; Oberthuer, Dominik; Gati, Cornelius; Subramanian, Ganesh; James, Daniel; Zhao, Yun; Koralek, Jake; Brayshaw, Jennifer; Kupitz, Christopher; Conrad, Chelsie; Roy-Chowdhury, Shatabdi; Coe, Jesse D; Metz, Markus; Xavier, Paulraj Lourdu; Grant, Thomas D; Koglin, Jason E; Ketawala, Gihan; Fromme, Raimund; Šrajer, Vukica; Henning, Robert; Spence, John C H; Ourmazd, Abbas; Schwander, Peter; Weierstall, Uwe; Frank, Matthias; Fromme, Petra; Barty, Anton; Chapman, Henry N; Moffat, Keith; van Thor, Jasper J; Schmidt, Marius

    2016-05-06

    A variety of organisms have evolved mechanisms to detect and respond to light, in which the response is mediated by protein structural changes after photon absorption. The initial step is often the photoisomerization of a conjugated chromophore. Isomerization occurs on ultrafast time scales and is substantially influenced by the chromophore environment. Here we identify structural changes associated with the earliest steps in the trans-to-cis isomerization of the chromophore in photoactive yellow protein. Femtosecond hard x-ray pulses emitted by the Linac Coherent Light Source were used to conduct time-resolved serial femtosecond crystallography on photoactive yellow protein microcrystals over a time range from 100 femtoseconds to 3 picoseconds to determine the structural dynamics of the photoisomerization reaction.

  19. Isomerization of One Molecule Observed through Tip-Enhanced Raman Spectroscopy.

    Science.gov (United States)

    Tallarida, Nicholas; Rios, Laura; Apkarian, Vartkess A; Lee, Joonhee

    2015-10-14

    While exploring photoisomerization of azobenzyl thiols (ABT) adsorbed on Au(111), through joint scanning tunneling microscopy (STM) and tip-enhanced Raman scattering (TERS) studies, the reversible photoisomerization of one molecule is captured in TERS trajectories. The unique signature of single molecule isomerization is observed in the form of anticorrelated flip-flops between two distinct spectra with two discrete, on- and off-levels. The apparently heterogeneously photocatalyzed reaction is assigned to cis-trans isomerization of an outlier, which is chemisorbed on the silver tip of the STM. Otherwise, the ensemble of ABT molecules that lie flat on Au(111) remain strongly coupled to the surface, excluding the possibility of photoisomerization or detection through TERS.

  20. Pin1-Induced Proline Isomerization in Cytosolic p53 Mediates BAX Activation and Apoptosis.

    Science.gov (United States)

    Follis, Ariele Viacava; Llambi, Fabien; Merritt, Parker; Chipuk, Jerry E; Green, Douglas R; Kriwacki, Richard W

    2015-08-20

    The cytosolic fraction of the tumor suppressor p53 activates the apoptotic effector protein BAX to trigger apoptosis. Here we report that p53 activates BAX through a mechanism different from that associated with activation by BH3 only proteins (BIM and BID). We observed that cis-trans isomerization of proline 47 (Pro47) within p53, an inherently rare molecular event, was required for BAX activation. The prolyl isomerase Pin1 enhanced p53-dependent BAX activation by catalyzing cis-trans interconversion of p53 Pro47. Our results reveal a signaling mechanism whereby proline cis-trans isomerization in one protein triggers conformational and functional changes in a downstream signaling partner. Activation of BAX through the concerted action of cytosolic p53 and Pin1 may integrate cell stress signals to induce a direct apoptotic response. Copyright © 2015 Elsevier Inc. All rights reserved.

  1. Model-based design and analysis of glucose isomerization process operation

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; Pedersen, Sven; Kumar Tula, Anjan

    2017-01-01

    reactor is developed. Next, model analysis, model identification and model validation based on available reactor operational data are performed. The reactor model is found to describe accurately important phenomena, such as, reaction kinetics, enzyme decay and internal diffusion of the substrate......The application of model-based methods for design and analysis of operational improvements of an industrial glucose isomerization (GI) process is highlighted. First, a multi-scale mathematical model representing important phenomena encountered in the reaction system of a glucose isomerization...... in the enzymatic pellet as a function of the temperature, thereby confirming that the model is ready for use in design-analysis studies. Operation of the GI process is then analyzed in a single reactor and based on this, the reactor model is used as a building block to represent the operation of a GI reactor plant...

  2. Conformational isomerization of N-(naphthalen-1-yl)-N-(phenyl(quinolin-3-yl)methyl)amide derivatives

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A series of N-(naphthalen-1-yl)-N-(phenyl(quinolin-3-yl)methyl)amide derivatives were designed and synthesized as anti-Mycobacterium tuberculosis drugs. NMR spectra showed that two conformational isomers of these compounds exist in solution,which is not due to cis-trans isomerization of amide bond. We proposed that the spatial interactions between three large aromatic groups caused the conformational isomerization,which was supported by molecular modeling and X-ray diffraction.

  3. Synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones.

    Science.gov (United States)

    Zhuo, Lian-Gang; Yao, Zhong-Ke; Yu, Zhi-Xiang

    2013-09-20

    Developing olefin isomerization reactions to reach kinetically controlled Z-alkenes is challenging because formation of trans-alkenes is thermodynamically favored under the traditional catalytic conditions using acids, bases, or transition metals as the catalysts. A new synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones to α,β-unsaturated ketones was developed, providing an easy and efficient way to access various Z-enones.

  4. Reactions of platinum(IV)-bound nitriles with isomeric nitroanilines: addition vs. substitution.

    Science.gov (United States)

    Chernyshev, Alexander N; Bokach, Nadezhda A; Gushchin, Pavel V; Haukka, Matti; Kukushkin, Vadim Yu

    2012-11-07

    The platinum(IV) complex trans-[PtCl(4)(EtCN)(2)] reacts smoothly and under mild conditions with isomeric o-, m- and p-nitroanilines (NAs) yielding two different types of products depending on the NA isomer, viz. the nitroaniline complexes cis/trans-[PtCl(4)(NA)(2)] (cis/trans-1-3) and the amidine species trans-[PtCl(4){NH=C(Et)NHC(6)H(4)NO(2)-m}(EtCN)] (4), trans-[PtCl(4){NH=C(Et)NHC(6)H(4)NO(2)-m}(2)] (5) and trans-[PtCl(4){NH=C(Et)NHC(6)H(4)NO(2)-p}(EtCN)] (6). Complexes 4 and 5 undergo cyclometalation, furnishing mer-[PtCl(3){NH=C(Et)NHC(6)H(3)NO(2)-m}(EtCN)] (7) and mer-[PtCl(3){NH=C(Et)NHC(6)H(4)NO(2)-m}{NH=C(Et)NHC(6)H(3)NO(2)-m}] (8), respectively. Moreover, 8 both in the solid state and in solution undergoes the second step of the cyclometalation, generating [PtCl(2){NH=C(Et)NHC(6)H(3)NO(2)-m}(2)] (9). In 4, the nitrile ligand is highly reactive toward nucleophilic addition and it undergoes facile hydration accompanied by the elimination of the nitrile, thus producing cis-[PtCl(4)(NH(2)C(6)H(4)NO(2)-m){NH=C(OH)Et}] (10), or methanol addition providing trans-[PtCl(4){NH=C(Et)NHC(6)H(4)NO(2)-m}{NH=C(Et)OMe}] (11). All compounds, besides 9, were characterized by C, H, and N elemental analyses, high-resolution ESI-MS, IR, (1)H and (13)C{(1)H} NMR spectroscopic techniques. Complex 9, which was not isolated as a pure compound, was identified in the reaction mixture by ESI-MS and (1)H and (13)C{(1)H} NMR spectroscopies. Complexes trans-1, trans-2, 4, 5, 6, 8, 10, and 11 were additionally studied by X-ray diffraction.

  5. Ligand noninnocence of thiolate/disulfide in dinuclear copper complexes: solvent-dependent redox isomerization and proton-coupled electron transfer.

    Science.gov (United States)

    Thomas, Andrew M; Lin, Bo-Lin; Wasinger, Erik C; Stack, T Daniel P

    2013-12-18

    Copper thiolate/disulfide interconversions are related to the functions of several important proteins such as human Sco1, Cu-Zn superoxide dismutase (SOD1), and mammalian zinc-bonded metallothionein. The synthesis and characterization of well-defined synthetic analogues for such interconversions are challenging yet provide important insights into the mechanisms of such redox processes. Solvent-dependent redox isomerization and proton-coupled electron transfer mimicking these interconversions are observed in two structurally related dimeric μ,η(2):η(2)-thiolato Cu(II)Cu(II) complexes by various methods, including X-ray diffraction, XAS, NMR, and UV-vis. Spectroscopic evidence shows that a solvent-dependent equilibrium exists between the dimeric μ-thiolato Cu(II)Cu(II) state and its redox isomeric μ-disulfido Cu(I)Cu(I) form. Complete formation of μ-disulfido Cu(I)Cu(I) complexes, however, only occurs after the addition of 2 equiv of protons, which promote electron transfer from thiolate to Cu(II) and formation of disulfide and Cu(I) via protonation of the coordinating ligand. Proton removal reverses this reaction. The reported unusual reductive protonation/oxidative deprotonation of the metal centers may serve as a new chemical precedent for how related proteins manage Cu ions in living organisms.

  6. Structural isomerism leading to variable proton conductivity in indium(III) isophthalic acid based frameworks.

    Science.gov (United States)

    Panda, Tamas; Kundu, Tanay; Banerjee, Rahul

    2013-07-14

    Proton conductivity has been studied thoroughly in two isomeric In(III)-isophthalate based MOFs. In-IA-2D-1 is capable of showing proton conductivity (3.4 × 10(-3) S cm(-1)) under humidified conditions (98% RH), whereas In-IA-2D-2 can conduct protons (2.6 × 10(-5) S cm(-1)) under humidified as well as anhydrous conditions.

  7. Bimetallic Pt-Ni catalysts supported on usy zeolite for n-hexane isomerization

    Directory of Open Access Journals (Sweden)

    F. V. Barsi

    2009-06-01

    Full Text Available Isomerization of linear alkanes has had considerable importance for the refining industry because the isomers formed in this reaction have high octane number. Most works reported in the literature studied the use of bifunctional catalysts, i.e., ones that have acid sites and metallic sites. In this study, bifunctional monometallic (Ni or Pt and bimetallic catalysts (Pt-Ni, using HUSY zeolite as the support, were prepared in order to verify the role of the metal content and composition on the catalytic properties for n-hexane isomerization. The method used for metal dispersion in the zeolite was competitive ion exchange using ammine complexes [Ni(NH36]Cl2 and [Pt(NH34]Cl2 as precursors. Four series of catalysts with constant atomic metal content had total metal amounts between 130 and 280 µmol M/g cat. Catalysts were characterized by temperature programmed reduction (TPR and subjected to catalytic evaluation for n-hexane isomerization at 250 ºC and 1 atm using H2/C6 = 9 molar ratio. TPR results show an easier reducibility of Ni+2 cations in the presence of Pt, which was evidenced by the displacement of the reduction peak of those cations towards lower temperatures in bimetallic catalysts. The bimetallic catalysts presented a higher activity in the isomerization of n-hexane when compared to the monometallic ones, as well better stability as the Pt content in the solid increases. The results of the activity as a function of the Pt content in the bimetallic catalysts show a maximum value around 50% of Pt. An addition of Pt above this critical value leads to a small decrease of the catalytic activity.

  8. Bimetallic Pt-Ni catalysts supported on usy zeolite for n-hexane isomerization

    OpenAIRE

    F. V. Barsi; Cardoso,D.

    2009-01-01

    Isomerization of linear alkanes has had considerable importance for the refining industry because the isomers formed in this reaction have high octane number. Most works reported in the literature studied the use of bifunctional catalysts, i.e., ones that have acid sites and metallic sites. In this study, bifunctional monometallic (Ni or Pt) and bimetallic catalysts (Pt-Ni), using HUSY zeolite as the support, were prepared in order to verify the role of the metal content and composition on th...

  9. Theoretical Study on the Isomerization Mechanism of Enol Ester from 2-Acyl-1, 3-cyclohexanediones

    Institute of Scientific and Technical Information of China (English)

    Yan Hua WANG; Jian Wei ZOU; Bing ZHANG; Min ZENG; Gui Xiang HU; Ke Wen ZHENG; Qing Sen YU

    2005-01-01

    The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a),respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.

  10. Viscosities of Binary Mixtures Containing Isomeric Chlorobutanes and Diisopropylether: Experimental and Predicted Values

    Science.gov (United States)

    Montaño, D.; Guerrero, H.; Bandrés, I.; López, M. C.; Lafuente, Carlos

    2010-03-01

    In this work, viscosities of binary mixtures of isomeric chlorobutanes with diisopropylether have been determined as a function of composition under atmospheric pressure and in the temperature range from 283.15 K to 313.15 K with steps of 5 K. Kinematics viscosities were measured using an Ubbelohde viscosimeter; absolute viscosities were obtained from kinematic viscosities and densities. Finally, we have used the Asfour method for predicting the dependence of viscosity with composition and comparing it with our experimental data.

  11. Novel domino procedures for the synthesis of chromene derivatives and their isomerization.

    Science.gov (United States)

    Zonouzi, Afsaneh; Izakian, Zakieh; Ng, Seik Weng

    2016-08-01

    Novel tricyclic keto diesters have been synthesized by a one-pot three-component procedure via DABCO-catalyzed domino Knoevenagel-Michael addition reactions. Also, an efficient four-component reaction for the synthesis of another new group of tricyclic keto diesters has been developed via domino Knoevenagel-intramolecular oxo-Diels-Alder reactions. A selective thermal isomerization of the synthesized chromenes to fumarates is also described. X-ray analyses confirm unambiguously the structures of the products.

  12. Solution phase isomerization of vibrationally excited singlet nitrenes to vibrationally excited 1,2-didehydroazepine.

    Science.gov (United States)

    Burdzinski, Gotard T; Middleton, Chris T; Gustafson, Terry L; Platz, Matthew S

    2006-11-22

    Photolysis of phenyl and o-biphenylyl azide (at 270 nm) releases vibrationally excited singlet nitrene which isomerizes to the corresponding hot 1,2-didehydroazepine at a rate competitive with thermal relaxation. Using ultrafast vibrational spectroscopy we observe the formation of vibrationally excited 1,2-4,6-azacycloheptatetraene (1,2-didehydroazepine) in picoseconds following photolysis of phenyl azide in chloroform and o-biphenylyl azide in acetonitrile at ambient temperature.

  13. Aspartate-bond isomerization affects the major conformations of synthetic peptides.

    Science.gov (United States)

    Szendrei, G I; Fabian, H; Mantsch, H H; Lovas, S; Nyéki, O; Schön, I; Otvos, L

    1994-12-15

    The aspartic acid bond changes to an beta-aspartate bond frequently as a side-reaction during peptide synthesis and often as a post-translational modification of proteins. The formation of beta-asparate bonds is reported to play a major role not only in protein metabolism, activation and deactivation, but also in pathological processes such as deposition of the neuritic plaques of Alzheimer's disease. Recently, we reported how conformational changes following the aspartic-acid-bond isomerization may help the selective aggregation and retention of the amyloid beta peptide in affected brains (Fabian et al., 1994). In the current study we used circular dichroism, Fourier-transform infrared spectroscopy, and molecular modeling to characterize the general effect of the beta-aspartate-bond formation on the conformation of five sets of synthetic model peptides. Each of the non-modified, parent peptides has one of the major secondary structures as the dominant spectroscopically determined conformation: a type I beta turn, a type II beta turn, short segments of alpha or 3(10) helices, or extended beta strands. We found that both types of turn structures are stabilized by the aspartic acid-bond isomerization. The isomerization at a terminal position did not affect the helix propensity, but placing it in mid-chain broke both the helix and the beta-pleated sheet with the formation of reverse turns. The alteration of the geometry of the lowest energy reverse turn was also supported by molecular dynamics calculations. The tendency of the aspartic acid-bond isomerization to stabilize turns is very similar to the effect of incorporating sugars into synthetic peptides and suggests a common feature of these post-translational modifications in defining the secondary structure of protein fragments.

  14. Investigation Solvation Dynamics and Isomerization of Dye IR-140 Using pump supercontinuum-probing Technique

    CERN Document Server

    Wang, D; Wu, S; Yang, H; Xiang, Q G J; Xu, G; Wang, Danling; Jiang, Hongbing; Wu, Songjiang; Yang, Hong; Xiang, Qihuang Gong Junfeng; Xu, Guangzhi

    2001-01-01

    The solvation dynamics and isomerization process of an organic dye, IR-140, in polar solvents and nonpolar solvents have been investigated using pump supercontinuum-probing (PSCP) technique. In all solvents, the dynamics exhibits solvent-dependent. Solvent induced spectral shifts of the absorption and emission spectra of IR-140 have also been studied in a variety of solvents. At the same time, the photoisomerization process has been examined. The approximate energy-band structure of IR-140 was also supposed firstly.

  15. Simultaneous assessment of Asp isomerization and Asn deamidation in recombinant antibodies by LC-MS following incubation at elevated temperatures.

    Directory of Open Access Journals (Sweden)

    Katharina Diepold

    Full Text Available The degradation of proteins by asparagine deamidation and aspartate isomerization is one of several chemical degradation pathways for recombinant antibodies. In this study, we have identified two solvent accessible degradation sites (light chain aspartate-56 and heavy chain aspartate-99/101 in the complementary-determining regions of a recombinant IgG1 antibody susceptible to isomerization under elevated temperature conditions. For both hot-spots, the degree of isomerization was found to be significantly higher than the deamidation of asparagine-(387, 392, 393 in the conserved CH3 region, which has been identified as being solvent accessible and sensitive to chemical degradation in previous studies. In order to reduce the time for simultaneous identification and functional evaluation of potential asparagine deamidation and aspartate isomerization sites, a test system employing accelerated temperature conditions and proteolytic peptide mapping combined with quantitative UPLC-MS was developed. This method occupies the formulation buffer system histidine/HCl (20 mM; pH 6.0 for denaturation/reduction/digestion and eliminates the alkylation step. The achieved degree of asparagine deamidation and aspartate isomerization was adequate to identify the functional consequence by binding studies. In summary, the here presented approach greatly facilitates the evaluation of fermentation, purification, formulation, and storage conditions on antibody asparagine deamidation and aspartate isomerization by monitoring susceptible marker peptides located in the complementary-determining regions of recombinant antibodies.

  16. Characterization of phycoviolobilin phycoerythrocyanin-alpha 84-cystein-lyase-(isomerizing) from Mastigocladus laminosus.

    Science.gov (United States)

    Zhao, Kai-Hong; Wu, Dong; Wang, Lu; Zhou, Ming; Storf, Max; Bubenzer, Claudia; Strohmann, Brigitte; Scheer, Hugo

    2002-09-01

    Cofactor requirements and enzyme kinetics have been studied of the novel, dual-action enzyme, the isomerizing phycoviolobilin phycoerythrocyanin-alpha84-cystein-lyase(PVB-PEC-lyase) from Mastigocladus laminosus, which catalyses both the covalent attachment of phycocyanobilin to PecA, the apo-alpha-subunit of phycoerythrocyanin, and its isomerization to phycoviolobilin. Thiols and the divalent metals, Mg2+ or Mn2+, were required, and the reaction was aided by the detergent, Triton X-100. Phosphate buffer inhibits precipitation of the proteins present in the reconstitution mixture, but at the same time binds the required metal. Kinetic constants were obtained for both substrates, the chromophore (Km = 12-16 micro m, depending on [PecA], kcat approximately 1.2 x 10-4.s-1) and the apoprotein (Km = 2.4 micro m at 14 micro m PCB, kcat = 0.8 x 10-4.s-1). The kinetic analysis indicated that the reconstitution reaction proceeds by a sequential mechanism. By a combination of untagged and His-tagged subunits, evidence was obtained for a complex formation between PecE and PecF (subunits of PVB-PEC-lyase), and by experiments with single subunits for the prevalent function of PecE in binding and PecF in isomerizing the chromophore.

  17. Effect of iridium loading on HZSM-5 for isomerization of n-heptane

    Institute of Scientific and Technical Information of China (English)

    Herma Dina Setiabudi; Sugeng Triwahyono; Aishah Abdul Jalil; Nur Hidayatul Nazirah Kamarudin; Muhammad Arif Ab Aziz

    2011-01-01

    The effect of iridium loading on the properties and catalytic isomerization of n-heptane over Ir-HZSM-5 is studied.Ir-HZSM-5 was prepared by impregnation method and subjected to isomerization process in the presence of flowing hydrogen gas.XRD and BET studies show that the presence of iridium stabilizes the crystalline structure of HZSM-5,leading to more ordered framework structure and larger surface area.TGA and FTIR results substantiate that iridium species interacts with OH group on the surface of HZSM-5.Pyridine FT-IR study verifies the interaction between iridium and surface OH group slightly increased the Br(o)nsted and Lewis acid sites without changing the lattice structure of HZSM-5.The presence of iridium and the increase of strong Lewis acid sites on HZSM-5 were found to bring an increase about 4.1%,33.2% and 11.8% in conversion,selectivity and yield of n-heptane isomerization,respectively.

  18. 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).

  19. Comparison of homogeneous and heterogeneous catalysts for glucose-to-fructose isomerization in aqueous media.

    Science.gov (United States)

    Choudhary, Vinit; Pinar, Ana B; Lobo, Raul F; Vlachos, Dionisios G; Sandler, Stanley I

    2013-12-01

    Herein, the first comparison of the mechanisms of glucose-to-fructose isomerization in aqueous media enabled by homogeneous (CrCl3 and AlCl3 ) and heterogeneous catalysts (Sn-beta) by using isotopic-labeling studies is reported. A pronounced kinetic isotope effect (KIE) was observed if the deuterium label was at the C2 position, thus suggesting that a hydrogen shift from the C2 to C1 positions was the rate-limiting step with the three catalysts. (13) C and (1) H NMR spectroscopic investigations confirmed that an intra-hydride-transfer reaction pathway was the predominant reaction channel for all three catalysts in aqueous media. Furthermore, the deuterium atom in the labeled glucose could be mapped onto hydroxymethylfurfural and formic acid through reactions that followed the isomerization step in the presence of Brønsted acids. In all three catalysts, the active site appeared to be a bifunctional Lewis-acidic/Brønsted-basic site, based on a speciation model and first-principles calculations. For the first time, a mechanistic similarities between the homogeneous and heterogeneous catalysis of aldose-to-ketose isomerization is established and it is suggested that learning from homogeneous catalysis could assist in the development of improved heterogeneous catalysts.

  20. Femtosecond infrared spectroscopy of channelrhodopsin-1 chromophore isomerization

    Directory of Open Access Journals (Sweden)

    T. Stensitzki

    2016-07-01

    Full Text Available Vibrational dynamics of the retinal all-trans to 13-cis photoisomerization in channelrhodopsin-1 from Chlamydomonas augustae (CaChR1 was investigated by femtosecond visible pump mid-IR probe spectroscopy. After photoexcitation, the transient infrared absorption of C-C stretching modes was detected. The formation of the 13-cis photoproduct marker band at 1193 cm−1 was observed within the time resolution of 0.3 ps. We estimated the photoisomerization yield to (60 ± 6 %. We found additional time constants of (0.55 ± 0.05 ps and (6 ± 1 ps, assigned to cooling, and cooling processes with a back-reaction pathway. An additional bleaching band demonstrates the ground-state heterogeneity of retinal.

  1. Core-coupled states and split proton-neutron quasi-particle multiplets in 122-126Ag

    CERN Document Server

    Lalkovski, S; Jungclaus, A; Gorska, M; Pfutzner, M; Caceres, L; Naqvi, F; Pietri, S; Podolyak, Zs; Simpson, G S; Andgren, K; Bednarczyk, P; Beck, T; Benlliure, J; Benzoni, G; Casarejos, E; Cederwall, B; Crespi, F C L; Cuenca-Garcia, J J; Cullen, I J; Bacelar, A M Denis; Detistov, P; Doornenbal, P; Farrelly, G F; Garnsworthy, A B; Geissel, H; Gelletly, W; Gerl, J; Grebosz, J; Hadinia, B; Hellstrom, M; Hinke, C; Hoischen, R; Ilie, G; Jaworski, G; Jolie, J; Khaplanov, A; Kisyov, S; Kmiecik, M; Kojouharov, I; Kumar, R; Kurz, N; Maj, A; Mandal, S; Modamio, V; Montes, F; Myalski, S; Palacz, M; Prokopowicz, W; Reiter, P; Regan, P H; Rudolph, D; Schaffner, H; Sohler, D; Steer, S J; Tashenov, S; Walker, J; Walker, P M; Weick, H; Werner-Malento, E; Wieland, O; Wollersheim, H J; Zhekova, M

    2012-01-01

    Neutron-rich silver isotopes were populated in the fragmentation of a 136Xe beam and the relativistic fission of 238U. The fragments were mass analyzed with the GSI Fragment separator and subsequently implanted into a passive stopper. Isomeric transitions were detected by 105 HPGe detectors. Eight isomeric states were observed in 122-126Ag nuclei. The level schemes of 122,123,125Ag were revised and extended with isomeric transitions being observed for the first time. The excited states in the odd-mass silver isotopes are interpreted as core-coupled states. The isomeric states in the even-mass silver isotopes are discussed in the framework of the proton-neutron split multiplets. The results of shell-model calculations, performed for the most neutron-rich silver nuclei are compared to the experimental data.

  2. Identification of isomerization and racemization of aspartate in the Asp-Asp motifs of a therapeutic protein.

    Science.gov (United States)

    Zhang, Jennifer; Yip, Holly; Katta, Viswanatham

    2011-03-15

    A thermally stressed Fab molecule showed a significant increase of basic variants in imaged capillary isoelectric focusing (iCIEF) analysis. Mass analyses of the reduced protein found an increase in -18Da species from both light chain and heavy chain. A tryptic peptide map identified two isoAsp-containing peptides, both containing Asp-Asp motifs and located in complementarity-determining regions (CDRs) of light chains and heavy chains, respectively. The approaches of hydrolyzing succinimide in H(2)(18)O followed by tryptic digestion were used to label and identify the sites of isomerization. This method enabled identification of the isomerization site by comparing the MS/MS spectra of isomerized peptides with and without (18)O incorporation. The light chain peptide L2 VTITCITSTDID(12)DDMNWYQQKPGK underwent simultaneous isomerization and recemization at residue Asp-12 after thermal stress as evidenced by the coinjection of synthetic peptide L2 with l-Asp-12, l-isoAsp-12, d-Asp-12, and d-isoAsp-12, respectively. A thermal stress study of the synthetic peptide (l-)L2 showed that the isomerization and racemization did not occur, indicating that the Asp degradation in this Asp-Asp motif is more related to the protein conformation than the primary sequence. Another isomerization site was identified as Asp-24 in the heavy chain peptide H5 QAPGQGLEWMGWINTYTGETTYAD(24)DFK. No other isomerizations were detected in CDR peptides containing either Asp-Ser or Asp-Thr motifs. Copyright © 2010 Elsevier Inc. All rights reserved.

  3. An Optimized Glutamate Receptor Photoswitch with Sensitized Azobenzene Isomerization.

    Science.gov (United States)

    Gascón-Moya, Marta; Pejoan, Arnau; Izquierdo-Serra, Mercè; Pittolo, Silvia; Cabré, Gisela; Hernando, Jordi; Alibés, Ramon; Gorostiza, Pau; Busqué, Félix

    2015-10-16

    A new azobenzene-based photoswitch, 2, has been designed to enable optical control of ionotropic glutamate receptors in neurons via sensitized two-photon excitation with NIR light. In order to develop an efficient and versatile synthetic route for this molecule, a modular strategy is described which relies on the use of a new linear fully protected glutamate derivative stable in basic media. The resulting compound undergoes one-photon trans-cis photoisomerization via two different mechanisms: direct excitation of its azoaromatic unit and irradiation of the pyrene sensitizer, a well-known two-photon sensitive chromophore. Moreover, 2 presents large thermal stability of its cis isomer, in contrast to other two-photon responsive switches relying on the intrinsic nonlinear optical properties of push-pull substituted azobenzenes. As a result, the molecular system developed herein is a very promising candidate for evoking large photoinduced biological responses during the multiphoton operation of neuronal glutamate receptors with NIR light, which require accumulation of the protein-bound cis state of the switch upon repeated illumination.

  4. Development of ultrafast photochromic organometallics and photoinduced linkage isomerization of arene chromium carbonyl derivatives.

    Science.gov (United States)

    To, Tung T; Heilweil, Edwin J; Duke, Charles B; Ruddick, Kristie R; Webster, Charles Edwin; Burkey, Theodore J

    2009-03-26

    We review recent studies of processes relevant to photoinduced linkage isomerization of organometallic systems with the goal of preparing organometallics with an efficient and ultrafast photochromic response. The organometallic system thus corresponds to two linkage isomers with different electronic environments that are responsible for different optical properties. Much of this work has focused on examining processes following irradiation of cyclopentadienyl manganese tricarbonyl derivatives (compounds 3-21) including solvent coordination, thermal relaxation, solvent displacement by tethered functional groups (chelation), dissociation of tethered functional groups, and linkage isomerization. A new platform is investigated for obtaining a photochromic response in new experiments with arene chromium dicarbonyl complexes. A photochromic response is observed for arene chromium dicarbonyl complexes with tethered pyridine and olefin functional groups based on light-driven linkage isomerization on the nanosecond time scale. Irradiation at 532 nm of 23 ([Cr{eta(6)-C(6)H(5)CH(2-Py-kappaN)CH(2)CH=CH(2)}(CO)(2)]) (Py = pyridine) results in the isomerization to 22 ([Cr{eta(6)-C(6)H(5)CH(2-Py)CH(2)-eta(2)-CH=CH(2)}(CO)(2)]), and 355 nm irradiation isomerizes 22 to 23. The ultrafast linkage isomerization has been investigated at room temperature in n-heptane solution on the picosecond to microsecond time scale with UV- or visible-pump and IR-probe transient absorption spectroscopy by comparing the dynamics with model compounds containing only a tethered pyridine. Irradiation of 24 ([Cr{eta(6)-C(6)H(5)(CH(2))(3)(2-Py)}(CO)(3)]) and 25 ([Cr{eta(6)-C(6)H(5)(CH(2))(2)(2-Py)}(CO)(3)]) at 289 nm induces CO loss to immediately yield a Cr-heptane solvent coordinated intermediate of the unsaturated Cr fragment, which then converts to the kappaN(1)-pyridine chelate within 200 and 100 ns, respectively. Irradiation of 26 ([Cr{eta(6)-C(6)H(5)CH(2)(2-Py)}(CO)(3)]) also induces CO loss to

  5. Thermal Degradation and Isomerization of β-Carotene in Oil-in-Water Nanoemulsions Supplemented with Natural Antioxidants.

    Science.gov (United States)

    Yi, Jiang; Fan, Yuting; Yokoyama, Wallace; Zhang, Yuzhu; Zhao, Liqing

    2016-03-09

    The goal of this study was to see the impact on the retention and isomerization of encapsulated β-carotene (BC) in nanoemulsions fortified with natural antioxidants (α-tocopherol (AT) and l-ascorbic acid (AA)). The physical stability of nanoemulsion, oxidative stability, and isomerization of all-trans-β-carotene (BC) in oil-in-water (O/W) nanoemulsions were determined in the presence or absence of natural antioxidants at 25 and 50 °C at certain intervals of time by high-performance liquid chromatography (HPLC). Sodium caseinate was used as the emulsifier, and corn oil (CO) was more protective than medium-chain triglycerides (MCT) and used for isomerization studies. Mean diameters of control (without antioxidants) and AA- and AT-fortified particles were similar. Mean particle diameter of nanoemulsions increased from 10 to 25 nm at 25 °C and from 40 to 50 nm at 50 °C during 30 days of storage. The isomerization from all-trans-BC to cis-BC isomers was inhibited by antioxidants. The isomerization rates were in the following order: 13-cis-BC > 15-cis-BC > 9-cis-BC. AT had better antioxidant activities than AA in inhibiting BC degradation in O/W nanoemulsions. The results indicated that BC encapsulated in nanoemulsions supplemented with antioxidants could significantly improve BC's chemical stability.

  6. The Effect of Sulfate Ion on the Isomerization of n-Butane to iso-Butane

    Institute of Scientific and Technical Information of China (English)

    Sugeng Triwahyono; Zalizawati Abdullah; Aishah Abdul Jalil

    2006-01-01

    The effect of sulfate ion (SO24-) loading on the properties of Pt/SO24--ZrO2 and on the catalytic isomerization of n-butane to iso-butane was studied. The catalyst was prepared by impregnation of Zr(OH)4 with H2SO4 and platinum solution followed by calcination at 600 ℃. Ammonia TPD and FT-IR were used to confirm the distribution of acid sites and the structure of the sulfate species. Nitrogen physisorption and X-ray diffraction were used to confirm the physical structures of Pt/SO24--ZrO2. XRD pattern showed that the presence of sulfate ion stabilized the metastable tetragonal phase of zirconia and hindered the transition of amorphous phase to monoclinic phase of zirconia. Ammonia TPD profiles indicated the distributions of weak and medium acid sites observed on 0.1 N and 1.0 N sulfate in the loaded catalysts. The addition of 2.0 N and 4.0 N sulfate ion generated strong acid site and decreased the weak and medium acid sites. However, the XRD results and the specific surface area of the catalysts indicated that the excessive amount of sulfate ion collapsed the structure of the catalyst. The catalysts showed high activity and stability for isomerization of n-butane to iso-butane at 200 ℃ under hydrogen atmosphere. The conversion of n-butane to iso-butane per specific surface area of the catalyst increased with the increasing amount of sulfate ion owing to the existence of the bidentate sulfate and/or polynucleic sulfate species ((ZrO)2SO2), which acts as an active site for the isomerization.

  7. Importance of Membrane Structural Integrity for RPE65 Retinoid Isomerization Activity

    Energy Technology Data Exchange (ETDEWEB)

    Golczak, Marcin; Kiser, Philip D.; Lodowski, David T.; Maeda, Akiko; Palczewski, Krzysztof (Case Western)

    2010-04-05

    Regeneration of visual chromophore in the vertebrate visual cycle involves the retinal pigment epithelium-specific protein RPE65, the key enzyme catalyzing the cleavage and isomerization of all-trans-retinyl fatty acid esters to 11-cis-retinol. Although RPE65 has no predicted membrane spanning domains, this protein predominantly associates with microsomal fractions isolated from bovine retinal pigment epithelium (RPE). We have re-examined the nature of RPE65 interactions with native microsomal membranes by using extraction and phase separation experiments. We observe that hydrophobic interactions are the dominant forces that promote RPE65 association with these membranes. These results are consistent with the crystallographic model of RPE65, which features a large lipophilic surface that surrounds the entrance to the catalytic site of this enzyme and likely interacts with the hydrophobic core of the endoplasmic reticulum membrane. Moreover, we report a critical role for phospholipid membranes in preserving the retinoid isomerization activity and physical properties of RPE65. Isomerase activity measured in bovine RPE was highly sensitive to phospholipase A{sup 2} treatment, but the observed decline in 11-cis-retinol production did not directly reflect inhibition by products of lipid hydrolysis. Instead, a direct correlation between the kinetics of phospholipid hydrolysis and retinoid isomerization suggests that the lipid membrane structure is critical for RPE65 enzymatic activity. We also provide evidence that RPE65 operates in a multiprotein complex with retinol dehydrogenase 5 and retinal G protein-coupled receptor in RPE microsomes. Modifications in the phospholipid environment affecting interactions with these protein components may be responsible for the alterations in retinoid metabolism observed in phospholipid-depleted RPE microsomes. Thus, our results indicate that the enzymatic activity of native RPE65 strongly depends on its membrane binding and

  8. 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.

  9. A Promising MoOx-based Catalyst for n-Heptane Isomerization

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The SiO2 and γ-Al2O3 supported MoOx catalyst and a MoOx-SiO2 catalyst have been studied in a conventional fixed-bed flow reactor for n-alkanes isomerization. It is shown that the MoOx-SiO2 catalyst with SiO2 framework, in which the bulk MoOx phase is large enough to form typical mesoporous structure, is promising in terms of its advantages of both improved mechanical strength and high catalytic properties over the supported MoOx and bulk MoOx catalyst.

  10. The effect of rotational isomerism on the first hyperpolarizability of chromophores with divinyl quinoxaline conjugated bridge

    Science.gov (United States)

    Levitskaya, A. I.; Kalinin, A. A.; Fominykh, O. D.; Balakina, M. Yu.

    2017-08-01

    The effect of rotational isomerism on the values of first hyperpolarizability is studied by the example of two chromophores 7-DMA-VQV-TCP and 3-DMA-VQonV-TCP with quinoxaline and quinoxalinone moieties in the π-electron bridge. At the isomers formation the rotations about three single bonds are considered, thus providing eight possible conformers for each chromophore. The analysis of the results of DFT calculations demonstrates the presence of one lowest-energy conformer characterized by dominating probability for each chromophore. The calculations show that for both chromophores all rotational isomers are characterized by the first hyperpolarizability values rather close (within 8% and 11%) to statistically averaged ones.

  11. 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.

  12. Flexible synthesis of isomeric pyranoindolones and evaluation of cytotoxicity towards HeLa cells

    Indian Academy of Sciences (India)

    J C JEYAVEERAN; CHANDRASEKAR PRAVEEN; Y ARUN; A A M PRINCE; P T PERUMAL

    2016-05-01

    A hybrid pharmacophore approach for the synthesis of isomeric pyranoindolones was achievedby employing gold(III) chloride-catalyzed cycloisomerization of alkyne-tethered indole carboxylic acids ingood to excellent yield. All the synthesized compounds were evaluated for their tumor cell growth inhibitoryactivity against human cervix adenocarcinoma (HeLa) which revealed that three compounds exhibited activitycomparable with the standard cis-platin $(IC_{50} = 0.μM)$. Molecular docking of all the compounds in Vaccinia H1-Related (VHR) Phosphatase receptor also supported that compound 7d as the most active with a free energyof binding as - 8.27 kcal/mol.

  13. 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.

  14. The role of angular-momentum removal in photonuclear reactions as deduced from the isomeric ratios for ? and ?

    Science.gov (United States)

    Kolev, D.; Ernst, J.

    1998-03-01

    A model interpretation of isomeric ratios for 0954-3899/24/3/010/img7 and 0954-3899/24/3/010/img8 produced in the reactions 0954-3899/24/3/010/img9, 0954-3899/24/3/010/img10, 0954-3899/24/3/010/img11, 0954-3899/24/3/010/img12, 0954-3899/24/3/010/img13 and 0954-3899/24/3/010/img14 is presented. The experimental isomeric ratios were obtained using bremsstrahlung radiation with end-point energies of 18 and 43 MeV. The calculations were performed by means of the well known code STAPRE and the new code COMPLET. Angular-momentum removal in pre-equilibrium emission was found to be much more important for the observed isomeric ratios than subsequent compound-nucleus evaporation.

  15. Poisoning and regeneration of Pt-Pd/WO{sub 3}-ZrO{sub 2} short paraffin isomerization catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Canavese, Sergio; Finelli, Zunilda; Busto, Mariana; Benitez, Viviana M.; Vera, Carlos R.; Yori, Juan C., E-mail: jyori@fiq.unl.edu.a [Universidad Nacional del Litoral (UNL), Santa Fe (Argentina). Inst. de Investigaciones en Catalisis y Petroquimica

    2010-07-01

    WO{sub 3}-ZrO{sub 2} catalysts promoted with Pt and Pd were tested as paraffin isomerization catalysts using n-hexane as model compound. Sulfur and amine poisoning and regeneration tests were used to assess the impact of the addition of Pt and Pd on the deactivation resistance and regenerability. Pt and Pt Pd catalysts were the most active for n-hexane isomerization. The low activity of the Pd catalyst was attributed to poor Pd metal properties when supported over WO{sub 3}-ZrO{sub 2} and to a decrease of the number of Broensted acid sites. Pt Pd was the only catalyst capable of full regeneration after S poisoning. Amine poisoning completely suppressed the isomerization activity and the original activity could only be restored by calcination and reduction. (author)

  16. Poisoning and regeneration of Pt-Pd/WO3-ZrO2 short paraffin isomerization catalysts

    Directory of Open Access Journals (Sweden)

    Sergio Canavese

    2010-01-01

    Full Text Available WO3-ZrO2 catalysts promoted with Pt and Pd were tested as paraffin isomerization catalysts using n-hexane as model compound. Sulfur and amine poisoning and regeneration tests were used to assess the impact of the addition of Pt and Pd on the deactivation resistance and regenerability. Pt and PtPd catalysts were the most active for n-hexane isomerization. The low activity of the Pd catalyst was attributed to poor Pd metal properties when supported over WO3-ZrO2 and to a decrease of the number of BrQnsted acid sites. PtPd was the only catalyst capable of full regeneration after S poisoning. Amine poisoning completely supressed the isomerization activity and the original activity could only be restored by calcination and reduction.

  17. Why base-catalyzed isomerization of N-propargyl amides yields mostly allenamides rather than ynamides

    Directory of Open Access Journals (Sweden)

    Armando Navarro-Vázquez

    2015-08-01

    Full Text Available The base-catalyzed isomerization of N-propargylamides or carbamates may furnish N-allenyl compounds (allenamides/allencarbamates or further evolve to N-alkynyl compounds (ynamides or yncarbamates. The particular fate of this reaction varies from experiment to experiment and there is no clear rule for predicting the reaction outcome for a particular structure. With the support of ab initio and DFT computations, this work shows that observed results can be explained by assuming an exchange equilibrium between energetically close N-propargyl, allenyl and N-alkynyl forms and that the reaction outcome correlates to a particular equilibrium mixture. Due to the very small energy gap between the N-allenyl and N-alkynyl forms, small structural changes may easily alter the equilibrium position, explaining the variety of observed experimental results. Based on CBS-QB3 computations, the ωB97 functional provided reasonably accurate isomerization energies and could successfully predict the experimentally observed behavior for several examples from the literature.

  18. Kinetic Studies of Solvent and Pressure Effects on the Thermal Isomerization of Palladium Dithizonate

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    @@ Introduction The photo- and thermo-chromisms of organometallic compounds have been intensively studied during the last 10 years. Meriwether et al.[1,2] examined the chromic behavior of metal-dithizone(phenyldiazenecarbothionic acid 2-phenylhydrazide) complexes in detail. From the kinetic and infrared studies, they showed that the central metal of a dithizonate complex determined the photochemical stability, the rate of the thermal return reaction, and the color of the dithizonate complex. As reported by Meriwether et al.[2], the isomerization of mercury bisdithizonate[Hg(HDz)2] having tetrahedral stereochemistry occurs in each ligand independently and is unaffected by the presence of the second ligand attached to the same central metal. On the other hand, the spectral evidence suggesting the possibility of ligand-ligand interaction via a central metal was found in the square-planar dithizone complexes of Ni, Pd, and Pt[1]. Though there have been many studies regarding the thermochromism of tetrahedral Hg(HDz)2, the reaction mechanism of the thermal isomerization of the square-planar bisdithizonate complex involving the ligand-ligand interaction has not been well established yet.

  19. Separation and identification of isomeric glycopeptides by high field asymmetric waveform ion mobility spectrometry.

    Science.gov (United States)

    Creese, Andrew J; Cooper, Helen J

    2012-03-01

    The analysis of intact glycopeptides by mass spectrometry is challenging due to the numerous possibilities for isomerization, both within the attached glycan and the location of the modification on the peptide backbone. Here, we demonstrate that high field asymmetric wave ion mobility spectrometry (FAIMS), also known as differential ion mobility, is able to separate isomeric O-linked glycopeptides that have identical sequences but differing sites of glycosylation. Two glycopeptides from the glycoprotein mucin 5AC, GT(GalNAc)TPSPVPTTSTTSAP and GTTPSPVPTTST(GalNAc)TSAP (where GalNAc is O-linked N-acetylgalactosamine), were shown to coelute following reversed-phase liquid chromatography. However, FAIMS analysis of the glycopeptides revealed that the compensation voltage ranges in which the peptides were transmitted differed. Thus, it is possible at certain compensation voltages to completely separate the glycopeptides. Separation of the glycopeptides was confirmed by unique reporter ions produced by supplemental activation electron transfer dissociation mass spectrometry. These fragments also enable localization of the site of glycosylation. The results suggest that glycan position plays a key role in determining gas-phase glycopeptide structure and have implications for the application of FAIMS in glycoproteomics.

  20. Effect of thermal processing on the degradation, isomerization, and bioaccessibility of lycopene in tomato pulp.

    Science.gov (United States)

    Colle, Ines; Lemmens, Lien; Van Buggenhout, Sandy; Van Loey, Ann; Hendrickx, Marc

    2010-01-01

    Thermal processing affects the nutritional value of food products. The nutritional value is not only determined by the content but also by the bioaccessibility of nutrients. The present study was performed to gain detailed insight into the influence of thermal processing on the degradation, isomerization, and bioaccessibility of lycopene isomers in tomato pulp, without adding any other ingredient. The bioaccessibility, which is defined as the fraction of the nutrient that can be released from the food matrix, was measured using an in vitro method. The results demonstrated the rather high thermal stability of lycopene. Although a treatment at 140 °C induced isomerization, the contribution of cis-lycopene to the total lycopene content remained small. Results also confirmed that thermal processing as such can improve the in vitro bioaccessibility of lycopene in tomato pulp, but the improvement was only significant upon treatments at temperatures of 130 and 140 °C. At such intense process conditions, one should be aware of the negative effect on other quality and nutrient parameters. Possibilities of thermal processing as such to improve the nutritional value of tomato pulp (without the addition of other ingredients) thus looks rather limited.

  1. 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; Troy, Tyler; Kostko, Oleg; Ahmed, Musahid; Stanton, John F.; Daily, John W.; Ellison, Barney

    2016-06-01

    he thermal decomposition of cyclohexanone (C_6H10=O) has been studied in a set of flash-pyrolysis micro-reactors. Samples of C_6H10=O were first observed to decompose at 1200 K. Short residence times of 100 μsec and dilution of samples (cyclohexanone appeared to result from a variety of competing pathways pictured to the right. Isomerization of cyclohexanone to the enol, cyclohexen-1-ol (C_6H_9OH), is followed by retro-Diels-Alder cleavage to CH_2=CH_2 and CH_2=C(OH)-CH=CH_2. Further isomerization of CH_2=C(OH)CH=CH_2 to methyl vinyl ketone (CH_3COCH=CH_2, MVK) was also observed. Photoionization spectra identified both enols, C_6H_9OH and CH=C(OH)CH=CH_2, and the ionization threshold of C_6H_9OH was measured to be 8.2 ± 0.1 eV. At 1200 K, the products of cyclohexanone pyrolysis were found to be: C_6H_9OH, CH_2=C(OH)CH=CH_2, MVK, CH_2CHCH_2, CO, CH_2=C=O, CH_3, CH_2=C=CH_2, CH_2=CH-CH=CH_2, CH_2=CHCH_2CH_3, CH_2=CH_2, and HCCH.

  2. 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

  3. 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.

  4. Isomeric [RuCl2(dmso)2(indazole)2] complexes: ruthenium(II)-mediated coupling reaction of acetonitrile with 1H-indazole.

    Science.gov (United States)

    Reisner, Erwin; Arion, Vladimir B; Rufińska, Anna; Chiorescu, Ion; Schmid, Wolfgang F; Keppler, Bernhard K

    2005-07-21

    Reaction of the antitumor complex trans-[Ru(III)Cl4(Hind)2]- (Hind = indazole) with an excess of dimethyl sulfoxide (dmso) in acetone afforded the complex trans,trans,trans-[Ru(II)Cl2(dmso)2(Hind)2] (1). Two other isomeric compounds trans,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (2) and cis,cis,cis-[Ru(II)Cl2(dmso)2(Hind)2] (3) have been obtained on refluxing cis-[Ru(II)Cl(2)(dmso)(4)] with 2 equiv. of indazole in ethanol and methanol, respectively. Isomers 1 and 2 react with acetonitrile yielding the complexes trans-[Ru(II)Cl2(dmso)(Hind){HN=C(Me)ind}].CH3CN (4.CH3CN) and trans,cis-[Ru(II)Cl2(dmso)2{HN=C(Me)ind}].H2O (5.H2O), respectively, containing a cyclic amidine ligand resulting from insertion of the acetonitrile C triple bond N group in the N1-H bond of the N2-coordinated indazole ligand in the nomenclature used for 1H-indazole. These are the first examples of the metal-assisted iminoacylation of indazole. The products isolated have been characterized by elemental analysis, IR spectroscopy, UV-vis spectroscopy, electrospray mass-spectrometry, thermogravimetry, differential scanning calorimetry, 1H NMR spectroscopy, and solid-state 13C CP MAS NMR spectroscopy. The isomeric structures of 1-3 and the presence of a chelating amidine ligand in 4 and 5 have been confirmed by X-ray crystallography. The electrochemical behavior of 1-5 and the formation of 5 have been studied by cyclic voltammetry.

  5. Investigation of glassy state molecular motions in thermoset polymers

    Science.gov (United States)

    Tu, Jianwei

    This dissertation presents the investigation of the glassy state molecular motions in isomeric thermoset epoxies by means of solid-state deuterium (2H) NMR spectroscopy technique. The network structure of crosslinked epoxies was altered through monomer isomerism; specifically, diglycidyl ether of bisphenol A (DGEBA) was cured with isomeric amine curatives, i.e., the meta-substituted diaminodiphenylsulfone (33DDS) and para-substituted diaminodiphenylsulfone (44DDS). The use of structural isomerism provided a path way for altering macroscopic material properties while maintaining identical chemical composition within the crosslinked networks. The effects of structural isomerism on the glassy state molecular motions were studied using solid-state 2H NMR spectroscopy, which offers unrivaled power to monitor site-specific molecular motions. Three distinctive molecular groups on each isomeric network, i.e., the phenylene rings in the bisphenol A structure (BPA), the phenylene rings in the diaminodiphenylsulfone structure (DDS), and the hydroxypropoyl ether group (HPE) have been selectively deuterated for a comprehensive study of the structure-dynamics- property relationships in thermoset epoxies. Quadrupolar echo experiments and line shape simulations were employed as the main research approach to gain both qualitative and quantitative motional information of the epoxy networks in the glassy state. Quantitative information on the geometry and rate of the molecular motions allows the elucidation of the relationship between molecular motions and macro physical properties and the role of these motions in the mechanical relaxation. Specifically, it is revealed that both the BPA and HPE moieties in the isomeric networks have almost identical behaviors in the deep glassy state, which indicates that the molecular motions in the glassy state are localized, and the correlation length of the motions does not exceed the length of the DGEBA repeat unit. BPA ring motions contribute

  6. Structural characterization of the HIV-1 Vpr N terminus: evidence of cis/trans-proline isomerism.

    Science.gov (United States)

    Bruns, Karsten; Fossen, Torgils; Wray, Victor; Henklein, Peter; Tessmer, Uwe; Schubert, Ulrich

    2003-10-31

    The 96-residue human immunodeficiency virus (HIV) accessory protein Vpr serves manifold functions in the retroviral life cycle including augmentation of viral replication in non-dividing host cells, induction of G2 cell cycle arrest, and modulation of HIV-induced apoptosis. Using a combination of dynamic light scattering, circular dichroism, and NMR spectroscopy the N terminus of Vpr is shown to be a unique domain of the molecule that behaves differently from the C-terminal domain in terms of self-association and secondary structure folding. Interestingly, the four highly conserved proline residues in the N terminus are predicted to have a high propensity for cis/trans isomerism. Thus the high resolution structure and folding of a synthetic N-terminal peptide (Vpr1-40) and smaller fragments thereof have been investigated. 1H NMR data indicate Vpr1-40 possesses helical structure between residues 17-32, and for the first time, this helix, which is bound by proline residues, was observed even in aqueous solution devoid of any detergent supplements. In addition, NMR data revealed that all of the proline residues undergo a cis/ trans isomerism to such an extent that approximately 40% of all Vpr molecules possess at least one proline in a cis conformation. This phenomenon of cis/trans isomerism, which is unprecedented for HIV-1 Vpr, not only provides an explanation for the molecular heterogeneity observed in the full-length molecule but also indicates that in vivo the folding and function of Vpr should depend on a cis/trans-proline isomerase activity, particularly as two of the proline residues in positions 14 and 35 show considerable amounts of cis isomers. This prediction correlates well with our recent observation (Zander, K., Sherman, M. P., Tessmer, U., Bruns, K., Wray, V., Prechtel, A. T., Schubert, E., Henklein, P., Luban, J., Neidleman, J., Greene, W. C., and Schubert, U. (2003) J. Biol. Chem. 278, 43170-43181) of a functional interaction between the major

  7. 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.

  8. Efficient, regioselective palladium-catalyzed tandem Heck-isomerization reaction of aryl bromides and non-allylic benzyl alcohols.

    Science.gov (United States)

    Crawley, Matthew L; Phipps, Kristin M; Goljer, Igor; Mehlmann, John F; Lundquist, Joseph T; Ullrich, John W; Yang, Cuijian; Mahaney, Paige E

    2009-03-05

    An efficient and mild method to couple aryl bromides and activated non-allylic alcohols in a Heck reaction with tandem isomerization to selectively afford high yields of 1,5-diarylalkan-1-ones has been developed. Mechanistic insight was gained through NMR studies of products derived from deuterium-labeled intermediates.

  9. Maya chemistry of organic inorganic hybrid materials: isomerization, cyclicization and redox tuning of organic dyes attached to porous silicates

    OpenAIRE

    ANTONIO DOMÉNECH CARBÓ; Valle-Algarra, Francisco M.; Domenech Carbo, Mª Teresa; Osete Cortina, Laura; Domine ., Marcelo Eduardo

    2013-01-01

    [EN] Association of indigo and lapachol dyes to aluminosilicate clays yields polyfunctional organic – inorganic hybrid materials forming Maya Blue-like systems. Upon partial removing of clay's zeolitic water by moderate thermal treatment, abundant isomerization, cyclicization and oxidation reactions occur defining a‘ Maya chemistry whose complexity could explain the versatile use of such materials in the pre-Columbian cultures and permits the...

  10. Enantioselective Nickel-Catalyzed anti-Carbometallative Cyclizations of Alkynyl Electrophiles Enabled by Reversible Alkenylnickel E/Z Isomerization

    Science.gov (United States)

    2016-01-01

    Nickel-catalyzed additions of arylboronic acids to alkynes, followed by enantioselective cyclizations of the alkenylnickel species onto tethered ketones or enones, are reported. These reactions are reliant upon the formal anti-carbonickelation of the alkyne, which is postulated to occur by the reversible E/Z isomerization of an alkenylnickel species. PMID:27333360

  11. Spectra of carbanions formed from allyl cyanide during isomerization in zeolite NaY-FAU with strong basic sites

    Science.gov (United States)

    Hannus, István; Förster, Horst; Tasi, Gyula; Kiricsi, Imre; Molnár, Árpád

    1995-03-01

    Double bond isomerization of allyl cyanide to crotononitrile over a basic zeolite catalyst was monitored by IR and UV-VIS spectroscopy in order to get information on the surface intermediates involved. Due to the spectral changes the occurence of a carbanionic intermediate seems to be highly probable characterized by an absorption at 400 nm.

  12. 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.

  13. The effect of the formyl group position upon asymmetric isomeric diarylethenes bearing a naphthalene moiety

    Directory of Open Access Journals (Sweden)

    Renjie Wang

    2012-07-01

    Full Text Available Three new isomeric asymmetric diarylethenes with a naphthyl moiety and a formyl group at the para, meta or ortho position of the terminal benzene ring were synthesized. Their photochromism, fluorescent-switch, and electrochemical properties were investigated. Among these diarylethenes, the one with a formyl group at the ortho position of benzene displayed the largest molar absorption coefficients and fluorescence quantum yield. The cyclization quantum yields of these compounds increased in the order of para para > ortho. Additionally, all of these diarylethenes functioned as effective fluorescent switches in both solution and PMMA films. Cyclic voltammograms proved that the formyl group and its position could effectively modulate the electrochemical behaviors of these diarylethene derivatives.

  14. Resolution of isomeric multi-ruthenated porphyrins by travelling wave ion mobility mass spectrometry.

    Science.gov (United States)

    Lalli, Priscila M; Iglesias, Bernardo A; Deda, Daiana K; Toma, Henrique E; de Sa, Gilberto F; Daroda, Romeu J; Araki, Koiti; Eberlin, Marcos N

    2012-02-15

    The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (R(p-p)). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N(2) and CO(2) were tested as the drift gas, and similar α but considerably better values of R(p) and R(p-p) were always observed for CO(2).

  15. Ring positional differentiation of isomeric N-alkylated fluorocathinones by gas chromatography/tandem mass spectrometry.

    Science.gov (United States)

    Westphal, Folker; Junge, Thomas

    2012-11-30

    In analogy to our previously published procedure for the differentiation of regioisomeric fluoroamphetamines a method was developed, to differentiate ring positional isomeric fluorocathinones by product ion spectrometry of ions generated by chemical ionization (CI) under GC-MS conditions using methane as reagent gas. N-alkylated ortho-, meta- and para-fluorocathinones could be unequivocally differentiated by product ion spectrometry of the hydrogen fluoride loss ions [M+H-HF](+) using a triple quadrupole mass spectrometer with argon as collision gas under normalized collision conditions. This method enables the differentiation of ring positional isomers of fluorocathinones even in complex mixtures and low concentrations. The applicability of the method was shown by the analysis of synthesized N-alkylated ortho-, meta- and para-fluorocathinones and seized designer drug mixtures.

  16. Influence of reaction channel on the isomeric cross-section ratio

    OpenAIRE

    Qaim, S. M.; Sudár, S.; Fessler, A.

    2005-01-01

    The influence of reaction channel on the isomeric cross-section ratio was investigated by analysing the experimental data on the reactions Cr-52(p, n)Mn-52m,Mn-g, Cr-52(He-3, t)Mn-52m.g, Fe-54(d, alpha)Mn-52m.g, Fe-54(n, t)Mn-52m.g and Fe-54(He-3, alpha p)Mn-52m.g over the incident particle energy range extending up to 35MeV. The influence is most pronounced when the channels differ widely, for example (p,n) and (He-3, t) processes, i.e. when the reaction mechanisms are different. The nuclear...

  17. Structural Isomerization of the Gas Phase 2-NORBORNYL Cation Revealed with Infrared Spectroscopy and Computational Chemistry

    Science.gov (United States)

    Mauney, Daniel; Mosley, Jonathan; Duncan, Michael A.

    2014-06-01

    The non-classical structure of the 2-norborny cation (C_7H11+) which was at the center of "the most heated chemical controversy of our time" has been observed in the condensed phase and recently using X-ray crystallography. However, no gas phase vibrational spectrum has been collected. The C_7H11+ cation is produced via H_3+ protonation of norbornene by pulsed discharge in a supersonic expansion of H_2/Ar. Ions are mass-selected and probed using infrared photodissociation spectroscopy. Due to high exothermicity, protonation via H_3+ leads to a structural isomerization to the global minimum structure 1,3-dimethylcyclopentenyl (DMCP+). Experiments are currently being conducted to find softer protonation techniques that could lead to the authentic 2-norbornyl cation. Schleyer,P.v.R. et. al.; Stable Carbocation Chemistry, John Wiley & Sons,Inc.; New York, 1997, Chapter 2

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

    DEFF Research Database (Denmark)

    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......The application of computer-aided model based methods within an integrated systematic framework is illustrated with the objective to assist the multi-purpose pharmaceutical/biochemical industry to systematically solve the complex problems that are experienced when aiming at improving the process...... 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...

  19. Measurement of isomeric ratios in sup 2 sup 3 sup 2 Th photofission products

    CERN Document Server

    Besshejko, O A; Zheltonozhskij, V A; Strilchuk, N V

    2002-01-01

    Measurement of activity of sup 2 sup 3 sup 2 Th photofission products with T sub 1 sub / sub 2 1 min / 10 h has been carried out using g-spectroscopy technique. The targets were irradiated by Bremsstrahlung gamma-quanta from Mevatron KD2 linear electron accelerator with boundary energy of 23 MeV. Using obtained data about photofission fragments yield isomeric ratios for sup 1 sup 1 7In, sup 1 sup 3 sup 0 Sb, sup 1 sup 3 sup 3 Te, sup 1 sup 3 sup 4 sup g I and sup 1 sup 3 sup 5 Xe nuclei have been measured for the first time at boundary energy of 23 MeV. For the first time mean angular momenta for mentioned above nuclei at sup 2 sup 3 sup 2 Th photofission have been determined.

  20. Relating n-pentane isomerization activity to the tungsten surface density of WO(x)/ZrO2.

    Science.gov (United States)

    Soultanidis, Nikolaos; Zhou, Wu; Psarras, Antonis C; Gonzalez, Alejandro J; Iliopoulou, Eleni F; Kiely, Christopher J; Wachs, Israel E; Wong, Michael S

    2010-09-29

    Zirconia-supported tungsten oxide (WO(x)/ZrO(2)) is considered an important supported metal oxide model acid catalyst, for which structure-property relationships have been studied for numerous acid-catalyzed reactions. The catalytic activity for xylene isomerization, alcohol dehydration, and aromatic acylation follows a volcano-shape dependence on tungsten surface density. However, WO(x)/ZrO(2) has not been studied for more acid-demanding reactions, like n-pentane isomerization, with regard to surface density dependence. In this work, WO(x)/ZrO(2) was synthesized using commercially available amorphous ZrO(x)(OH)(4-2x) and model crystalline ZrO(2) as support precursors. They were analyzed for n-pentane isomerization activity and selectivity as a function of tungsten surface density, catalyst support type, and calcination temperature. Amorphous ZrO(x)(OH)(4-2x) led to WO(x)/ZrO(2) (WZrOH) that exhibited maximum isomerization activity at ∼5.2 W·nm(-2), and the crystalline ZrO(2) led to a material (WZrO(2)) nearly inactive at all surface densities. Increasing the calcination temperature from 773 to 973 K increased the formation of 0.8-1 nm Zr-WO(x) clusters detected through direct imaging on an aberration-corrected high-resolution scanning transmission electron microscope (STEM). Calcination temperature further increased catalytic activity by at least two times. Brønsted acidity was not affected but Lewis acidity decreased in number, as quantified via pyridine adsorption infrared spectroscopy. WO(x)/ZrO(2) exhibited isomerization activity that peaked within the first 2 h time-on-stream, which may be due to Zr-WO(x) clusters undergoing an activation process.

  1. Isomerization of fenbuconazole under UV-visible irradiation - chemical and toxicological approaches.

    Science.gov (United States)

    Lassalle, Yannick; Nicol, Edith; Genty, Christophe; Bourcier, Sophie; Bouchonnet, Stéphane

    2015-07-30

    Fenbuconazole is a fungicide commonly used for the protection of vineyards, vegetables and grain crops. Under UV-visible irradiation, it undergoes isomerization through various cyclization processes. Isomeric structures were elucidated by liquid chromatography/high-resolution multiple-stage mass spectrometry (LC/HR-MS(n) ) coupling. The potential toxicities of these isomers were estimated by in silico tests. Aqueous solutions of fenbuconazole and grapes treated with this fungicide were irradiated in a self-made reactor equipped with a mercury vapor lamp. Analyses were carried out using high-performance liquid chromatography (HPLC) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS). High-resolution m/z measurements, multiple-stage mass spectrometry and isotopic labeling experiments allowed structural elucidation of the isomers of fenbuconazole. In silico toxicity estimations were carried out using the T.E.S.T. Seven isomers of fenbuconazole were detected after irradiation of the fungicide in aqueous solution; the major ones were also detected in the flesh of treated grapes irradiated under laboratory conditions. Elucidation of their chemical structures owing to high resolution measurements and multi-stage collision induced dissociation experiments allowed confirmation of photo-transformation pathways mainly dominated by cyclization processes. Photo-induced isomers exhibited higher potential toxicities than fenbuconazole for Daphnia magna and fathead minnow species. UV-visible irradiation of fenbuconazole in aqueous solution and on grapes leads to the formation of isomers, all of which being potentially much more toxic than the parent fungicide. Copyright © 2015 John Wiley & Sons, Ltd.

  2. Evaluation of ion mobility-mass spectrometry for determining the isomeric heterogeneity of oligosaccharide-alditols derived from bovine submaxillary mucin.

    Science.gov (United States)

    Li, Hongli; Bendiak, Brad; Kaplan, Kimberly; Davis, Eric; Siems, William F; Hill, Herbert H

    2013-10-15

    Rapid separation and independent analysis of isomeric species are needed for the structural characterization of carbohydrates in glycomics research. Ion mobility-mass spectrometry techniques were used to examine a series of isomeric neutral oligosaccharide-alditols derived from bovine submaxillary mucin. Several analytical techniques were employed: (1) off line separation of the oligosaccharide-alditol mixture by HPLC; (2) direct and rapid evaluation of isomeric heterogeneity of oligosaccharides by electrospray ionization-ion mobility-time of flight mass spectrometry; and (3) mobility-selected MS(2) and MS(3) to evaluate isomeric mobility peaks by dual gate ion mobility-tandem mass spectrometry. Multiple isomeric ion mobility peaks were observed for the majority of oligosaccharide-alditols, which was achieved on the millisecond time scale after LC separation. Fragmentation spectra obtained from the collision-induced dissociation of isomeric precursor ions could be essentially identical, or dramatically different for a given precursor m/z using the dual-gate ion mobility quadrupole ion trap mass spectrometer. This further confirmed the need for rapid physical resolution of isomeric precursor species prior to their tandem mass spectral analysis.

  3. Excitation functions and isomeric cross section ratios of the {sup 63}Cu({ital n},{alpha}){sup 60}Co{sup {ital m},}{ital g}, {sup 65}Cu({ital n},{alpha}){sup 62}Co{sup {ital m},}{ital g}, and

    Energy Technology Data Exchange (ETDEWEB)

    Cserpak, F.; Sudar, S.; Csikai, J.; Qaim, S.M. [Institute fuer Nuklearchemie, Forschungszentrum Juelich GmbH, D-52425 Juelich (Germany)]|[Institute of Experimental Physics, Kossuth University, 4001 Debrecen (Hungary)

    1994-03-01

    Excitation functions were measured for the {sup 63}Cu({ital n},{alpha}){sup 60}Co{sup {ital m}}, {sup 65}Cu({ital n},{alpha}){sup 62}Co{sup {ital m}}, and {sup 65}Cu({ital n},{alpha}){sup 62}Co{sup {ital g}} reactions over the neutron energy range of 6.3 to 14.8 MeV. Use was made of the activation technique in combination with high resolution {gamma}-ray spectroscopy. The nuetrons were produced via the {sup 2}H({ital d},{ital n}){sup 3}He reaction using a deuterium gas target at a variable energy compact cyclotron ({ital E}{sub {ital n}}=6.3--11.9 MeV) and via the {sup 3}H({ital d},{ital n}){sup 4}He reaction using a solid Ti-T target at a neutron generator ({ital E}{sub {ital n}}=13.7--14.8 MeV). From the available experimental data isomeric cross section ratios were determined for the isomeric pair {sup 60}Co{sup {ital m},}{ital g} in {sup 63}Cu({ital n},{alpha}) and {sup 60}Ni({ital n},{ital p}) reactions, and for the pair {sup 62}Co{sup {ital m},}{ital g} in the {sup 65}Cu({ital n},{alpha}) reaction. Statistical model calculations taking into account precompound effects were performed for the formation of both the isomeric and ground states of the products. The calculational results on the total ({ital n},{ital p}) and ({ital n},{alpha}) cross sections agree well with the experimental data; in the case of isomeric states, however, some deviations occur. The experimental isomeric cross section ratios are reproduced only approximately by the calculation; at 15 MeV the spin distribution of the level density has a significant effect on the calculation. For low-lying levels the isomeric cross section ratio depends strongly on the spins of the levels involved and not on their excitation energies. At a given neutron energy the population of the higher spin isomer appears to be higher in the ({ital n},{alpha}) process than in the ({ital n},{ital p}) reaction.

  4. Spectroscopic Investigation on the Primary Photoreaction of Bathy Phytochrome Agp2-Pr of Agrobacterium fabrum: Isomerization in a pH-dependent H-bond Network.

    Science.gov (United States)

    Singer, Patrick; Wörner, Sybille; Lamparter, Tilman; Diller, Rolf

    2016-05-04

    Bathy phytochrome Agp2 from Agrobacterium fabrum exhibits an unusually low pKa =7.6 in the Pr state in contrast to a pKa >11 in the Pfr state, indicating a pH-dependent charge distribution and H-bond network in the Pr chromophore binding pocket around neutral pH. Here, we report on ultrafast UV/Vis absorption spectroscopy of the primary Pr photoisomerization of Agp2 at pH 6 and pH 9 and upon H2 O/D2 O buffer exchange. The triexponential Pr kinetics slows down at increased pH and pronounced pH-dependent kinetic isotope effects are observed. The results on the Pr photoreaction suggest: 1) component-wise hindered dynamics on the chromophore excited-state potential energy surface at high pH and 2) proton translocation processes either via single-proton transfer or via significant reorganization of H-bond networks. Both effects reflect the interplay between the pH-dependent charge distribution in the Pr chromophore binding pocket on the one hand and chromophore excitation and its Z→E isomerization on the other hand.

  5. Vibrational memory in quantum localized states

    Science.gov (United States)

    Ajili, Y.; Trabelsi, T.; Denis-Alpizar, O.; Stoecklin, T.; Császár, A. G.; Mogren Al-Mogren, M.; Francisco, J. S.; Hochlaf, M.

    2016-05-01

    The rovibrational eigenenergy set of molecular systems is a key feature needed to understand and model elementary chemical reactions. A unique class of molecular systems, represented by an 4A'' excited electronic state of the [H,S ,N ] - system comprising several distinct dipole-bound isomers, is found to contain both bent and linear minima separated by relatively small barriers. Full-dimensional nuclear-motion computations performed in Jacobi coordinates using three-dimensional potential energy surfaces describing the stable isomers and the related transition states yield rovibrational eigenstates located both below and above the barriers. The rovibrational wave functions are well localized, regardless of whether the state's energy is below or above the barriers. We also show that the states preserve the memory of the isomeric forms they "originate from," which is signature of a strong vibrational memory effect above isomerization barriers.

  6. Mg(OMe)2 promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters to synthesize γ-ketone esters.

    Science.gov (United States)

    Lai, Luhao; Li, A-Ni; Zhou, Jiawei; Guo, Yarong; Lin, Li; Chen, Wei; Wang, Rui

    2017-03-08

    This work concerns the Mg(OMe)2 promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters with TMEDA as an additive. The isomerization proceeded under mild conditions and afforded γ-keto esters in high yield (up to 96%) within 2 h. Both (Z)- and (E)-γ-hydroxy-α,β-alkenoic esters were tolerated under the reaction conditions. This transformation involves the in situ formation of a dienolate intermediate from the easily accessible γ-hydroxy-α,β-alkenoic ester. The in situ generated dienolate can react with benzaldehyde and undergo a practical, useful tandem allylic isomerization-Aldol reaction to afford more functionalized compounds.

  7. Rearrangements in ground and excited states

    CERN Document Server

    de Mayo, Paul

    1980-01-01

    Rearrangements in Ground and Excited States, Volume 3 presents essays on the chemical generation of excited states; the cis-trans isomerization of olefins; and the photochemical rearrangements in trienes. The book also includes essays on the zimmerman rearrangements; the photochemical rearrangements of enones; the photochemical rearrangements of conjugated cyclic dienones; and the rearrangements of the benzene ring. Essays on the photo rearrangements via biradicals of simple carbonyl compounds; the photochemical rearrangements involving three-membered rings or five-membered ring heterocycles;

  8. Pin1 Modulates the Synaptic Content of NMDA Receptors via Prolyl-Isomerization of PSD-95.

    Science.gov (United States)

    Antonelli, Roberta; De Filippo, Roberto; Middei, Silvia; Stancheva, Stefka; Pastore, Beatrice; Ammassari-Teule, Martine; Barberis, Andrea; Cherubini, Enrico; Zacchi, Paola

    2016-05-18

    Phosphorylation of serine/threonine residues preceding a proline regulates the fate of its targets through postphosphorylation conformational changes catalyzed by the peptidyl-prolyl cis-/trans isomerase Pin1. By flipping the substrate between two different functional conformations, this enzyme exerts a fine-tuning of phosphorylation signals. Pin1 has been detected in dendritic spines and shafts where it regulates protein synthesis required to sustain the late phase of long-term potentiation (LTP). Here, we demonstrate that Pin1 residing in postsynaptic structures can interact with postsynaptic density protein-95 (PSD-95), a key scaffold protein that anchors NMDA receptors (NMDARs) in PSD via GluN2-type receptor subunits. Pin1 recruitment by PSD-95 occurs at specific serine-threonine/proline consensus motifs localized in the linker region connecting PDZ2 to PDZ3 domains. Upon binding, Pin1 triggers structural changes in PSD-95, thus negatively affecting its ability to interact with NMDARs. In electrophysiological experiments, larger NMDA-mediated synaptic currents, evoked in CA1 principal cells by Schaffer collateral stimulation, were detected in hippocampal slices obtained from Pin1(-/-) mice compared with controls. Similar results were obtained in cultured hippocampal cells expressing a PSD-95 mutant unable to undergo prolyl-isomerization, thus indicating that the action of Pin1 on PSD-95 is critical for this effect. In addition, an enhancement in spine density and size was detected in CA1 principal cells of Pin1(-/-) or in Thy-1GFP mice treated with the pharmacological inhibitor of Pin1 catalytic activity PiB.Our data indicate that Pin1 controls synaptic content of NMDARs via PSD-95 prolyl-isomerization and the expression of dendritic spines, both required for LTP maintenance. PSD-95, a membrane-associated guanylate kinase, is the major scaffolding protein at excitatory postsynaptic densities and a potent regulator of synaptic strength and plasticity. The

  9. Acidic and basic properties of zeolite-containing cracking catalyst in the process of butene-1 isomerization

    Science.gov (United States)

    Mursalova, L. A.; Guseinova, E. A.; Adzhamov, K. Yu.

    2016-08-01

    The process of butene-1 isomerization in the presence of two groups of samples of zeolite-containing catalyst (ZCC) that earlier participated in the traditional and oxidative catalytic cracking of vacuum gasoil is investigated. It is established that the nature of the reaction mixture and conditions of the cracking process are key factors in forming the acidic and basic properties of the catalyst. It is shown that the highest activity in the butene-1 isomerization into cis-/ trans-butene-2 is demonstrated by ZCC samples that participated in the oxidative catalytic cracking (oxycracking). It is suggested that the enhanced catalytic activity of this group of ZCC samples was related to the availability of acid-base centers in the form of radical-like oxygen along with protic- and aprotic-type acidic centers in the structure of the oxidative compaction products.

  10. Results of a direct search using synchrotron radiation for the low-energy $^{229}$Th nuclear isomeric transition

    CERN Document Server

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

    2015-01-01

    We report the results of a direct search for the $^{229}$Th ($I^{p} = 3/2^+\\leftarrow 5/2^+$) 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 $7.3 \\mbox{eV}$ and $8.8 \\mbox{eV}$ with transition lifetime $(1-2)\\mbox{s} \\lesssim \\tau \\lesssim (2000-5600)\\mbox{s}$. This measurement excludes roughly half of the favored transition search area and can be used to direct future searches.

  11. Isomeric ratio measurements for the radiative neutron capture 176Lu(n ,γ ) at the LANL DANCE facility

    Science.gov (United States)

    Denis-Petit, D.; Roig, O.; Méot, V.; Morillon, B.; Romain, P.; Jandel, M.; Kawano, T.; Vieira, D. J.; Bond, E. M.; Bredeweg, T. A.; Couture, A. J.; Haight, R. C.; Keksis, A. L.; Rundberg, R. S.; Ullmann, J. L.

    2016-11-01

    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. The experiment was carried out with the Detector for Advanced Neutron Capture Experiments (DANCE) at the Los Alamos National Laboratory. Measured isomeric ratios are compared with talys calculations using different models for photon strength functions, level densities, and optical potentials. In order to reproduce the experimental γ -ray spectra, a low-energy resonance must be added in the photon strength function used in our Hauser-Feshbach calculations.

  12. Approaching isomerism in organic and inorganic compounds: activity based on the use of problem situations during initial chemistry teacher training

    Directory of Open Access Journals (Sweden)

    osé Euzébio Simões Neto

    2013-08-01

    Full Text Available This study sought investigate: i the understanding of isomerism by future chemistry teachers during initial training; and ii the construction of isomer concepts after an approach centered on problem situations (SP’s. Two problem situations related to isomerism (historical context and medicinal applications were elaborated. A textual learning material developed for this purpose and concrete molecular models were used of system resources in the problem situation resolution process. Data were colleted using a questionnaire, field observation and semi-structured interview, and analyzed according to the ideas presented by Meirieu (1998. The two SP’s had obstacles, transposable to only a few of the nine groups that responded. Inadequate use of the isomer concept was observed in many of the responses considered scarcely satisfactory or unsatisfactory.

  13. Kinetics of n-butoxy and 2-pentoxy isomerization and detection of primary products by infrared cavity ringdown spectroscopy.

    Science.gov (United States)

    Sprague, Matthew K; Garland, Eva R; Mollner, Andrew K; Bloss, Claire; Bean, Brian D; Weichman, Marissa L; Mertens, Laura A; Okumura, Mitchio; Sander, Stanley P

    2012-06-21

    The primary products of n-butoxy and 2-pentoxy isomerization in the presence and absence of O(2) have been detected using pulsed laser photolysis-cavity ringdown spectroscopy (PLP-CRDS). Alkoxy radicals n-butoxy and 2-pentoxy were generated by photolysis of alkyl nitrite precursors (n-butyl nitrite or 2-pentyl nitrite, respectively), and the isomerization products with and without O(2) were detected by infrared cavity ringdown spectroscopy 20 μs after the photolysis. We report the mid-IR OH stretch (ν(1)) absorption spectra for δ-HO-1-C(4)H(8)•, δ-HO-1-C(4)H(8)OO•, δ-HO-1-C(5)H(10)•, and δ-HO-1-C(5)H(10)OO•. The observed ν(1) bands are similar in position and shape to the related alcohols (n-butanol and 2-pentanol), although the HOROO• absorption is slightly stronger than the HOR• absorption. We determined the rate of isomerization relative to reaction with O(2) for the n-butoxy and 2-pentoxy radicals by measuring the relative ν(1) absorbance of HOROO• as a function of [O(2)]. At 295 K and 670 Torr of N(2) or N(2)/O(2), we found rate constant ratios of k(isom)/k(O(2)) = 1.7 (±0.1) × 10(19) cm(-3) for n-butoxy and k(isom)/k(O(2)) = 3.4(±0.4) × 10(19) cm(-3) for 2-pentoxy (2σ uncertainty). Using currently known rate constants k(O(2)), we estimate isomerization rates of k(isom) = 2.4 (±1.2) × 10(5) s(-1) and k(isom) ≈ 3 × 10(5) s(-1) for n-butoxy and 2-pentoxy radicals, respectively, where the uncertainties are primarily due to uncertainties in k(O(2)). Because isomerization is predicted to be in the high pressure limit at 670 Torr, these relative rates are expected to be the same at atmospheric pressure. Our results include corrections for prompt isomerization of hot nascent alkoxy radicals as well as reaction with background NO and unimolecular alkoxy decomposition. We estimate prompt isomerization yields under our conditions of 4 ± 2% and 5 ± 2% for n-butoxy and 2-pentoxy formed from photolysis of the alkyl nitrites at 351 nm. Our

  14. Broad Separation of Isomeric Lipids by High-Resolution Differential Ion Mobility Spectrometry with Tandem Mass Spectrometry

    Science.gov (United States)

    Bowman, Andrew P.; Abzalimov, Rinat R.; Shvartsburg, Alexandre A.

    2017-08-01

    Maturation of metabolomics has brought a deeper appreciation for the importance of isomeric identity of lipids to their biological role, mirroring that for proteoforms in proteomics. However, full characterization of the lipid isomerism has been thwarted by paucity of rapid and effective analytical tools. A novel approach is ion mobility spectrometry (IMS) and particularly differential or field asymmetric waveform IMS (FAIMS) at high electric fields, which is more orthogonal to mass spectrometry. Here we broadly explore the power of FAIMS to separate lipid isomers, and find a 75% success rate across the four major types of glycero- and phospho- lipids ( sn, chain length, double bond position, and cis/ trans). The resolved isomers were identified using standards, and (for the first two types) tandem mass spectrometry. These results demonstrate the general merit of incorporating high-resolution FAIMS into lipidomic analyses.

  15. 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.

  16. Isomeric C12-alkamides isolated from purple coneflower (Echinacea purpurea (L.) Moench) exhibit characteristics of a PPARγ partial agonist

    DEFF Research Database (Denmark)

    El-Houri, Rime Bahij; Kotowska, Dorota; Wolber, Gerhard

    Nuclear hormone receptor PPARγ is predominantly found in adipose tissue and plays a role in regulating adipogenesis and glucose homeostasis. PPARγ belongs to the superfamily of transcription factors that bind DNA and regulate transcription in a ligand-dependent manner. A dichloromethane extract...... of Echinacea purpurea roots increasing glucose uptake (GU) and activating PPARγ was subjected to bioassay-guided chromatographic fractionation. Basal and insulin-dependent GU in 3T3-L1 adipocytes and PPARγ transactivation assay were used to assess the bioactivity of extract, fractions and isolated metabolites....... Two novel isomeric dodeca-2E,4E,8Z,10E/Z-tetraenoic acid 2-methylbutylamides together with two known C12-alkamides and -linolenic acid were isolated from active fractions. The compounds were found to activate PPARγ but only the isomeric alkamides were able to increase basal and insulin-dependent GU...

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

    Energy Technology Data Exchange (ETDEWEB)

    Croteau, R.; Gershenzon, J.; Wheeler, C.J.; Satterwhite, D.M. (Washington State Univ., Pullman (USA))

    1990-03-01

    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.

  18. Light induced E-Z isomerization in a multi-responsive organogel: elucidation from (1)H NMR spectroscopy.

    Science.gov (United States)

    Mondal, Sanjoy; Chakraborty, Priyadarshi; Bairi, Partha; Chatterjee, Dhruba P; Nandi, Arun K

    2015-07-07

    A multiresponsive organogel of (E)-N'-(anthracene-10-ylmethylene)-3,4,5-tris(dodecyloxy)benzohydrazide (I) showed a decrease of fluorescence intensity, decrease in mechanical strength and a change in gel morphology on irradiation with a wavelength of 365 nm. This is attributed to the E-Z isomerization across the C=N bond of I as evidenced from (1)H NMR spectroscopy.

  19. 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.

  20. Solution NMR structure and inhibitory effect against amyloid-β fibrillation of Humanin containing a d-isomerized serine residue.

    Science.gov (United States)

    Alsanousi, Nesreen; Sugiki, Toshihiko; Furuita, Kyoko; So, Masatomo; Lee, Young-Ho; Fujiwara, Toshimichi; Kojima, Chojiro

    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.

  1. An Exceptionally Facile Two-Step Structural Isomerization and Detoxication via a Water-Assisted Double Lossen Rearrangement

    Science.gov (United States)

    Li, Feng; Huang, Chun-Hua; Xie, Lin-Na; Qu, Na; Shao, Jie; Shao, Bo; Zhu, Ben-Zhan

    2016-12-01

    N-hydroxyphthalimide (NHPI), which is best known as an organocatalyst for efficient C-H activation, has been found to be oxidized by quinoid compounds to its corresponding catalytically active nitroxide-radical. Here, we found that NHPI can be isomerized into isatoic anhydride by an unusually facile two-step method using tetrachloro-1,4-benzoquinone (TCBQ, p-chloranil), accompanied by a two-step hydrolytic dechlorination of highly toxic TCBQ into the much less toxic dihydroxylation product, 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone (chloranilic acid). Interestingly, through the complementary application of oxygen-18 isotope-labeling, HPLC combined with electrospray ionization quadrupole time-of-flight and high resolution Fourier transform ion cyclotron resonance mass spectrometric studies, we determined that water was the source and origin of oxygen for isatoic anhydride. Based on these data, we proposed that nucleophilic attack with a subsequent water-assisted Lossen rearrangement coupled with rapid intramolecular addition and cyclization in two consecutive steps was responsible for this unusual structural isomerization of NHPI and concurrent hydroxylation/detoxication of TCBQ. This is the first report of an exceptionally facile double-isomerization of NHPI via an unprecedented water-assisted double-Lossen rearrangement under normal physiological conditions. Our findings may have broad implications for future research on hydroxamic acids and polyhalogenated quinoid carcinogens, two important classes of compounds of major chemical and biological interest.

  2. Effect of Asp 96 isomerization on the properties of a lens αB-crystallin-derived short peptide.

    Science.gov (United States)

    Takata, Takumi; Fujii, Noriko

    2015-12-10

    One of the major reasons for age-related cataract formation is an accumulation of insoluble lens proteins. In particular, higher-order α-crystallin aggregates, comprising αA and αB subunits, are insolubilized by the build up of various post-translational modifications over time. Although we previously found an exceptional amount of Asp96 isomerization in αB-crystallin from aged human lens, the biological effect remains unknown. To approximate the effect of Asp 96 isomerization in αB-crystallin, here residues 93-103 of αB-crystallin were chemically synthesized as peptides in which l-α-Asp was replaced with l-β-Asp, D-α-Asp, or D-β-Asp. The resulting peptides were then compared in a biological assay. The results showed that isomerization of Asp 96 altered both the local structure of peptide and its stability against enzymatic digestion. In addition, the synthesized peptides decreased the insoluble fraction of heated α-crystallin. The D-β-Asp-containing peptide further decreased heat-induced precipitation of α-crystallin, and a chaperone assay based on heated alcohol dehydrogenase implied differential interaction of the peptides with substrate depending on the Asp isomer present in each. Our results suggest that the formation of Asp isomers is likely to affect the higher-order oligomer structure of α-crystallin and thereby its chaperone functions in aged lens. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Distribution, isomerization and enantiomer selectivity of hexabromocyclododecane (HBCD) diastereoisomers in different tissue and subcellular fractions of earthworms.

    Science.gov (United States)

    Li, Bing; Chen, Hao; Sun, Hongwen; Lan, Zhonghui

    2017-05-01

    In this study, earthworms Eisenia fetida (E. fetida) were exposed to a soil artificially contaminated with individual hexabromocyclododecane (HBCD) diastereoisomers (α-, β- and γ-HBCDs) to investigate the distribution, isomerization and enantiomer selectivity of HBCDs at tissue and subcellular levels. At the tissue level, the concentrations of HBCDs all followed the order of gut>bodyfluid>body wall, which suggested that earthworms accumulated HBCDs mainly via ingesting soil particles. At the subcellular level, the concentrations of HBCDs in an extracellular fraction consisting of granules, tissue fragment, cell membrane and intact cells (fraction A) were higher than those in an intracellular fractions consisting of the microsomal and cytosol (fraction B+C). This confirmed the passive diffusion during the distribution of HBCDs into the intracellular compartment. The distribution proportions of HBCDs varied among different tissue and subcellular fractions, and all changed over time within 14 days. The variable distributions of HBCDs in different fractions were a result of the comprehensive effects of dynamics and thermodynamics processes. The β- and γ-HBCDs were isomerized to α-HBCD in all tissue and subcellular fractions except for fraction C, and the isomerization ratios varied a lot, which seemed to be related to HBCDs residence time. The selective enrichment of (-) α-, (-) β and (-) γ-HBCDs was found in all fractions and this is consistent with that in the whole earthworm. Besides, the extents of enantio-selectivity did not change significantly among different tissue and subcellular fractions.

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

    Science.gov (United States)

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

    2017-01-01

    We have determined the isomeric ratios of isomeric pairs 97m,gNb, 95m,gNb and 91m,gMo produced in 98Mo(γ, p)97m,gNb, 96Mo(γ, p)95m,gNb and 92Mo(γ, n)91m,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 97m,gNb from 14 to 19 MeV, for 195m,gNb from14 to 24 MeV except 20 and 23.5 MeV and for 91m,gMo at 14 and 15 MeV are the first time measurements.

  5. Characterization of the acid properties of tungsten/zirconia catalysts using adsorption microcalorimetry and n-pentane isomerization activity

    Energy Technology Data Exchange (ETDEWEB)

    Vartuli, J.C.; Santiesteban, J.G.; Traverso, P.; Cardona-Martinez, N.; Chang, C.D.; Stevenson, S.A.

    1999-10-01

    Ammonia adsorption microcalorimetry was conducted on various solid acid tungsten/zirconia catalysts prepared by different techniques. The calorimetric data were compared to catalytic test results using n-pentane isomerization as a measure of acid activity. The results show that (1) the co-precipitation method of making the tungsten/zirconia catalyst produces a greater number of acidic sites than impregnating tungsten on hydrous zirconia, resulting in a more active catalyst, and (2) the addition of small amounts of iron to the tungsten/zirconia catalyst increases the acid site strength as determined by ammonia adsorption and improves the paraffin isomerization activity. The calorimetry data indicate that the acid site strength of the tungsten/zirconia materials is similar to or slightly higher than that found in zeolites or sulfated zirconia and is comparable to sulfuric acid. However, the paraffin isomerization activity results suggest that the acid sites of the tungsten/zirconia catalyst should be about four orders of magnitude more active than that of zeolite {beta} on the basis of turnover frequency. Their experimental results indicate a lack of correlation between the heat of ammonia adsorption with catalytic activity. Comparisons of catalytic activity between materials based entirely on acid strength may not be valid, and kinetic probes would be more appropriate.

  6. n-Hexane hydro-isomerization over promoted Pd/HZSM-5 catalysts

    Science.gov (United States)

    Thoa Dao, Thi Kim; Loc Luu, Cam

    2015-09-01

    A series of Pd/HZSM-5 catalysts modified by various metallic species, including Co, Ni, Fe, Re, and Cu, was prepared by sequential impregnation. Contents of Pd and second metals in modified catalysts were 0.8 and 1.0 wt%, respectively. Physico-chemical characteristics of catalysts were investigated by nitrogen physi-sorption (BET), x-ray diffraction (XRD), transmission electron microscopy (TEM), ammonia temperature programmed desorption (NH3-TPD), temperature programmed reduction (TPR) and hydrogen pulse chemisorption (HPC). Coke formation was studied by the method of thermogravimetric analysis (TGA). The activities of catalysts in n-hexane isomerization were studied in a micro-flow reactor under atmospheric pressure at 250 °C, and molar ratio of H2: n-hexane of 5.92. It was found that Co, Ni, Fe, and Re additives exhibited geometric and electronic effects toward Pd/HZSM-5 catalyst, leading to an enhancement of its activity and stability. On the contrary, Cu additive caused Pd/HZSM-5 to become poorer in activity and stability.

  7. Interfaces Select Specific Stereochemical Conformations: The Isomerization of Glyoxal at the Liquid Water Interface.

    Science.gov (United States)

    Zhu, Chongqin; Kais, Sabre; Zeng, Xiao Cheng; Francisco, Joseph S; Gladich, Ivan

    2017-01-11

    Interfacial chemistry involving glyoxal at aerosol surfaces is postulated to catalyze aerosol growth. This chemistry remains speculative due to a lack of detailed information concerning the physicochemical behavior of glyoxal at the interface of atmospheric aerosols. Here, we report results from high-level electronic structure calculations as well as both classical and Born-Oppenheimer ab initio molecular dynamics simulations of glyoxal solvation at the air/liquid water interface. When compared to the gas phase, the trans to cis isomerization of glyoxal at the liquid water interface is found to be catalyzed; additionally, the trans conformation is selectively solvated within the bulk to a greater degree than is the cis conformation. These two processes, i.e., the catalytic effect at the water interface and the differentially selective solvation, act to enhance the concentration of the cis isomer of glyoxal at the water interface. This has important consequences for the interpretation of experiments and for the modeling of glyoxal chemistry both at the interface of water clouds and at aerosols. Broader implications of this work relate to describing the role of interfaces in selecting specific stereo molecular structures at interfacial environments.

  8. 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 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.

  9. 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.

  10. Failure in closure of the anterior neural tube causes left isomerization of the zebrafish epithalamus.

    Science.gov (United States)

    Lu, Po-Nien; Lund, Caroline; Khuansuwan, Sataree; Schumann, Adelle; Harney-Tolo, Marijah; Gamse, Joshua T; Liang, Jennifer O

    2013-02-15

    Differences between the left and right sides of the brain are present in many animal species. For instance, in humans the left cerebral hemisphere is largely responsible for language and tool use and the right for processing spatial information. Zebrafish have prominent left-right asymmetries in their epithalamus that have been associated with differential left and right eye use and navigational behavior. In wild-type (WT) zebrafish embryos, Nodal pathway genes are expressed in the left side of the pineal anlage. Shortly thereafter, a parapineal organ forms to the left of the pineal. The parapineal organ causes differences in gene expression, neuropil density, and connectivity of the left and right habenula nuclei. In embryos that have an open neural tube, such as embryos that are deficient in Nodal signaling or the cell adhesion protein N-cadherin, the left and right sides of the developing epithalamus remain separated from one another. We find that the brains of these embryos often become left isomerized: both sides of the brain develop morphology and gene expression patterns that are characteristic of the left side. However, other aspects of epithalamic development, such as differentiation of specific neuronal cell types, are intact. We propose that there is a mechanism in embryos with closed neural tubes that prevents both sides from developing like the left side. This mechanism fails when the two sides of the epithalamus are widely separated from one another, suggesting that it is dependent upon a signaling protein with limited range.

  11. Iodobenzene diacetate-mediated isomerization of pyrazolyl chalcones and their cytotoxicity and anti-microbial activity

    Indian Academy of Sciences (India)

    Mahavir Parshad; Vikas Verma; Devinder Kumar; Balasubramanian Narasimhan; Smit Kour; Shashank Singh; Payare Lal Sangwan

    2015-03-01

    Synthesis of cis (E)-1-(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-3-phenyl/aryl/heteroarylprop-2-en-1-ones from 1-phenyl-3-methyl-4-acetylpyrazol-5-one was achieved in good yield. s-cis (E)-1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-3-arylprop-2-en-1-ones were isomerized to s-trans (E)-4-(3-(phenyl/aryl/heteroaryl)acryloyl)-5-methyl-2-phenyl-1H-pyrazol-3(2H)-ones using iodobenzene diacetate in dichloromethane at room temperature in excellent yield. The structure and geometry of these , -unsaturated ketones (pyrazolyl ketones) were established with the help of NMR, 2D NMR and HRMS techniques. The cytotoxicity of pyrazolyl chalcones showed that s-cis (E) 1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-3-(4-methylphenyl)-prop-2-en-1-one is active at very low concentrations (IC50 13.3 M) against colon cancer cell line (HCT-116). The in vitro anti-microbial studies of pyrazolyl chalcones were also tested against grampositive (B. subtilis, S. aureus) and gram-negative bacteria (E. coli) and for anti-fungal activity against C. albicans and A. niger.

  12. 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.

  13. Effect of Concentration on Isomerization of Rhodanine Derivatives of Merocyanine Dyes in Polar Solvents

    Directory of Open Access Journals (Sweden)

    O. P. Dimitriev

    2014-01-01

    Full Text Available Rhodanine derivatives of merocyanine dyes with residues of 1,3,3-trimethyl-3H-indole and 3-ethylbenzothiazoline have been found to possess two molecular forms in diluted solutions of polar solvents such as dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidinone. The first molecular form was observed to prevail at low concentrations of the dyes, normally up to 10−5 M. The second one prevails at higher concentrations and is displayed through a new band in the electronic absorption spectrum, which is red-shifted with respect to the absorption band of the first form. No similar effect was found for these dyes by use of nonpolar solvents or upon alkyl-substitution of the molecules at nitrogen atom in the rhodanine moiety. We assign the above two forms to different molecular isomers and the analogous spectral changes were shown to take place by light or heat influence which correspond to a typical isomerization effect for the related merocyanine dyes. It is discussed that the isomer transformation is facilitated by the increased mobility of the proton bonded to the nitrogen atom of the rhodanine moiety in the polar environment and the increased amount of dye-dye collisions.

  14. Chain Conformation and Local Rigidity of Soluble Polyimides(Ⅱ): Isomerized Polyimides in THF

    Institute of Scientific and Technical Information of China (English)

    LIU Gui-hua; QIU Xue-peng; BO Shu-qin; JI Xiang-ling

    2012-01-01

    Two soluble isomerized polyimides(PIs)synthesized from 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride(6FDA)with either 2,2′-dimethylbenzidine(2,2′-DMB)or 3,3′-DMB were investigated by means of size-exclusion chromatography coupled with multi-angle laser light scattering,a viscometer and a refractive index detector in tetrahydrofuran(THF)with tetrabutylammonium bromide(TBAB)at 35 ℃.The corresponding parameters related to conformations α and v,evaluated from the scaling relationships[η]=KηMa and Rg=KgMv,respectively,were 0.66±0.01 and 0.55±0.02 for poly(6FDA/3,3'-DMB),and 0.67±0.01 and 0.56±0.01 for poly(6FDA/2,2'-DMB),indicating a random coil conformation for both the samples in this mobile system.The persistence length lp and shift factor ML(relative molecular weight per unit contour length)were estimated from the relationship between intrinsic viscosity and molecular weight for the wormlike cylinder model proposed by Bohdanecky.Both lp and ML showed that the two PIs in THF are flexible chains and exhibit some local rigidity to some extent.

  15. 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.

  16. Characteristics of the isomeric flavonoids apigenin and genistein binding to hemoglobin by spectroscopic methods

    Science.gov (United States)

    Yuan, Jiang-Lan; Liu, Hui; Kang, Xu; Lv, Zhong; Zou, Guo-Lin

    2008-11-01

    Apigenin (Ap) and genistein (Ge), a couple of isomeric flavonoids with extensive bioactivities, are the most common dietary ingredients. They have been widely investigated due to their potential therapeutic actions for some diseases. In our work, binding characteristics of Ap and Ge to hemoglobin (Hb) were analyzed with fluorescence spectroscopy, circular dichroism (CD) and UV-vis absorption spectroscopy. The results indicated that Ap and Ge caused strong fluorescence quenching of Hb by static quenching mechanism, but their quenching efficiency and mechanisms were different. The binding site n suggested that there was a single binding site in Hb for Ap and Ge. The results of synchronous fluorescence showed that the microenvironment around Tyr residues of Hb had a slight trend of polarity decreasing, but the polarity around Trp residues increased by adding Ap. Results of CD indicated that the Ap and Ge did not changed the secondary structure of Hb. According to the theory of Förster resonance energy transfer, the binding distance r between Trp 37 and Ap/Ge was predicted to be 3.4 nm and 3.32 nm, respectively. The affinity of Ge toward Hb was higher than that of Ap.

  17. Lycopene: Heterogeneous Catalytic E/Z Isomerization and In Vitro Bioaccessibility Assessment Using a Diffusion Model.

    Science.gov (United States)

    Sun, Qingrui; Yang, Cheng; Li, Jing; Raza, Husnain; Zhang, Lianfu

    2016-10-01

    Highly efficient heterogeneous catalytic E/Z isomerization of lycopene was achieved using an iodine-doped titanium dioxide (I-TiO2 ) catalyst prepared by sol-gel method. The effects of reaction temperature and reaction time were investigated in detail. The maximum total Z-ratio of lycopene exceeded 78% after 2 h of refluxing at 75 °C in ethyl acetate. Moreover, lycopene samples with a series of total Z-ratios were prepared and the bioaccessibility of these samples was estimated using a diffusion model, the results showed that the bioaccessibility of lycopene markedly increased conforming to a linear regression model with increasing of the total Z-ratio of lycopene from 3.6% to 78.5%. Furthermore, the specific role of the microstructure and melting point of 3.6% and 78.5% total Z-ratio of lycopene was also investigated to understand the probable mechanism for the enhanced bioaccessbility of (Z)-lycopenes.

  18. Reaction Ensemble Monte Carlo Simulation of Xylene Isomerization in Bulk Phases and under Confinement.

    Science.gov (United States)

    Mullen, Ryan Gotchy; Maginn, Edward J

    2017-08-17

    The original reaction move for the reaction ensemble Monte Carlo (RxMC) method is adapted to align both the position and orientation of inserted product molecules and deleted reactant molecules. The accuracy and efficiency of this move is demonstrated for xylene isomerization in vapor, liquid, and supercritical phases. Classical RxMC requires the ideal gas free energy of reaction ΔGrxn(ideal) as an input. We compare three methods for computing ΔGrxn(ideal): using tabulated enthalpies and entropies of formation, using the harmonic oscillator and rigid rotor approximations and using QM/MM alchemical transformation combined with multistate Bennett acceptance ratio. We find that the tabulated free energies of reaction give the best agreement with experimental equilibrium compositions in bulk fluids. RxMC simulations in a carbon nanotube with an inner diameter of approximately 6 Å show that p-xylene becomes the dominant isomer under confinement, an effect consistent with the production of p-xylene in the zeolite ZSM-5. We also show that o-xylene becomes the dominant isomer in nanotubes with an inner diameter of 7-8 Å. We find that both m- and p-xylene exhibit a loss of rotational entropy in nanotubes of this diameter, effectively allowing o-xylene to fit into cavities inaccessible to the other isomers.

  19. Comparisons of Caenorhabditis Fucosyltransferase Mutants Reveal a Multiplicity of Isomeric N-Glycan Structures.

    Science.gov (United States)

    Yan, Shi; Jin, Chunsheng; Wilson, Iain B H; Paschinger, Katharina

    2015-12-01

    Recent studies have shown a remarkable degree of plasticity in the N-glycome of the model nematode Caenorhabditis elegans; ablation of glycosylation-relevant genes can result in radically altered N-glycan profiles despite only minor biological phenotypic effects. Up to four fucose residues and five different linkages of fucose are known on the N-glycans of C. elegans. Due to the complexity in the wild type, we established three mutant strains defective in two core fucosyltransferases each (fut-1;fut-6, fut-1;fut-8, and fut-6;fut-8). Enzymatically released N-glycans were subject to HPLC and MALDI-TOF MS/MS, in combination with various treatments, to verify structural details. The N-glycome of the fut-1;fut-6 mutant was the most complex of the three double-mutant strains due to the extension of the core α1,6-fucose as well as the presence of fucose on the bisecting galactose. In contrast, maximally two fucoses were found on N-glycans of the fut-1;fut-8 and fut-6;fut-8 strains. The different locations and capping of fucose meant that up to 13 isomeric structures, many highly galactosylated, were determined for some single masses. These data not only show the high variability of the N-glycomic capacity of a "simple" nematode but also exemplify the need for multiple approaches to reveal individual glycan structures within complex invertebrate glycomes.

  20. 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.

  1. Investigating the position isomerism effect of dihydroxybenzoic acid compounds by terahertz time-domain spectroscopy

    Science.gov (United States)

    Du, Yong; Hao, Guohui; Zhao, Rongjiao; Hong, Zhi

    2012-03-01

    Far-infrared vibrational absorption of a series of dihydroxybenzoic acid (DHBA) compounds with different substituted hydroxy group at different positions have been investigated using terahertz time-domain spectroscopy (THz-TDS) at room temperature. The experimental results show large difference among absorption spectra of different DHBA (2,3-DHBA, 2,4-DHBA, 2,5-DHBA, 2,6-DHBA) compounds in 0.2 ~ 2.0 THz region, which probably originated from the difference of intra-molecular and inter-molecular hydrogen bonds due to the presence of two hydroxyl group in different positions with respect to the carboxylic group in different DHBAs. All the experimental DHBAs vibrational modes showed distinct fingerprint absorption in THz region and theorectical calculation based on density functional theory (DFT) was carried out to assist the analysis and assignment of the vibrational modes. The results indicate that THz-TDS technology can not only give a new experimental method to identify and characterize the position isomerism effect of hydroxyl group between such different kinds of DHBAs from molecule-level, but also provide a useful suggestion for further assessing the possible relationships between the DHBAs vibrational properties and the effects of the substituted hydroxy group position to better know their biochemical activities in food, pharmaceutical and cosmetic fields.

  2. Molecular and cellular specificity of post-translational aminoacyl isomerization in the crustacean hyperglycaemic hormone family.

    Science.gov (United States)

    Ollivaux, Céline; Gallois, Dominique; Amiche, Mohamed; Boscaméric, Maryse; Soyez, Daniel

    2009-09-01

    D-aminoacyl residues have been detected in various animal peptides from several taxa, especially vertebrates and arthropods. This unusual polymorphism was shown to occur in isoforms of the crustacean hyperglycaemic hormone (CHH) of the American lobster because a D-phenylalanyl residue was found in position 3 of the sequence (CHH and D-Phe3 CHH). In the present study, we report the detailed strategy used to characterize, in the lobster neuroendocrine system, isomers of another member of the CHH family, vitellogenesis inhibiting hormone (VIH). We have demonstrated that the fourth residue is either an L- or a D- tryptophanyl residue (VIH and D-Trp4 VIH). Furthermore, use of antisera specifically recognizing the epimers of CHH and VIH reveals that aminoacyl isomerization occurs in specialized cells of the X organ-sinus gland neurosecretory system and that the D-forms of the two neuropeptides are not only present in the same cells, but, importantly, also are co-packaged within the same secretory vesicles.

  3. Valence and spin situations in isomeric [(bpy)Ru(Q')2]n (Q' = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine). An experimental and DFT analysis.

    Science.gov (United States)

    Das, Dipanwita; Mondal, Tapan Kumar; Chowdhury, Abhishek Dutta; Weisser, Fritz; Schweinfurth, David; Sarkar, Biprajit; Mobin, Shaikh M; Urbanos, Francisco A; Jiménez-Aparicio, Reyes; Lahiri, Goutam Kumar

    2011-09-07

    The article deals with the ruthenium complexes, [(bpy)Ru(Q')(2)] (1-3) incorporating two unsymmetrical redox-noninnocent iminoquinone moieties [bpy = 2,2'-bipyridine; Q' = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, aryl = C(6)H(5) (Q'(1)), 1; m-Cl(2)C(6)H(3) (Q'(2)), 2; m-(OCH(3))(2)C(6)H(3) (Q'(3)), 3]. 1 and 3 have been preferentially stabilised in the cc-isomeric form while both the ct- and cc-isomeric forms of 2 are isolated [ct: cis and trans and cc: cis and cis with respect to the mutual orientations of O and N donors of two Q']. The isomeric identities of 1-3 have been authenticated by their single-crystal X-ray structures. The collective consideration of crystallographic and DFT data along with other analytical events reveals that 1-3 exhibit the valence configuration of [(bpy)Ru(II)(Q'(Sq))(2)]. The magnetization studies reveal a ferromagnetic response at 300 K and virtual diamagnetic behaviour at 2 K. DFT calculations on representative 2a and 2b predict that the excited triplet (S = 1) state is lying close to the singlet (S = 0) ground state with singlet-triplet separation of 0.038 eV and 0.075 eV, respectively. In corroboration with the paramagnetic features the complexes exhibit free radical EPR signals with g∼2 and (1)HNMR spectra with broad aromatic proton signals associated with the Q' at 300 K. Experimental results in conjunction with the DFT (for representative 2a and 2b) reveal iminoquinone based preferential electron-transfer processes leaving the ruthenium(ii) ion mostly as a redox insensitive entity: [(bpy)Ru(II)(Q'(Q))(2)](2+) (1(2+)-3(2+)) ⇋ [(bpy)Ru(II)(Q(')(Sq))(Q(')(Q))](+) (1(+)-3(+)) ⇋ [(bpy)Ru(II)(Q(')(Sq))(2)] (1-3) ⇋ [(bpy)Ru(II)(Q(')(Sq))(Q(')(Cat))](-)/[(bpy)Ru(III)(Q(')(Cat))(2)](-) (1(-)-3(-)). The diamagnetic doubly oxidised state, [(bpy)Ru(II)(Q'(Q))(2)](2+) in 1(2+)-3(2+) has been authenticated further by the crystal structure determination of the representative [(bpy)Ru(II)(Q'(3))(2)](ClO(4))(2) [3](ClO(4

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

    Energy Technology Data Exchange (ETDEWEB)

    Kim, K. [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Kim, G.N., E-mail: gnkim@knu.ac.kr [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Naik, H. [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Rediochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai 400085 (India); Zaman, M. [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Yang, S.-C.; Song, T.-Y. [Nuclear Data Center, Korea Atomic Energy Research Institute, Daejeon 305-353 (Korea, Republic of); Guin, R.; Das, S.K. [Variable Energy Cyclotron Centre, 1/AF Bidhan Nagar, Kolkata 700064 (India)

    2015-03-15

    The excitation functions of {sup 94–96}Tc isotopes and independent isomeric ratios of {sup 93m, g}Tc, {sup 94m, g}Tc, and {sup 95m, g}Tc from the {sup 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 {sup 94–96}Tc in the {sup 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 {sup 93m, g}Tc, {sup 94m, g}Tc, and {sup 95m, g}Tc in the {sup 93}Nb(α, xn) reactions from the present work and literature data were compared with similar data in the {sup 93}Nb({sup 3}He, xn) and {sup 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 {sup 93m, g}Tc, {sup 94m, g}Tc, and {sup 95m, g}Tc in the {sup 93}Nb(α, xn) and {sup 93}Nb({sup 3}He, xn) reactions are higher than those in the {sup 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 {sup 95m, g}Tc, {sup 94m, g}Tc, and {sup 93m, g}Tc decrease in all the {sup 93}Nb(α, xn), {sup 93}Nb({sup 3}He, xn) and {sup 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.

  5. Potential energy surfaces and approximate kinetic model for the excited state dynamics of Pigment Yellow 101

    NARCIS (Netherlands)

    Fletcher, Katharyn; Dreuw, Andreas; Faraji, Shirin

    2014-01-01

    Pigment Yellow 101 (PY101) exhibits a rich photochemistry in its S-1 state as it undergoes excited state intramolecular proton transfer and trans-cis isomerizations upon photoexcitation. Relaxed scans of its potential energy surface are thus computed along the reaction paths connecting the six most

  6. Differential Gelation and Self-Sorting Properties of Two Isomeric Polyamides Due to the Parallel vs Anti-Parallel Alignment of Backbone Dipoles.

    Science.gov (United States)

    Leung, Chui-Fan; Chow, Hak-Fun

    2017-02-14

    Two isomeric bottlebrush polyamides P-1 and A-1 having the same repeating monomer dipole units aligned along the polymer backbone in pseudo-parallel and pseudo-anti-parallel, respectively, were synthesized and characterized. Both polymers can form thermoreversible gels with aromatic solvents but P-1 was found to show inferior gelation strength as compared to that of A-1. Furthermore, despite their close structural resemblance, a 1:1 mixture of the P-1 and A-1 polymers was shown to exhibit self-sorting in the gel state. Gel formation was found to be a kinetically trapped process via H-bonding, π-π stacking interactions and side chain interdigitation. The differential gelation and self-sorting properties can be explained by the local dipole-dipole interactions originated from the different modes of backbone dipole alignment. In single gel systems, the antiparallel-aligned dipoles in A-1 facilitated a more compact molecular packing due to the enthalpically more favorable polymer chain association. On the other hand, the parallel-aligned dipoles in P-1 gave rise to a less stable head-to-head packing, which had difficulties to convert to the more stable head-to-tail packing in a kinetically trapped environment. In the mixed gel system, it is the unfavorable hetero-polymer mismatch dipole-dipole interaction that inhibited the mixing of the A-1 and P-1 polymers and led to self-sorting.

  7. High-spin states in /sup 86/Y

    Energy Technology Data Exchange (ETDEWEB)

    Bucurescu, D.; Constantinescu, G.; Cutiou, D.; Ivascu, M.; Zamfir, N.V.; Haliem, A.A. (Institutul Central de Fizica, Bucharest (Romania))

    1984-09-01

    The level scheme of /sup 86/Y was investigated by ..gamma..-ray spectroscopy with /sup 76/Ge(/sup 14/N, 4n) and /sup 73/Ge(/sup 16/O,p2n) reactions. New energy levels, spins and parities in the yrast sequence above the known isomeric 8+ states were indicated. The possible structure of these states is discussed in connection with an observed similarity with the yrast states in both odd and even-even neighbouring nuclei.

  8. Cis→Trans Isomerization of Pro7 in Oxytocin Regulates Zn2+ Binding

    Science.gov (United States)

    Fuller, Daniel R.; Glover, Matthew S.; Pierson, Nicholas A.; Kim, DoYong; Russell, David H.; Clemmer, David E.

    2016-08-01

    Ion mobility/mass spectrometry techniques are employed to investigate the binding of Zn2+ to the nine-residue peptide hormone oxytocin (OT, Cys1-Tyr2-Ile3-Gln4-Asn5-Cys6-Pro7-Leu8-Gly9-NH2, having a disulfide bond between Cys1 and Cys6 residues). Zn2+ binding to OT is known to increase the affinity of OT for its receptor [Pearlmutter, A. F., Soloff, M. S.: Characterization of the metal ion requirement for oxytocin-receptor interaction in rat mammary gland membranes. J. Biol. Chem. 254, 3899-3906 (1979)]. In the absence of Zn2+, we find evidence for two primary OT conformations, which arise because the Cys6-Pro7 peptide bond exists in both the trans- and cis-configurations. Upon addition of Zn2+, we determine binding constants in water of KA = 1.43 ± 0.24 and 0.42 ± 0.12 μM-1, for the trans- and cis-configured populations, respectively. The Zn2+ bound form of OT, having a cross section of Ω = 235 Å2, has Pro7 in the trans-configuration, which agrees with a prior report [Wyttenbach, T., Liu, D., Bowers, M. T.: Interactions of the hormone oxytocin with divalent metal ions. J. Am. Chem. Soc. 130, 5993-6000 (2008)], in which it was proposed that Zn2+ binds to the peptide ring and is further coordinated by interaction of the C-terminal, Pro7-Leu8-Gly9-NH2, tail. The present work shows that the cis-configuration of OT isomerizes to the trans-configuration upon binding Zn2+. In this way, the proline residue regulates Zn2+ binding to OT and, hence, is important in receptor binding.

  9. Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S2 state

    Science.gov (United States)

    Zhao, Li; Zhou, Pan-Wang; Zhao, Guang-Jiu

    2016-07-01

    The trans-urocanic acid, a UV chromophore in the epidermis of human skin, was found to exhibit a wavelength dependent isomerization property. The isomerization quantum yield to cis-urocanic is greatest when being excited to the S1 state, whereas exciting the molecule to the S2 state causes almost no isomerization. The comparative photochemical behavior of the trans-urocanic on the S1 and S2 states continues to be the subject of intense research effort. This study is concerned with the unique photo-behavior of this interesting molecule on the S2 state. Combining the on-the-fly surface hopping dynamics simulations and static electronic structure calculations, three decay channels were observed following excitation to the S2 state. An overwhelming majority of the molecules decay to the S1 state through a planar or pucker characterized minimum energy conical intersection (MECI), and then decay to the ground state along a relaxation coordinate driven by a pucker deformation of the ring. A very small fraction of molecules decay to the S1 state by a MECI characterized by a twisting motion around the CC double bond, which continues to drive the molecule to deactivate to the ground state. The latter channel is related with the photoisomerization process, whereas the former one will only generate the original trans-form products. The present work provides a novel S2 state decay mechanism of this molecule, which offers useful information to explain the wavelength dependent isomerization behavior.

  10. New Synthetic Route of Two Active Isomeric Metabolites of Erlotinib and Their Bioactivity Studies against Several Tumor Cell Lines%New Synthetic Route of Two Active Isomeric Metabolites of Erlotinib and Their Bioactivity Studies against Several Tumor Cell Lines

    Institute of Scientific and Technical Information of China (English)

    李汉青; 李梦瑶; 李载权; 李良; 毕姗姗; 邓晨辉; 陈睿; 周田彦; 卢炜

    2011-01-01

    The synthesis and differential antiproliferative activity of two active isomeric metabolites of erlotinib were in- vestigated. This synthetic process had demonstrated to avoid the unstable 4-chloroquinazoline intermediates and long procedures. New intermediates and final compounds were identified by IH NMR, 13C NMR and ESI-TOF MS, and their purities were determined by high performance liquid chromatography. In vitro proliferative assay indi- cated that these two metabolites possessed antiproliferative activity against some conventional tumor cell lines and EGFR tyrosine kinase over-expression tumor cell lines as compared to erlotinib control, and their antitumor activity in cellular level was first reported here.

  11. Investigation of isomeric flavanol structures in black tea thearubigins using ultraperformance liquid chromatography coupled to hybrid quadrupole/ion mobility/time of flight mass spectrometry.

    Science.gov (United States)

    Yassin, Ghada H; Grun, Christian; Koek, Jean H; Assaf, Khaleel I; Kuhnert, Nikolai

    2014-11-01

    Ultra performance liquid chromatography (UPLC) when coupled to ion mobility (IMS)/orthogonal acceleration time of flight mass spectrometry is a suitable technique for analyzing complex mixtures such as the black tea thearubigins. With the aid of this advanced instrumental analysis, we were able to separate and identify different isomeric components in the complex mixture which could previously not be differentiated by a conventional high performance liquid chromatography/tandem mass spectrometry. In this study, the difference between isomeric structures theasinensins, proanthocyanidins B-type and rutin (quercetin-3O-rutinoside) were studied, and these are present abundantly in many botanical sources. The differentiation between these structures was accomplished according to their acquired mobility drift times differing from the traditional investigations in mass spectrometry, where calculation of theoretical collisional cross sections allowed assignment of the individual isomeric structures. The present work demonstrates UPLC-IMS-MS as an efficient technology for isolating and separating isobaric and isomeric structures existing in complex mixtures discriminating between them according to their characteristic fragment ions and mobility drift times. Therefore, a rational assignment of isomeric structures in many phenolic secondary metabolites based on the ion mobility data might be useful in mass spectrometry-based structure analysis in the future.

  12. 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

  13. PREPARATION OF ISOMERIZED METHYL TETRAHYDROPHTHALIC ANHYDRIDE%异构化甲基四氢苯酐的研制

    Institute of Scientific and Technical Information of China (English)

    吴光杰

    2001-01-01

    Isomerized methyl tetrahydrophthalic anhydride with low viscosity,a curing agent of epoxy resin (N-570D),was prepared in this paper.Effect of some factors,such as catalyst,temperature et al on product gield and method of inhibitting side reaction were also discussed.%制备了低粘度环氧树脂固化剂(N-570D),即:异构化甲基四氢苯酐(MeTHPA),讨论催化剂等因素对收率的影响,并论述了抑制副反应的方法。

  14. Experimental apparatus at KUR-ISOL to identify isomeric transitions from fission products, and decay spectroscopy of 151Ce

    OpenAIRE

    Kojima, Yasuaki; M. Shibata(High Energy Accelerator Research Organization); Taniguchi, A.; Kawase, Y; Doi, R; Nagao, A; Shizuma, Kiyoshi

    2006-01-01

    Decay studies on 151Ce have been performed using the on-line isotope separator connected to the Kyoto University Reactor. In addition to conventional γ and conversion electron spectroscopy, β-gated measurements were carried out on mass-separated 151Ce to identify an isomeric transition. From the analysis of the obtained data, the half-life of the isotope was ascertained to be 1.76(6) s and a decay scheme containing six excited levels was constructed for the first time. The excited level at 35...

  15. Formation of the isomeric pair 194Irm,g in interactions of [alpha] particles with 192Os

    OpenAIRE

    Uddin, M. S.; Sudár Sándor (1946-) (fizikus); Qaim, Syed M.

    2011-01-01

    Cross sections were measured by the activation technique for the nuclear processes Os-192(alpha,d+pn+np)Ir-194(m,g) up to alpha-particle energies of 39 MeV. From the measured data the isomeric cross-section ratio was deduced as a function of projectile energy. The present experimental data as well as those for the Pt-194(n,p)Ir-194(m,g) reaction, given in the literature, were compared with the results of nuclear model calculations using the code TALYS, which combines the statistical, precompo...

  16. Effects of torsional disorder and position isomerism on two-photon absorption properties of polar chromophore dimers

    Science.gov (United States)

    Jia, Hai-Hong; Zhao, Ke; Wu, Xiang-Lian

    2014-09-01

    Two-photon absorption properties of a push-pull molecule and its covalent dimers have been studied by density functional response theory in combination with polarizable continuum model. A set of constrained geometries with different torsional angles are optimized and used to calculate two-photon absorption spectra. It is found that the torsional disorder could possibly produce the experimental two-photon absorption additive behavior. We have also designed a series of covalent dimers and investigated the effects of position isomerism. Our results suggest that the cooperative two-photon absorption enhancement can be achieved when the subunits are substituted in closer proximity and have larger interchromophore angle.

  17. Volumetric and acoustic behaviour of systems containing n-hexane, or n-heptane and isomeric chlorobutanes

    Energy Technology Data Exchange (ETDEWEB)

    Guerrero, H.; Pera, G.; Giner, I.; Bandres, I. [Departamento de Quimica Organica - Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain); Lafuente, C., E-mail: celadi@unizar.e [Departamento de Quimica Organica - Quimica Fisica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza (Spain)

    2010-11-15

    Densities and speeds of sound at atmospheric pressure and temperatures of (283.15, 298.15, and 313.15) K for the binary mixtures formed by n-hexane or n-heptane with isomeric chlorobutanes were determined. Afterwards excess volumes, excess isentropic compressibilities and excess speeds of sound were calculated using the experimental data and correlated using a Redlich-Kister type equation. Finally, the results were studied using the Prigogine-Flory-Patterson theory showing excellent predictions for speed of sound and isentropic compressibility values of mixtures as well as a strong influence of the interactional contribution term for excess volume values.

  18. Bulky guanidinato nickel(I) complexes: synthesis, characterization, isomerization, and reactivity studies.

    Science.gov (United States)

    Jones, Cameron; Schulten, Christian; Fohlmeister, Lea; Stasch, Andreas; Murray, Keith S; Moubaraki, Boujemaa; Kohl, Stuart; Ertem, Mehmed Z; Gagliardi, Laura; Cramer, Christopher J

    2011-01-24

    Reactions of lithium complexes of the bulky guanidinates [{(Dip)N}(2)CNR(2)](-) (Dip=C(6)H(3)iPr(2)-2,6; R=C(6)H(11) (Giso(-)) or iPr (Priso(-)), with NiBr(2) have afforded the nickel(II) complexes [{Ni(L)(μ-Br)}(2)] (L=Giso(-) or Priso(-)), the latter of which was crystallographically characterized. Reduction of [{Ni(Priso)(μ-Br)}(2)] with elemental potassium in benzene or toluene afforded the diamagnetic species [{Ni(Priso)}(2)(μ-C(6)H(5)R)] (R=H or Me), which were shown, by X-ray crystallographic studies, to possess nonplanar bridging arene ligands that are partially reduced. A similar reduction of [{Ni(Priso)(μ-Br)}(2)] in cyclohexane yielded a mixture of the isomeric complexes [{Ni(μ-κ(1)-N-,η(2)-Dip-Priso)}(2)] and [{Ni(μ-κ(2)-N,N'-Priso)}(2)], both of which were structurally characterized. These complexes were also formed through arene elimination processes if [{Ni(Priso)}(2)(μ-C(6)H(5)R)] (R=H or Me) were dissolved in hexane. In that solvent, diamagnetic [{Ni(μ-κ(1)-N-,η(2)-Dip-Priso)}(2)] was found to slowly convert to paramagnetic [{Ni(μ-κ(2)-N,N'-Priso)}(2)], suggesting that the latter is the thermodynamic isomer. Computational analysis of a model of [{Ni(μ-κ(2)-N,N'-Priso)}(2)] showed it to have a Ni-Ni bond that has a multiconfigurational electronic structure. An analogous copper(I) complex [{Cu(μ-κ(2)-N,N'-Giso)}(2)] was prepared, structurally authenticated, and found, by a theoretical study, to have a negligible Cu···Cu bonding interaction. The reactivity of [{Ni(Priso)}(2)(μ-C(6)H(5)Me)] and [{Ni(μ-κ(2)-N,N'-Priso)}(2)] towards a range of small molecules was examined and this gave rise to diamagnetic complexes [{Ni(Priso)(μ-CO)}(2)] and [{Ni(Priso)(μ-N(3))}(2)]. Taken as a whole, this study highlights similarities between bulky guanidinate ligands and the β-diketiminate ligand class, but shows the former to have greater coordinative flexibility.

  19. Synthesis and Isomeric Analysis of Ru(II) Complexes Bearing Pentadentate Scaffolds.

    Science.gov (United States)

    Gil-Sepulcre, Marcos; Axelson, Jordan C; Aguiló, Joan; Solà-Hernández, Lluís; Francàs, Laia; Poater, Albert; Blancafort, Lluís; Benet-Buchholz, Jordi; Guirado, Gonzalo; Escriche, Lluís; Llobet, Antoni; Bofill, Roger; Sala, Xavier

    2016-11-07

    A Ru(II)-pentadentate polypyridyl complex [Ru(II)(κ-N(5)-bpy2PYMe)Cl](+) (1(+), bpy2PYMe = 1-(2-pyridyl)-1,1-bis(6-2,2'-bipyridyl)ethane) and its aqua derivative [Ru(II)(κ-N(5)-bpy2PYMe)(H2O)](2+) (2(2+)) were synthesized and characterized by experimental and computational methods. In MeOH, 1(+) exists as two isomers in different proportions, cis (70%) and trans (30%), which are interconverted under thermal and photochemical conditions by a sequence of processes: chlorido decoordination, decoordination/recoordination of a pyridyl group, and chlorido recoordination. Under oxidative conditions in dichloromethane, trans-1(2+) generates a [Ru(III)(κ-N(4)-bpy2PYMe)Cl2](+) intermediate after the exchange of a pyridyl ligand by a Cl(-) counterion, which explains the trans/cis isomerization observed when the system is taken back to Ru(II). On the contrary, cis-1(2+) is in direct equilibrium with trans-1(2+), with absence of the κ-N(4)-bis-chlorido Ru(III)-intermediate. All these equilibria were modeled by density functional theory calculations. Interestingly, the aqua derivative is obtained as a pure trans-[Ru(II)(κ-N(5)-bpy2PYMe)(H2O)](2+) isomer (trans-2(2+)), while the addition of a methyl substituent to a single bpy of the pentadentate ligand leads to the formation of a single cis isomer for both chlorido and aqua derivatives [Ru(II)(κ-N(5)-bpy(bpyMe)PYMe)Cl](+) (3(+)) and [Ru(II)(κ-N(5)-bpy(bpyMe)PYMe)(H2O)](2+) (4(2+)) due to the steric constraints imposed by the modified ligand. This system was also structurally and electrochemically compared to the previously reported [Ru(II)(PY5Me2)X](n+) system (X = Cl, n = 1 (5(+)); X = H2O, n = 2 (6(2+))), which also contains a κ-N(5)-Ru(II) coordination environment, and to the newly synthesized [Ru(II)(PY4Im)X](n+) complexes (X = Cl, n = 1 (7(+)); X = H2O, n = 2 (8(2+))), which possess an electron-rich κ-N(4)C-Ru(II) site due to the replacement of a pyridyl group by an imidazolic carbene.

  20. ‘Horror vacui’ or topological in-out isomerism in perhydrogenated fullerenes: C60H60 and monoalkylated perhydrogenated fullerenes

    Science.gov (United States)

    Dodziuk, Helena; Nowinski, Krzysztof

    1996-02-01

    In endohedral chemistry, one of the exciting prospects offered by the cage-like structure of fullerenes, several aspects of the calculations on in-out isomerism of perhydrogenated fullerene and their consequences went unnoticed, e.g. the topological character of the isomerism, the instability of C 60F 60, which was thought to revolutionize industry as an ideal lubricant, as well as the possibility of in-out isomerism in alkylated fulleranes. Molecular mechanics calculations indicate that for smaller alkyl groups the 'in' isomer is significantly more stable extending the possibility of endohedral fullerene chemistry. C 60H 60 and its derivatives can be considered as examples of a manifestation of the ancient 'horror vacui' concept.

  1. Nuclear Quadrupole Hyperfine Structure in HC14N/H14NC and DC15N/D15NC Isomerization: A Diagnostic Tool for Characterizing Vibrational Localization

    CERN Document Server

    Wong, Bryan M

    2010-01-01

    Large-amplitude molecular motions which occur during isomerization can cause significant changes in electronic structure. These variations in electronic properties can be used to identify vibrationally-excited eigenstates which are localized along the potential energy surface. This work demonstrates that nuclear quadrupole hyperfine interactions can be used as a diagnostic marker of progress along the isomerization path in both the HC14N/H14NC and DC15N/D15NC chemical systems. Ab initio calculations at the CCSD(T)/cc-pCVQZ level indicate that the hyperfine interaction is extremely sensitive to the chemical bonding of the quadrupolar 14N nucleus and can therefore be used to determine in which potential well the vibrational wavefunction is localized. A natural bonding orbital analysis along the isomerization path further demonstrates that hyperfine interactions arise from the asphericity of the electron density at the quadrupolar nucleus. Using the CCSD(T) potential surface, the quadrupole coupling constants of...

  2. Excited electronic state decomposition mechanisms of clusters of dimethylnitramine and aluminum

    Indian Academy of Sciences (India)

    Anupam Bera; Atanu Bhattacharya

    2015-01-01

    In this report, electronically non-adiabatic decomposition pathways of clusters of dimethylnitramine and aluminum (DMNA-Al and DMNA-Al2) are discussed in comparison to isolated dimethylnitramine (DMNA). Electronically excited state processes of DMNA-Al and DMNA-Al2 are explored using the complete active space self-consistent field (CASSCF) and the restricted active space self-consistent field (RASSCF) theories, respectively. Similar to the nitro-nitrite isomerization reaction pathway of DMNA, DMNA-Al clusters also exhibit isomerization pathway. However, it involves several other steps, such as, first Al-O bond dissociation, then N-N bond dissociation followed by isomerization and finally NO elimination. Furthermore, DMNA-Al clusters exhibit overall exothermic decomposition reaction pathway and isolated DMNA shows overall endothermic reaction channel.

  3. New Vistas of the Structure of Neutron-Rich Nuclei - Single Particle States and g-FACTORS

    Science.gov (United States)

    Ramayya, A. V.; Hamilton, J. H.; Luo, Y. X.; Zhu, S. J.; Hwang, J. K.; Rasmussen, J. O.; Ter-Akopian, G. M.; Daniel, A. V.; Brewer, N.; Oganessian, Y.

    2012-01-01

    Prompt γ-γ-γ coincidence studies of neutron-rich nuclei populated in the spontaneous fission of 252Cf led to the discoveries of many important processes like neutron-less binary and ternary fragmentation in spontaneous fission, binary and ternary hot fission modes, hyper-deformation, cluster radioactivity and quasi-molecular states in ternary fission. The high statistics data, 5.7 × 1011 triples and higher folds, opened up discoveries of new band structures and significant extensions of previously known bands. These data were used to measure the angular correlations of cascades of γ-rays from the excited states of neutron-rich fission fragments stopped in an unmagnetized iron foil. By using this γ-γ angular correlation technique, the single particle configurations of the known rotational bands were assigned and confirmed in the present work. In other words, the multipole mixing ratios of ΔI=1 transitions in the rotational bands were measured. These experimental mixing ratios are compred with the theoretical ones of particle and axial-rotor model. The configuration of the ground states in 109,111Ru were, for the first time, assigned. And magnetic g-factors of excited states in even-even neutron-rich nuclei were meaured, too. Two sets of ΔI=1 alternating parity doublets with opposite parities were observed in Ba and Ce isotopes. The B(E1)/B(E2) branching ratios and D0 values may indicate that the octupole correlations are strong in Ba and Ce isotopes because of the Z=56 and N=88 octupole shell gaps. High-spin, even-parity bands in neutron-rich 108,110,112Ru nuclei indicate two-phonon quasi-gamma bands in 110,112Ru.

  4. Excitation of the isomeric ^{229m}Th nuclear state via an electronic bridge process in ^{229}Th^+

    CERN Document Server

    Porsev, S G; Peik, E; Tamm, Chr

    2010-01-01

    We consider the excitation of the nuclear transition ^{229g}Th - ^{229m}Th near 7.6 eV in singly ionized thorium via an electronic bridge process. The process relies on the excitation of the electron shell by two laser photons whose sum frequency is equal to the nuclear transition frequency. This scheme allows to determine the nuclear transition frequency with high accuracy. Based on calculations of the electronic level structure of Th^+ which combine the configuration-interaction method and many-body perturbation theory, we estimate that a nuclear excitation rate in the range of 10 s^{-1} can be obtained using conventional laser sources.

  5. TAGS measurements of 100Nb ground and isomeric states and 140Cs for neutrino physics with the new DTAS detector

    Directory of Open Access Journals (Sweden)

    Guadilla V.

    2017-01-01

    Full Text Available In this work we report on total absorption γ-ray spectroscopy measurements of the β decay of fission products that are important contributors to the antineutrino spectrum. The experiment was performed at IGISOL as a part of a campaign of measurements with the new DTAS spectrometer. Preliminary results of the analysis of the β decay of 100Nb,100mNb and 140Cs are presented.

  6. Mechanism responsible for D-transposition of the great arteries: Is this part of the spectrum of right isomerism?

    Science.gov (United States)

    Nakajima, Yuji

    2016-09-01

    D-transposition of the great arteries (TGA) is one of the most common conotruncal heart defects at birth and is characterized by a discordant ventriculoarterial connection with a concordant atrioventricular connection. The morphological etiology of TGA is an inverted or arrested rotation of the heart outflow tract (OFT, conotruncus), by which the aorta is transposed in the right ventral direction to the pulmonary trunk. The rotational defect of the OFT is thought to be attributed to hypoplasia of the subpulmonic conus, which originates from the left anterior heart field (AHF) residing in the mesodermal core of the first and second pharyngeal arches. AHF, especially on the left, at the early looped heart stage (corresponding to Carnegie stage 10-11 in the human embryo) is one of the regions responsible for the impediment that causes TGA morphology. In human or experimentally produced right isomerism, malposition of the great arteries including D-TGA is frequently associated. Mutations in genes involving left-right (L-R) asymmetry, such as NODAL, ACTRIIB and downstream target FOXH1, have been found in patients with right isomerism as well as in isolated TGA. The downstream pathways of Nodal-Foxh1 play a critical role not only in L-R determination in the lateral plate mesoderm but also in myocardial specification and differentiation in the AHF, suggesting that TGA is a phenotype in heterotaxia as well as the primary developmental defect of the AHF.

  7. Kinetic studies on the conformational isomerization reaction of the four diastereomers of beta,gamma-bidentate CrATP.

    Science.gov (United States)

    Gruys, K J; Gregory, P R; Schuster, S M

    1986-09-01

    The rates of the conformational isomerization reaction of the diastereomers of beta,gamma-bidentate CrATP were studied as a function of pH, buffer concentration, ionic strength, and temperature. The progress of the reaction was monitored by quenching the reaction at various times, and then isolating the individual diastereomers and quantitating the percent of each. This was accomplished using the reverse-phase high-performance liquid chromatography separation technique developed in this laboratory [K. J. Gruys, and S. M. Schuster, Anal. Biochem. 125, 66-73 (1982)]. The rate constants for this isomerization were then determined by obtaining the best computer fit of the data to a reversible binary mechanism (i.e., A in equilibrium B) using interative descent methods. The reaction rate was shown to be dependent on pH, temperature, and ionic strength, but independent of buffer concentration. Keq. constants were independent of all variables except ionic strength. The results from this study are interpreted in terms of a reaction mechanism involving a preequilibrium ionization of the diastereomers followed by a rate-limiting interconversion process.

  8. Surface chemistry and catalytic performance of amorphous NiB/Hβ catalyst for n-hexane isomerization

    Science.gov (United States)

    Chen, Jinshe; Cai, Tingting; Jing, Xiaohui; Zhu, Lijun; Zhou, Yulu; Xiang, Yuzhi; Xia, Daohong

    2016-12-01

    The amorphous NiB nanoparticles were synthesized and a novel type of NiB/Hβ catalyst was prepared for the isomerization of n-hexane. The optimum preparation conditions were investigated and the effect of preparation conditions on the surface chemistry information of catalysts was characterized by XRD, N2 sorption studies, XPS, TPD and other related means. It was demonstrated that the loading amounts of NiB have effect on textural properties and the acid properties of surface. The loading amounts of NiB were also related to the amount of strong Lewis acid sites and the ratios of weak acid to strong acid of samples. Meanwhile, calcination temperatures of samples were closely associated with the structure of active components that function as metal centers. When the loading amount of NiB was 5 wt.% and calcination temperature was 200 °C, the catalyst had proper surface acidity sites and metal active sites to provide suitable synergistic effects. The mechanism for n-hexane isomerization was also investigated and the existence of unique structure of Bsbnd Nisbnd H was proved, which could provide good hydrogenation-dehydrogenation functions.

  9. 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.

  10. 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.)

  11. Titanium-Beta Zeolites Catalyze the Stereospecific Isomerization of D-Glucose to L-Sorbose via Intramolecular C5-C1 Hydride Shift

    Energy Technology Data Exchange (ETDEWEB)

    Gounder, Rajamani [California Inst. of Technology (CalTech), Pasadena, CA (United States); Davis, Mark E. [California Inst. of Technology (CalTech), Pasadena, CA (United States)

    2013-06-03

    Pure-silica zeolite beta containing Lewis acidic framework Ti4+ centers (Ti-Beta) is shown to catalyze the isomerization of D-glucose to L-sorbose via an intramolecular C5–C1 hydride shift. Glucose–sorbose isomerization occurs in parallel to glucose–fructose isomerization on Ti-Beta in both water and methanol solvents, with fructose formed as the predominant product in water and sorbose as the predominant product in methanol (at 373 K) at initial times and over the course of >10 turnovers. Isotopic tracer studies demonstrate that 13C and D labels placed respectively at the C1 and C2 positions of glucose are retained respectively at the C6 and C5 positions of sorbose, consistent with its formation via an intramolecular C5–C1 hydride shift isomerization mechanism. This direct Lewis acid-mediated pathway for glucose–sorbose isomerization appears to be unprecedented among heterogeneous or biological catalysts and sharply contrasts indirect base-mediated glucose–sorbose isomerization via 3,4-enediol intermediates or via retro-aldol fragmentation and recombination of sugar fragments. Measured first-order glucose–sorbose isomerization rate constants (per total Ti; 373 K) for Ti-Beta in methanol are similar for glucose and glucose deuterated at the C2 position (within a factor of ~1.1), but are a factor of ~2.3 lower for glucose deuterated at each carbon position, leading to H/D kinetic isotope effects expected for kinetically relevant intramolecular C5–C1 hydride shift steps. Optical rotation measurements show that isomerization of D-(+)-glucose (92% enantiomeric purity) with Ti-Beta in water (373 K) led to the formation of L-(-)-sorbose (73% enantiomeric purity) and D-(-)-fructose (87% enantiomeric purity) as the predominant stereoisomers, indicating that stereochemistry is preserved at carbon centers not directly involved in intramolecular C5–C1 or C2–C1 hydride shift steps, respectively. This new Lewis acid

  12. Isomeric yield ratios of the {sup 90}Zr({gamma},n){sup 88m,g}Zr reaction up the giant dipole resonance

    Energy Technology Data Exchange (ETDEWEB)

    Bodrov, I.V.; Davydov, M.G.; Rakhmanov, I.B. [Rostov State Univ., Rostov-na-Donu (Russian Federation)] [and others

    1994-08-01

    The isomeric yield ratios Y{sub m}/Y{sub g} of the {sup 90}Zr({gamma},n){sup 88m,g}Zr reaction are measured in the energy range from 13 to 21 MeV with a step of 0.5 MeV. The experimental isomeric ratios are compared with the data obtained by other authors and with the results of theoretical calculations based on the statistical theory and on the model of {open_quotes}semidirect{close_quotes} decay of the giant dipole resonance. 30 refs., 1 fig., 2 tabs.

  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. 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

    Energy Technology Data Exchange (ETDEWEB)

    Wernisch, Stefanie, E-mail: stefanie.wernisch@univie.ac.at [Institute for Analytical Chemistry, University of Vienna, Währinger Straße 38, A-1090 Vienna (Austria); Trapp, Oliver, E-mail: trapp@oci.uni-heidelberg.de [Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg (Germany); Lindner, Wolfgang, E-mail: wolfgang.lindner@univie.ac.at [Institute for Analytical Chemistry, University of Vienna, Währinger Straße 38, A-1090 Vienna (Austria)

    2013-09-17

    Graphical abstract: -- Highlights: •X-Pro peptides produce interconverting elution profiles on zwitterionic stationary phases. •The cis–trans isomerization rate in solution is lower than in the chromatographic system. •Cinchona-based zwitterionic selectors apparently lower the isomerization barrier. •Rotamer separation is feasible <0 °C, enantiomer separation above room temperature. -- Abstract: 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.

  15. Estudio teórico de la isomerización del ácido maleico en ácido fumárico: un enfoque basado en el concepto de superficie de energía potencial Theoretical study of the isomerization of maleic acid into fumaric acid: an approach based on the concept of potential energy surface

    Directory of Open Access Journals (Sweden)

    Ricardo Ugarte

    2010-01-01

    Full Text Available A comparative study based on potential energy surfaces (PES of 2-butanedioic and hypothetic 2-butanedioic/HCl acids is useful for understanding the maleic acid isomerization. The PES enables locating conformers of minimum energy, intermediates of reactions and transition states. From contour diagrams, a set of possible reaction paths are depicted interconnecting the proposed structures. The study was carried out in absentia and in the presence of the catalyst (HCl, using an solvatation model provided by the Gaussian software package. Clearly, the effect of HCl is given by new reaction paths with lower energetic barriers in relation to the reaction without catalyzing.

  16. Probing Ir-Induced Isomerization of a Model Pentapeptide in a Cryo-Cooled Ion Trap Using Ir-Uv Double Resonance

    Science.gov (United States)

    Harrilal, Christopher P.; DeBlase, Andrew F.; Fischer, Joshua L.; Lawler, John T.; McLuckey, Scott A.; Zwier, Timothy S.

    2017-06-01

    In the past decade, infrared and ultraviolet spectroscopy in cryo-cooled ion traps have become workhorse techniques to characterize the gas-phase 3D structures of biological ions. Often, multiple conformers of a single molecular ion are observed. While slow collisional cooling should result in funneling of many structures into a single minimum, recent studies show evidence for the kinetic trapping of entropically-favored structures near room temperature when these species are cooled to about 10K. In order to elucidate how the initial population fractionates during the cooling process, we use a variety of conformer specific IR-UV double resonance techniques to measure population distributions of the peptide ion [YGPAA+H]^{+} in the gas phase at 10K. Previous studies conducted in our lab show the YGPAA peptide adopts two spectroscopically distinct conformers which differ principally in the cis/trans configuration of the carboxylic acid group at the C-terminus. By using IR-UV hole filing spectroscopy (HFS) and population transfer spectroscopy (PTS) we demonstrate the ability to selectively excite and interconvert between conformations and to quantitatively measure the distribution of conformer populations within the ion trap. Experimentally, we find a 65:35 ratio for the trans:cis conformer population. These conformers are connected through a single calculated transition state, allowing intramolecular isomerization rates and equilibrium population distributions to be calculated by Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The relationship between the observed population ratio and the temperature-dependent equilibrium constant will be discussed.

  17. Enhanced E/Z Isomerization of (All-E)-lycopene by Employing Iron(III) Chloride as a Catalyst.

    Science.gov (United States)

    Honda, Masaki; Kawana, Takahiro; Takehara, Munenori; Inoue, Yoshinori

    2015-07-01

    Catalytic isomerization of (all-E)-lycopene to Z-isomers using iron(III) chloride was investigated and optimized under various conditions of solvents, concentrations of iron(III) chloride, and reaction temperatures. The total contents of Z-isomers converted were higher in the order of CH2 Cl2 (78.4%) > benzene (61.4%) > acetone (51.5%) > ethyl acetate (50.8%) at 20 °C for 3 h using 1.0 × 10(-3) mg/mL iron(III) chloride for 0.1 mg/mL (all-E)-lycopene. However, the decomposition of lycopene was markedly accelerated in CH2 Cl2 : the remaining lycopene after the reaction for 3 h and 12 h was only 79.4% and 47.5%, respectively. As the concentration of catalyst increased in acetone, the Z-isomerization ratio of lycopene increased to more than 80%, followed by rapid degradation of lycopene to undetectable levels using >4.0 × 10(-3) mg/mL iron(III) chloride with the above concentration of (all-E)-lycopene. Finally, greater isomerization (79.9%) was attained at 60 °C in acetone for 3 h in the presence of 1.0 × 10(-3) mg/mL iron(III) chloride, largely without decomposition of lycopene (remaining ratio of total amount of lycopene isomers after the reaction, 96.5%). As iron(III) chloride has found general use as a food additive for iron fortification and acetone is also widely used in the food field, this method can be applied to the food and beverage processing industry. The dietary intake of lycopene, a natural red pigment found in brightly colored vegetables and fruits such as tomatoes and watermelons, has been reported to lower the risk of some diseases, including cancer. Lycopene molecules occur naturally in a long and “straight” shape, but on the other hand lycopene molecules with “bent” forms are highly absorbed by living cells, and showed good antioxidant activity. This study has demonstrated the efficient production of the “bent” lycopene using ionic iron as an accelerator, which is often contained in nutritional supplements. © 2015 Institute of Food

  18. 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

  19. Synthesis of Oxacyclic Scaffolds via Dual Ruthenium Hydride/Brønsted Acid‐Catalyzed Isomerization/Cyclization of Allylic Ethers

    DEFF Research Database (Denmark)

    Ascic, Erhad; Ohm, Ragnhild Gaard; Petersen, Rico;

    2014-01-01

    A ruthenium hydride/Brønsted acid‐catalyzed tandem sequence is reported for the synthesis of 1,3,4,9‐tetrahydropyrano[3,4‐b]indoles (THPIs) and related oxacyclic scaffolds. The process was designed on the premise that readily available allylic ethers would undergo sequential isomerization, first ...

  20. Influence of the isomeric composition of the acceptor on the performance of organic bulk heterojunction P3HT:bis-PCBM solar cells

    NARCIS (Netherlands)

    Bouwer, R.K.M.; Wetzelaer, G.-J.A.H.; Blom, P.W.M.; Hummelen, J.C.

    2012-01-01

    We synthesized three isomeric subpopulations of bisadduct analogues of [6,6]-phenyl-C61-butyric acid methyl ester (bis-PCBM) via tether-directed control. Bulk heterojunction solar cells prepared using these isomers together with poly(3-hexylthiophene) (P3HT) resulted in an increase of Jsc from 72.4

  1. 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

    Isomerism, also known as heterotaxy, is a clinical entity that impacts multiple organ systems both anatomically and functionally. The airways and lungs are involved in a great number of these patients, leading to increased sinopulmonary symptoms, increased need for oxygenation, and increased post...

  2. Effective Ion Mobility Peak Width as a New Isomeric Descriptor for the Untargeted Analysis of Complex Mixtures Using Ion Mobility-Mass Spectrometry

    Science.gov (United States)

    Farenc, Mathilde; Paupy, Benoit; Marceau, Sabrina; Riches, Eleanor; Afonso, Carlos; Giusti, Pierre

    2017-07-01

    Ion mobility coupled with mass spectrometry was proven to be an efficient way to characterize complex mixtures such as petroleum samples. However, the identification of isomeric species is difficult owing to the molecular complexity of petroleum and no availability of standard molecules. This paper proposes a new simple indicator to estimate the isomeric content of highly complex mixtures. This indicator is based on the full width at half maximum (FWHM) of the extracted ion mobility peak measured in millisecond or square angstrom that is corrected for instrumental factors such as ion diffusion. This value can be easily obtained without precisely identifying the number of isomeric species under the ion mobility peaks. Considering the Boduszynski model, the ion mobility profile for a particular elemental composition is expected to be a continuum of various isomeric species. The drift time-dependent fragmentation profile was studied and confirmed this hypothesis, a continuous evolution of the fragmentation profile showing that the larger alkyl chain species were detected at higher drift time values. This new indicator was proven to be a fast and efficient method to compare vacuum gas oils for which no difference was found using other analytical techniques.

  3. The 181Ta(7Li,5n)183Os reaction: Measurement and analysis of the excitation function and isomeric cross-section ratios

    Science.gov (United States)

    Ismail, M.; Sharma, R. P.; Rashid, M. H.

    1998-03-01

    Excitation function and isomeric cross-section ratios for the production of 183Osm,g by 7Li-induced reactions on 181Ta are obtained from the measurements of the residual activities by the conventional stacked-foils technique from threshold to 50 MeV. The excitation function and isomeric cross-section ratios for nuclear reaction 181Ta(7Li,5n)183Osm,g are compared with the theoretical statistical model calculation by using the ALICE/91, STAPRE, and CASCADE codes. In the energy range of the present measurement the excitation functions are fitted fairly well by both the geometry dependent hybrid (GDH) model and the hybrid model of Blann with initial exciton number n0=7 (nn=4, np=3, nh=0) using the ALICE/91 code. The experimental isomeric cross-section ratios are also reproduced fairly well by the calculation using the STAPRE code. However, the CASCADE code calculations slightly underpredict the cross section but reproduce the shape. In general, the statistical model under a suitable set of global assumptions, can reproduce the excitation function as well as isomeric cross-section ratios.

  4. Influence of the isomeric composition of the acceptor on the performance of organic bulk heterojunction P3HT:bis-PCBM solar cells

    NARCIS (Netherlands)

    Bouwer, R.K.M.; Wetzelaer, G.-J.A.H.; Blom, P.W.M.; Hummelen, J.C.

    2012-01-01

    We synthesized three isomeric subpopulations of bisadduct analogues of [6,6]-phenyl-C61-butyric acid methyl ester (bis-PCBM) via tether-directed control. Bulk heterojunction solar cells prepared using these isomers together with poly(3-hexylthiophene) (P3HT) resulted in an increase of Jsc from 72.4

  5. Synthesis of 2-azaanthracenes via a sequential Sonogashira coupling/alkynyl imine-allenyl imine isomerization/aza-Diels-Alder/elimination-aromatization reaction.

    Science.gov (United States)

    Cao, Jian; Yang, Xiongfa; Hua, Xilin; Deng, Yuan; Lai, Guoqiao

    2011-02-04

    An interesting sequential Sonogashira coupling/alkynyl imine-allenyl imine isomerization/aza-Diels-Alder/elimination-aromatization reaction, providing a facile synthesis of substituted 2-azaanthracenes from 1,6-diynes and imidoyl chlorides, is reported. The easy procedure accessing the products efficiently from readily available starting materials may imply a potential synthetic application.

  6. 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…

  7. 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

  8. Impact of the Solvent on the Conformational Isomerism of Calix[4]arenes:  A Study Based on Continuum Solvation Models

    NARCIS (Netherlands)

    Aleman, Carlos; Otter, den W.K.; Tolpekina, T.V.; Briels, W.J.

    2004-01-01

    The influence of solvation on the conformational isomerism of calix[4]arene and p-tert-butylcalix[4]arene has been investigated by using the continuum model reported by Miertus, Scrocco, and Tomasi (MST). The quantum mechanical (QM) and semiclassical (SC) formalisms of the MST model have been consid

  9. Analysis of gamma irradiated pepper constituents, 4. Analysis of piperine and its isomers by reversed phase HPLC and effect of gamma irradiation on isomerization of piperine

    Energy Technology Data Exchange (ETDEWEB)

    Takagi, Kazuko; Ochiai, Junko; Okuyama, Tsuneo

    1988-11-01

    A separation method for piperine and its isomers (isopiperine, isochavicine and chavicine) was investigated. These isomers were produced from piperine with irradiation. This reaction is photochemical isomerization. Piperine and its isomers were separated on a reversed phase C/sub 8/ (LiChrospher 300 RP-8 10 um 0.4 I.D. x 0.4 cm and LiChrosorb RP-8 SelectB 0.4 I.D. x 25 cm) column with a mixture of 0.1% trifluoroacetic acid (TFA) in water and 75% acetonitrile-0.1% TFA in water (92 : 8) and detected at 210 nm, 280 nm. By this method, four peaks derivded from piperine and its isomers were recognized. Piperine was identified by addition of piperine as a internal standard. Unknown peaks were fractionated by chromatography on the column for NMR structural identification. Isochavicine was identified by NMR. And the other peaks were presumed by the fact that chavicine dose not produce from piperine with mild irradiation condition. In contrast of photochemical isomerization, the effect of gamma irradiation on isomerization of piperine was investigated by HPLC analysis. Gamma irradiation had no effect on the isomerization of piperine.

  10. Kinetics of Light-Induced cis-trans Isomerization of Four Piperines and their Levels in Ground Black Peppers as Determined by HPLC and LC/MS

    Science.gov (United States)

    The pungent compound piperine, a secondary metabolite present in black, white, and green pepper fruit, undergoes light-induced isomerizations. To facilitate studies in this area, an HPLC method has been developed for analysis and isolation of the following four possible piperine photo-induced isomer...

  11. Definitive evidence for the existence of isomeric chlorophenyl radicals (C6H4Cl) from charge inversion mass spectrometry and DFT calculations

    Science.gov (United States)

    Hayakawa, Shigeo; Matsubara, Hiroshi; Kawamura, Yoshiaki; Iwamoto, Kenichi

    2007-05-01

    Free radical species are much more reactive than stable molecules, and so usually exist only as transient intermediates in chemical reactions. Charge inversion mass spectrometry using alkali metal targets is an effective method for determining the structure and dissociation processes of radicals, and can also enable differentiation between isomeric forms of compounds whose parent ions have similar mass spectra and similar collisionally activated dissociation spectra, such as the isomers of dichlorobenzene and chlorophenol. The charge inversion process using alkali metal targets proceeds via near-resonant neutralization, followed by spontaneous dissociation of the excited neutrals, and then endothermic negative ion formation. In the normalized charge inversion spectra of ortho-, meta-, and para-dichlorobenzene (C6H4Cl2) measured in this work, the intensities of the peaks associated with chlorine anions (Cl-) are almost same for each of the isomers, whereas the intensities of the peaks associated with the chlorophenyl anions (C6H4Cl-) display a strong dependence on the isomeric structure of the parent compound. The similarities of the Cl- ion peak intensities indicate that neutralization cross-sections and branching ratios to produce Cl radicals are the same for each of the isomeric precursor C6H4Cl2+ ions. The strong isomer-dependence of the peak intensities of C6H4Cl- anions suggests that the chlorophenyl radicals (C6H4Cl) formed from C6H4Cl2 by loss of Cl do not undergo isomerization, and that the electron transfer cross-sections to form the negative ions are strongly isomer-dependent. Density functional theory (DFT) calculations on the o-, m-, and p-C6H4Cl radicals show that the barriers to isomerization are in excess of 2.8 eV, and these high isomerization barriers are believed to be the reason for the absence of isomerization among the C6H4Cl radicals during the charge inversion process. Calculated adiabatic electron affinities and vertical electron affinities

  12. Theoretical study on the formation of tetraoxygen conformational isomerism in the CO 2 with O 3 reaction

    Science.gov (United States)

    Goodarzi, Moein; Piri, Farideh; Hajari, Nasim; Karimi, Leila

    2010-10-01

    The reaction mechanism of CO 2 with O 3 on the singlet potential energy surface has been investigated at the CBS-QB3//B3LYP/6-311++G(3df, 3pd) level of theory. The reactants are initially associated with adducts IN1 (OOO-OCO) and IN2 (OC-cyclic O 4) in a barrier-less process. Then, adducts undergo isomerization and dissociation processes to produce P 1 (CO + 2 3O 2) and P 2 (CO 3 + 3O 2) with two different mechanisms. The calculated results show that there is no favorable pathway for the formation of these two products in the atmospheric reaction of CO 2 with O 3.

  13. Elemental isomerization processes for a photochromic diarylethene film based on carrier injection toward all-electrically operable organic memory

    Science.gov (United States)

    Tsujioka, Tsuyoshi; Yamamoto, Kazuki

    2016-06-01

    We propose a basic concept of all-electrically operable organic memory with a photochromic diarylethene (DAE) film based on a transistor structure, in which the DAE memory layer is recordable, erasable, and nondestructively readable by an electrical method. To realize such memory, we investigated each elementary process for recording, erasing, or nondestructive reading by current injection and electrostatic methods for the DAE layer. Both ring-opening and ring-closure isomerization reactions were confirmed for the injection of both carriers (electrons and holes). Hole injection induced ring-opening reaction only. These reaction modes can be utilized in the recording and erasing modes. Since no reactions for electron injection and current modulation based on photoisomerization were observed, electron current injection can be applied to nondestructive readout.

  14. Atmospheric pressure ionization and gas phase ion mobility studies of isomeric dihalogenated benzenes using different ionization techniques

    Science.gov (United States)

    Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

    2004-03-01

    Ion mobility spectrometry (IMS) featuring different ionization techniques was used to analyze isomeric ortho-, meta- and para-dihalogenated benzenes in order to assess how structural features affect ion formation and drift behavior. The structure of the product ions formed was investigated by atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and IMS-MS coupling. Photoionization provided [M]+ ions for chlorinated and fluorinated compounds while bromine was cleaved from isomers of dibromobenzene and bromofluorobenzene. This ionization technique does not permit the different isomers to be distinguished. Comparable ions and additional clustered ions were obtained using 63Ni ionization. Depending on the chemical constitution, different clustered ions were observed in ion mobility spectra for the separate isomers of dichlorobenzene and dibromobenzene. Corona discharge ionization permits the most sensitive detection of dihalogenated compounds. Only clustered product ions were obtained. Corona discharge ionization enables the classification of different structural isomers of dichlorobenzene, dibromobenzene and bromofluorobenzene.

  15. Resolution and quantification of isomeric fatty acids by silver ion HPLC: fatty acid composition of aniseed oil (Pimpinella anisum, Apiaceae).

    Science.gov (United States)

    Denev, Roumen V; Kuzmanova, Ivalina S; Momchilova, Svetlana M; Nikolova-Damyanova, Boryana M

    2011-01-01

    A silver ion HPLC procedure is described that is suitable to determine the fatty acid composition of plant seed oils. After conversion of fatty acids to p-methoxyphenacyl derivatives, it was possible to achieve baseline resolution of all fatty acid components with 0 to 3 double bonds, including the positionally isomeric 18:1 fatty acids oleic acid (cis 9-18:1), petroselinic acid (cis 6-18:1), and cis-vaccenic acid (cis 11-18:1), in aniseed oil (Pimpinella anisum, Apiaceae) by a single gradient run on a single cation exchange column laboratory converted to the silver ion form. The UV detector response (280 nm) was linearly related to the fatty acid concentration in the range 0.01 to 3.5 mg/mL.

  16. 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.

  17. The role of nonbonding interactions and the presence of fluoride on the conformational isomerism of 1,2-ethanediol

    Science.gov (United States)

    Silva, Weslley G. D. P.; Silla, Josué M.; Cormanich, Rodrigo A.; Fernandes, Sergio A.; Freitas, Matheus P.

    2016-07-01

    This work reports the analysis of the effects ruling the conformational preference of 1,2-ethanediol (1,2-ED) using theoretical calculations, since there is no general consensus about the role of intramolecular hydrogen bond on the conformational isomerism of 1,2-ED. While the predominance of the gauche conformers along with the Osbnd Csbnd Csbnd O fragment relative to the trans ones was found to be mainly due to hyperconjugation, the orientation of the hydroxyl groups is better described by a balance between low steric hindrance and high stabilization from hyperconjugation than by intramolecular hydrogen bond. Nevertheless, the presence of a fluoride anion induces a conformational change in 1,2-ED that maximizes hydrogen bonds between the fluoride and the hydroxyl groups. This effect was observed experimentally by the shift of 1H(O) and 19F NMR signals upon complexation, then suggesting that compounds containing the 1,2-ED moiety can be possible anion transporters.

  18. Characterization of isomeric VX nerve agent adducts on albumin in human plasma using liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Saeidian, Hamid; Mirkhani, Valioallah; Mousavi Faraz, Sajjad; Taghi Naseri, Mohammad; Babri, Mehran

    2015-01-01

    This study includes the characterization of isomeric VX organophosphorus adducts on albumin in human plasma using liquid chromatography-tandem mass spectrometry (LC-MS/MS). VX or its structural isomers were spiked into a vial containing plasma in order to obtain phosphorylated albumin. After pronase and trypsin digestion, the resulting solutions were analyzed to confirm adduct formation with the amino acid tyrosine on the albumin in human plasma. The LC-MS/MS experiments show that VX and its isomers can be attached to tyrosine on the albumin in human blood. Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as ethylene, formic acid and ammonia elimination and an intermolecular electrophilic aromatic substitution reaction. The proposed mechanisms for the formation of the fragments were confirmed through the analysis of fragments of deuterated adducts.

  19. Efficient Computational Research Protocol to Survey Free Energy Surface for Solution Chemical Reaction in the QM/MM Framework: The FEG-ER Methodology and Its Application to Isomerization Reaction of Glycine in Aqueous Solution.

    Science.gov (United States)

    Takenaka, Norio; Kitamura, Yukichi; Nagaoka, Masataka

    2016-03-03

    In solution chemical reaction, we often need to consider a multidimensional free energy (FE) surface (FES) which is analogous to a Born-Oppenheimer potential energy surface. To survey the FES, an efficient computational research protocol is proposed within the QM/MM framework; (i) we first obtain some stable states (or transition states) involved by optimizing their structures on the FES, in a stepwise fashion, finally using the free energy gradient (FEG) method, and then (ii) we directly obtain the FE differences among any arbitrary states on the FES, efficiently by employing the QM/MM method with energy representation (ER), i.e., the QM/MM-ER method. To validate the calculation accuracy and efficiency, we applied the above FEG-ER methodology to a typical isomerization reaction of glycine in aqueous solution, and reproduced quite satisfactorily the experimental value of the reaction FE. Further, it was found that the structural relaxation of the solute in the QM/MM force field is not negligible to estimate correctly the FES. We believe that the present research protocol should become prevailing as one computational strategy and will play promising and important roles in solution chemistry toward solution reaction ergodography.

  20. Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

    Science.gov (United States)

    Xu, Z F; Raghunath, P; Lin, M C

    2015-07-16

    The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to

  1. Quadrupole moments of Cd and Zn nuclei: When solid-state, molecular, atomic, and nuclear theory meet

    DEFF Research Database (Denmark)

    Haas, Heinz; Sauer, Stephan P. A.; Hemmingsen, Lars Bo Stegeager

    2017-01-01

    The nuclear quadrupole moment (Q) of the 5/2+ isomeric state of 111Cd, of particular importance to the interpretation of Perturbed Angular Correlation experiments in condensed matter, was determined by combining existing PAC data with high-level ab initio (CCSD(T)) calculations for Cd-dimethyl an...

  2. The population of metastable states as a probe of relativistic-energy fragmentation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Denis Bacelar, A.M. [School of Computing, Engineering and Mathematics, University of Brighton, Brighton BN2 4GJ (United Kingdom); Bruce, A.M., E-mail: alison.bruce@brighton.ac.uk [School of Computing, Engineering and Mathematics, University of Brighton, Brighton BN2 4GJ (United Kingdom); Podolyák, Zs.; Al-Dahan, N. [Department of Physics, University of Surrey, Guildford GU2 7XH (United Kingdom); Górska, M. [GSI Helmholtzzentrum für Schwerionenforschung, Planckstr 1, D-64291 Darmstadt (Germany); Lalkovski, S. [School of Computing, Engineering and Mathematics, University of Brighton, Brighton BN2 4GJ (United Kingdom); Department of Physics, University of Sofia, 1164 Sofia (Bulgaria); Pietri, S.; Ricciardi, M.V. [GSI Helmholtzzentrum für Schwerionenforschung, Planckstr 1, D-64291 Darmstadt (Germany); Algora, A. [Instituto de Física Corpuscular, CSIC, Universitat de Valencia, E-40671 Valencia (Spain); Institute of Nuclear Research of the Hungarian Academy of Sciences, P.O. Box 51, Debrecen, 4001 (Hungary); Alkhomashi, N. [Department of Physics, University of Surrey, Guildford GU2 7XH (United Kingdom); Benlliure, J. [Universidad de Santiago de Compostela, 15706 (Spain); Boutachkov, P. [GSI Helmholtzzentrum für Schwerionenforschung, Planckstr 1, D-64291 Darmstadt (Germany); Bracco, A. [Department of Physics, Università degli Studi di Milano and INFN, 20133 Milano (Italy); Calore, E. [INFN, Laboratori Nazionali di Legnaro (Italy); Casarejos, E. [University of Vigo, E-36310, Vigo (Spain); Cullen, I.J.; Deo, A.Y. [Department of Physics, University of Surrey, Guildford GU2 7XH (United Kingdom); Detistov, P. [Department of Physics, University of Sofia, 1164 Sofia (Bulgaria); Laboratorio de Radiaciones Ionizantes, Universidad de Salamanca, 37008 (Spain); and others

    2013-06-25

    Isomeric ratios have been measured for high-spin states in {sup 198,200,206,208}{sub 84}Po, {sup 208,209,210,211}{sub 85}At, {sup 210,211,212,213,214}{sub 86}Rn, {sup 208,211,212,213,214}{sub 87}Fr, {sup 210,211,212,214,215}{sub 88}Ra, and {sup 215}{sub 89}Ac following the projectile fragmentation of a 1 A GeV {sup 238}U beam by a {sup 9}Be target at GSI Helmholtzzentrum für Schwerionenforschung. The fragments were separated in the fragment separator (FRS) and identified by means of energy loss and time-of-flight techniques. They were brought to rest at the centre of the RISING gamma-ray detector array and intensities of gamma rays emitted in the decay of isomeric states with half-lives between 100 ns and 40 μs and spin values up to 55/2 ℏ were used to obtain the corresponding isomeric ratios. The data are compared to theoretical isomeric ratios calculated in the framework of the abrasion–ablation model. Large experimental enhancements are obtained for high-spin isomers in comparison to expected values.

  3. A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

    Science.gov (United States)

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

    2015-10-14

    While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

  4. Effect of solvents on the barrierless reaction in the excited state of cyanine dye

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    UV-Vis, fluorescence spectroscopy and time resolved spectroscopic technique on picosecond and femto- second scales have been utilized to investigate the effect of steric hindrance and multiple hydroxyl groups of solvents on the barrierless isomerization in excited state of 3, 3′- di(3-sulfopropyl)thiacyanine triethylaminium salt. The results show that the factors mentioned above may be responsible for a different "short-time behavior" of the bleaching signal on the ground state and nonlinear viscosity dependence of the excited-state lifetime in isopropanol and glycol. These phenomena are distinguished from the situation reported in the long-chained monohydroxyl alcohol solvents. However, the dye molecule still exhibits the analyzing- wavelength dependence of the observed fluorescence lifetime, that is, the fluorescence lifetime increases with the increasing of analyzing-wavelength. The conclusions are in agreement with those drawn from femtosecond upconversion fluorescence experiments and further exemplify the barrierless isomerization model in the excited state.

  5. Platinum and Other Transition Metal Nanoclusters (Pd, Rh) Stabilized by PAMAM Dendrimer as Excellent Heterogeneous Catalysts: Application to the Methylcyclopentane (MCP) Hydrogenative Isomerization.

    Science.gov (United States)

    Deraedt, Christophe; Melaet, Gérôme; Ralston, Walter T; Ye, Rong; Somorjai, Gabor A

    2017-03-08

    Pt, Rh, and Pd nanoclusters stabilized by PAMAM dendrimer are used for the first time in a gas flow reactor at high temperature (150-250 °C). Pt nanoclusters show a very high activity for the hydrogenation of the methylcyclopentane (MCP) at 200-225 °C with turnover freqency (TOF) up to 334 h(-1) and selectivity up to 99.6% for the ring opening isomerization at very high conversion (94%). Rh nanoclusters show different selectivity for the reaction, that is, ring opening isomerization at 175 °C and cracking at higher temperature whereas Pd nanoclusters perform ring enlargement plus dehydrogenation, while maintaining a high activity. The difference in these results as compared to unsupported/uncapped nanoparticles, demonstrates the crucial role of dendrimer. The tunability of the selectivity of the reaction as well as the very high activity of the metal nanoclusters stabilized by dendrimer under heterogeneous conditions open a new application for dendrimer catalysts.

  6. Chain folding controlled by an isomeric repeat unit: helix formation versus random aggregation in acetylene-bridged carbazole-bipyridine co-oligomers.

    Science.gov (United States)

    Divya, Kizhmuri P; Sreejith, Sivaramapanicker; Suresh, Cherumuttathu H; Philips, Divya S; Ajayaghosh, Ayyappanpillai

    2013-07-01

    An unprecedented, positional effect of the isomeric repeat unit on chain folding in donor–acceptor-linked oligomers, which contain alternating bipyridine and carbazole moieties that are connected through an acetylinic linkage, is reported. 4,4′-Linked oligomer 1 adopts an intrachain helical conformation (CD-active) in CHCl3/MeCN (20:80 v/v), whereas oligomer 2, which contains an isomeric 6,6′-linkage, forms interchain randomly coiled aggregates (CD-inactive). The substitution position plays a significant role in controlling the variations in electronic effects and dipole moments around the bipyridyl moiety, which are responsible for this observed phenomenon. Two model compounds of oligomers 1 and 2 (3 and 4, respectively) were prepared and their properties were compared. A systematic investigation of the photophysical and CD properties of these structures, as well as theoretical studies, support our conclusions.

  7. Isomeric cross-section ratios resulted from reaction (p,n) on targets {sup 100}Ru and {sup 104,106,110}Pd

    Energy Technology Data Exchange (ETDEWEB)

    Hu Bitao [Lanzhou Univ., Gansu (China). Dept. of Modern Physics; Zarubin, P.P.; Juravlev, U.U. [Faculty of Physics, Saint-Petersburg University, Saint-Petersburg (Russian Federation)

    1998-06-01

    The isomeric cross section ratios for production {sup 100mg}Rh and {sup 104mg,106mg,110mg}Ag in reaction (p,n) were measured over energy range from {proportional_to}6 MeV to {proportional_to}9 MeV. Statistical model calculations were performed for analyzing the experimental isomeric ratios and it was found that the theoretically calculated ratios agree well with our experimental results. In the present work the tendency that theoretical values will be larger than experimental results for energy above 9 MeV was indicated and the influence of the optical model parameters and the level density model was discussed. (orig.) With 6 figs., 5 tabs., 17 refs.

  8. PREPARATION OF POLYMER—SUPPORTED RCpCpTiCl2 AND APPLICATION IN CATALYTIC ISOMERIZATION OF 1,5—HEXADIENE

    Institute of Scientific and Technical Information of China (English)

    QIANYanlong; HONGKunlun; 等

    1993-01-01

    Polymer-supported RCpCpTiCl2(Cp=η5-C5H4;RCp=η5-RC5H4)have been prepared and reduced by i-C3H7MgBr in situ,then used in catalytic isomerization of 1,5-hexadiene.The isomerization of 1,5-hexadiene leads to a mixture of cyclic and linear products.The ratio of cyclic to linear product depends on the nature of the supporter and the substituent on the cyclopentadienyl ring.The former contributes the most,for example,silica supported Cp2 TiCl2 gave cyclic-linear ratio of 99/1,while for polymer-supported Cp2TiCl2 species,linear compounds are the major products and the ratio of cyclic to linear product changes with different R groups on the cyclopentadienyl ring.

  9. Measurement of isomeric-yield ratios of 109m,gPd and 115m,gCd with 50-, 60-, and 70-MeV bremsstrahlung

    Science.gov (United States)

    Rahman, Md. Shakilur; Lee, Manwoo; Kim, Kyung-Sook; Kim, Guinyun; Kim, Eunae; Cho, Moo-Hyun; Shvetshov, Valery; Khue, Pham Duc; Van Do, Nguyen

    2012-04-01

    The isomeric-yield ratios of 109m,gPd and 115m,gCd were measured by the activation method with uncollimated bremsstrahlung beams of 50-, 60-, and 70-MeV generated from an electron linear accelerator at Pohang Accelerator Laboratory. The induced activities in the irradiated foils were measured by the high-resolution γ-ray spectrometric system consisting of a high-purity germanium detector and a multichannel analyzer. The obtained isomeric-yield ratios in the formation of 109m,gPd and 115m,gCd are compared with the corresponding values found in the other experiments and the calculated values based on the statistical model code TALYS. The present results for 109m,gPd and 115m,gCd in this energy region are the first measurement.

  10. Carbon Aerogel-Supported Pt Catalysts for the Hydrogenolysis and Isomerization of n-Butane: Influence of the Carbonization Temperature of the Support and Pt Particle Size

    Directory of Open Access Journals (Sweden)

    Marta B. Dawidziuk

    2012-10-01

    Full Text Available Carbon aerogels prepared at different carbonization temperatures and with varying mesopore volumes were used as supports for Pt catalysts to study the n-C4H10/H2 reaction. Mean Pt particle size depended on the mesopore volume of the support, showing a linear decrease when the mesopore volume increased. The turnover frequency (TOF for hydrogenolysis was much higher than for isomerization in catalysts supported on carbon aerogels obtained at 900–950 °C. However, both TOF values were similar in catalysts supported on the carbon aerogel obtained at 500 °C. TOF for hydrogenolysis and isomerization were related to the mean Pt particle size in catalysts supported on carbon aerogels obtained at 900–950 °C. In addition, both reactions showed a compensation effect between the activation energy and pre-exponential factor, indicating that they have the same intermediate, i.e., the chemisorbed dehydrogenated alkane.

  11. A Novel Way to Prepare γ-Al2O3 Supported SO42-/ZrO2 Solid Superacid Catalysts for n-Butane Isomerization

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Highly active solid superacid catalysts for n-butane isomerization, SZ/Al2O3-P, were prepared by supporting SO42-/ZrO2 (SZ) on γ-Al2O3 carrier using a precipitation method.The activities of some catalysts were enhanced significantly.The activity of the most active sample, 60%SZ/Al2O3-P, was even about 2 times more active than that of the SZ catalyst.

  12. Sex pheromone of the European grapevine moth,Lobesia botrana Schiff. (Lepidoptera: Tortricidae): Synthesis and effect of isomeric purity on biological activity.

    Science.gov (United States)

    Ideses, R; Klug, J T; Shani, A; Gothilf, S; Gurevitz, E

    1982-01-01

    A short synthesis of (E, Z)-7,9-dodecadien-1-yl acetate from propargyl alcohol and 6-bromohexanol via acetylenic-allenic isomerization of the resulting bis-THP-1,9-non-2-yn-diol is described. The field test of several preparations showed that theE,E isomer does not interfere with the biological activity of the pheromone. It was found that the "crude" preparation has higher activity than purified pheromone or virgin females.

  13. Fe-catalyzed novel domino isomerization/cyclodehydration of substituted 2-[(indoline-3-ylidene)(methyl)]benzaldehyde derivatives: an efficient approach toward benzo[b]carbazole derivatives.

    Science.gov (United States)

    Paul, Kartick; Bera, Krishnendu; Jalal, Swapnadeep; Sarkar, Soumen; Jana, Umasish

    2014-04-18

    A new and efficient protocol to synthesize substituted benzo[b]carbazole derivatives has been demonstrated involving iron-catalyzed domino isomerization/cyclodehydration sequences from substituted 2-[(indoline-3-ylidene)(methyl)]benzaldehyde derivatives. The substrates could be easily made via Pd-catalyzed domino Heck-Suzuki coupling from 2-bromo-N-propargylanilide derivatives in high yields. Notably, the generality and efficiency of this two-stage domino strategy was further exemplified by the synthesis of a polycyclic benzofuran derivative.

  14. Build/Couple/Pair Strategy Combining the Petasis 3-Component Reaction with Ru-Catalyzed Ring-Closing Metathesis and Isomerization

    DEFF Research Database (Denmark)

    Ascic, Erhad; Le Quement, Sebastian Thordal; Ishøy, Mette;

    2012-01-01

    A “build/couple/pair” pathway for the systematic synthesis of structurally diverse small molecules is presented. The Petasis 3-component reaction was used to synthesize anti-amino alcohols displaying pairwise reactive combinations of alkene moieties. Upon treatment with a ruthenium alkylidene-cat......-catalyst, these dienes selectively underwent ring-closing metathesis reactions to form 5- and 7-membered heterocycles and cyclic aminals via a tandem isomerization/N-alkyliminium cyclization sequence....

  15. Four-Quasiparticle High-K States in Neutron-Deficient Lead and Polonium Nuclei

    Science.gov (United States)

    Shi, Yue; Xu, Furong

    2012-06-01

    Configuration-constrained potential energy surface calculations have been performed to investigate four-quasiparticle high-K configurations in neutron-deficient lead and polonium isotopes. A good agreement between the calculations and the experimental data has been found for the excitation energy of the observed Kπ = 19- state in 188Pb. Several lowly excited high-K states are predicted, and the large oblate deformation and low energy indicate high-K isomerism in these nuclei.

  16. 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.

  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. Modulation of an active-site cysteine pKa allows PDI to act as a catalyst of both disulfide bond formation and isomerization.

    Science.gov (United States)

    Karala, Anna-Riikka; Lappi, Anna-Kaisa; Ruddock, Lloyd W

    2010-03-05

    Protein disulfide isomerase (PDI) plays a central role in disulfide bond formation in the endoplasmic reticulum. It is implicated both in disulfide bond formation and in disulfide bond reduction and isomerization. To be an efficient catalyst of all three reactions requires complex mechanisms. These include mechanisms to modulate the pK(a) values of the active-site cysteines of PDI. Here, we examined the role of arginine 120 in modulating the pK(a) values of these cysteines. We find that arginine 120 plays a significant role in modulating the pK(a) of the C-terminal active-site cysteine in the a domain of PDI and plays a role in determining the reactivity of the N-terminal active-site cysteine but not via direct modulation of its pK(a). Mutation of arginine 120 and the corresponding residue, arginine 461, in the a' domain severely reduces the ability of PDI to catalyze disulfide bond formation and reduction but enhances the ability to catalyze disulfide bond isomerization due to the formation of more stable PDI-substrate mixed disulfides. These results suggest that the modulation of pK(a) of the C-terminal active cysteine by the movement of the side chain of these arginine residues into the active-site locales has evolved to allow PDI to efficiently catalyze both oxidation and isomerization reactions.

  19. Isomerization and epimerization of the aspartyl tetrapeptide Ala-Phe-Asp-GlyOH at pH 10-A CE study.

    Science.gov (United States)

    Brückner, Christin; Bunz, Svenja-Catharina; Imhof, Diana; Neusüss, Christian; Scriba, Gerhard K E

    2013-09-01

    Isomerization and enantiomerization of Asp in the tetrapeptide Ala-Phe-Asp-GlyOH are studied at pH 10 and 80°C as well as 25°C. CE-MS allowed the distinction between α-Asp and β-Asp linkages in degradation products based on the ratio of the b and y fragment ions. Besides isomerization and enantiomerization of Asp, enantiomerization of Ala and Phe was also observed at both temperatures by chiral amino acid HPLC analysis using Marfey's reagent for derivatization. The rate of enantiomerization of the amino acids proceeded in the order Asp > Ala > Phe. The CE assay was validated with respect to linearity, LOQ, LOD, and precision and employed to characterize the time course of the degradation of the tetrapeptide upon incubation in borate buffer, pH 10. Isomerization to β-Asp peptides was identified as the major degradation reaction. The configuration of Asp or Ala affected the half-life of the starting peptide to a minor extent but did not influence the distribution of the individual products under equilibrium conditions at 80°C. Degradation at 25°C proceeded very slowly so that the equilibrium was not reached after 245 days. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Isomeric decay of sup 6 sup 7 Fe --Evidence for deformation

    CERN Document Server

    Sawicka, M; Daugas, J M; De France, G; Lewitowicz, M; Matea, I; Grawe, H; Hellström, M; Cwiok, S; Balabanski, D L; Béraud, R; Bingham, C; Borcea, C; Georgiev, G; aGórska, M; Grzywacz, R; Hass, M; Mach, H; Neyens, G; Oleari, C; Page, R D; Pfützner, M; Podolyák, Z; Rykaczewski, K; Stanoiu, M; Zylicz, J

    2003-01-01

    Decay-spectroscopy study of the sup 6 sup 7 sup m Fe isomer has been performed at GANIL. This isomer is found to have an energy of 387 keV and a half-life of 75(21) mu s. An intermediate excited state is introduced at 367 keV. The results are interpreted in terms of various nuclear models, and a deformed shape is inferred for sup 6 sup 7 Fe. (orig.)