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Sample records for 94ag isomeric states

  1. Isomeric states in 253No

    NASA Astrophysics Data System (ADS)

    Lopez-Martens, A.; Hauschild, K.; Yeremin, A. V.; Dorvaux, O.; Belozerov, A. V.; Briançon, Ch.; Chelnokov, M. L.; Chepigin, V. I.; Curien, D.; Désesquelles, P.; Gall, B.; Gorshkov, V. A.; Guttormsen, M.; Hanappe, F.; Kabachenko, A. P.; Khalfallah, F.; Korichi, A.; Larsen, A. C.; Malyshev, O. N.; Minkova, A.; Oganessian, Yu. Ts.; Popeko, A. G.; Rousseau, M.; Rowley, N.; Sagaidak, R. N.; Sharo, S.; Shutov, A. V.; Siem, S.; Stuttgé, L.; Svirikhin, A. I.; Syed, N. U. H.; Theisen, Ch.

    2007-06-01

    Isomeric states in 253No have been investigated by conversion electron and γ -ray spectroscopy with the GABRIELA detection system. The 31μs isomer reported more than 30 years ago is found to decay to the ground state of 253No by the emission of a 167keV M2 transition. The spin and parity of this low-lying isomeric state are established to be 5/2+ . The presence of another longer-lived isomeric state is also discussed.

  2. Nearly degenerate isomeric states of 75Cu

    NASA Astrophysics Data System (ADS)

    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.

  3. Spectroscopic Characterization of Isomerization Transition States

    NASA Astrophysics Data System (ADS)

    Baraban, Joshua H.; Changala, Bryan; Mellau, Georg Ch.; Stanton, John F.; Merer, Anthony; Field, Robert W.

    2016-06-01

    Transition state theory is central to our understanding of chemical reaction dynamics. We demonstrate here a method for extracting transition state energies and properties from a characteristic pattern found in frequency domain spectra of isomerizing systems. This pattern, a dip in the spacings of certain barrier-proximal vibrational levels, can be understood using the concept of effective frequency, ωeff. The method is applied to the cis-trans conformational change in the S_1 state of C2H2 and the bond-breaking HCN-HNC isomerization. In both cases, the barrier heights derived from spectroscopic data agree extremely well with previous ab initio calculations. We also show that it is possible to distinguish between vibrational modes that are actively involved in the isomerization process and those that are passive bystanders. (This work has been published in J. H. Baraban, P. B. Changala, G. Ch. Mellau, J. F. Stanton, A. J. Merer, and R. W. Field. Spectroscopic characterization of isomerization transition states. Science, 350(6266):1338--1342, 2015.)

  4. Further results in the search for the direct two-proton decay of ^94Ag^m (J^π= 21^+, 6.7 MeV)

    NASA Astrophysics Data System (ADS)

    Cerny, J.; Lee, D. W.; Perajarvi, K.; Moltz, D. M.; Barquest, B. R.; Grossman, L. E.; Jeong, W.; Jewett, C. C.

    2008-10-01

    Both direct one-proton decay and direct two-proton decay of ^94Ag^m from this 0.4 s isomeric state have been reported in experiments utilizing the GSI on-line mass separator [1]. In the latter decay, coincident events between silicon E detectors with a threshold energy of 0.4 MeV and a summed decay energy of 1.9±0.1 MeV were observed with a yield of 350±210 pb in coincidence with γ-decays in the ^92Rh daughter. We utilized our helium-jet system at the LBNL 88-inch cyclotron to repeat this experiment, again employing the ^58Ni(^40Ca,p3n) reaction at 197 MeV. Reaction products were transported via a capillary to a detection area and collected on a slowly rotating wheel in front of an assembly of 24 δEgas-δEgas-ESi detector telescopes with a threshold of 0.4 MeV for identifying protons. Five of these telescopes observe the 0.79 MeV single proton decay from ^94Ag^m at the reported yield of 1.3 nb. In the 240/276 identified proton detector combinations with low background, no proton-proton coincidences have been observed. Data from the remaining 36 detector combinations require a separate analysis, which is in progress. Monte Carlo analyses of our anticipated proton-proton coincidences for both sets of detector combinations will be presented. ^ 1Mukha et al., Nature 439, 298 (2006).

  5. Isomerism of low-lying states in 86Y

    NASA Astrophysics Data System (ADS)

    Rusu, C.; Bucurescu, D.; Mărginean, N.; Ionescu-Bujor, M.; Iordăchescu, A.; Căta-Danil, G.; Căta-Danil, I.; Deleanu, D.; Filipescu, D.; Ghiţa, D.; Glodariu, T.; Ivaşcu, M.; Mihai, C.; Mărginean, R.; Pascu, S.; Sava, T.; Stroe, L.; Suliman, G.; Zamfir, N. V.

    2010-04-01

    Low-energy isomeric states of 86Y were populated in the reaction 73Ge + 16O at 57MeV and were investigated by means of delayed n γ and γ γ coincidences. A half-life of 70(7)ns was measured for the 5- state at 208keV, yielding an exceptionally small B( M1) value of 2.0(7)×10-5 W.u. and a B( E2) value of 0.34(+24 -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- 208keV state, the re-analysis of earlier experimental data on the 302keV isomer led to a new spin-parity assignment, 6+, 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 5/2 , p 3/2 , p 1/2 , and g 9/2 valence orbitals. Effective spin, orbital, and “tensor” g -factors were determined empirically for protons and neutrons in the considered configuration space.

  6. Proton-proton correlations observed in two-proton radioactivity of 94Ag.

    PubMed

    Mukha, Ivan; Roeckl, Ernst; Batist, Leonid; Blazhev, Andrey; Döring, Joachim; Grawe, Hubert; Grigorenko, Leonid; Huyse, Mark; Janas, Zenon; Kirchner, Reinhard; La Commara, Marco; Mazzocchi, Chiara; Tabor, Sam L; Van Duppen, Piet

    2006-01-19

    The stability and spontaneous decay of naturally occurring atomic nuclei have been much studied ever since Becquerel discovered natural radioactivity in 1896. In 1960, proton-rich nuclei with an odd or an even atomic number Z were predicted to decay through one- and two-proton radioactivity, respectively. The experimental observation of one-proton radioactivity was first reported in 1982, and two-proton radioactivity has now also been detected by experimentally studying the decay properties of 45Fe (refs 3, 4) and 54Zn (ref. 5). Here we report proton-proton correlations observed during the radioactive decay of a spinning long-lived state of the lightest known isotope of silver, 94Ag, which is known to undergo one-proton decay. We infer from these correlations that the long-lived state must also decay through simultaneous two-proton emission, making 94Ag the first nucleus to exhibit one- as well as two-proton radioactivity. We attribute the two-proton emission behaviour and the unexpectedly large probability for this decay mechanism to a very large deformation of the parent nucleus into a prolate (cigar-like) shape, which facilitates emission of protons either from the same or from opposite ends of the 'cigar'.

  7. Isomeric state in {sup 53}Co: A mean field analysis

    SciTech Connect

    Patra, S. K.; Bhat, F. H.; Panda, R. N.; Arumugam, P.; Gupta, Raj K.

    2009-04-15

    We study the ground and the first excited intrinsic states of {sup 53}Co and its mirror nucleus {sup 53}Fe, within the frameworks of the relativistic and nonrelativistic mean field formalisms. The analysis of the single-particle energy spectra of these nuclei show a competition of spins 1/2{sup -} and 3/2{sup -} in a low-lying excited state, which agrees well with the recent experimental observation [D. Rudolph et al., Eur. Phys. J. A 36, 131 (2008)] of spin and parity J{sup {pi}}=3/2{sup -} for the isomeric configuration in {sup 53}Co.

  8. High-spin states and a new band based on the isomeric state in 152Nd

    NASA Astrophysics Data System (ADS)

    Yeoh, E. Y.; Zhu, S. J.; Hamilton, J. H.; Ramayya, A. V.; Yang, Y. C.; Sun, Y.; Hwang, J. K.; Liu, S. H.; Wang, J. G.; Luo, Y. X.; Rasmussen, J. O.; Lee, I. Y.; Ding, H. B.; Li, K.; Gu, L.; Xu, Q.; Xiao, Z. G.; Ma, W. C.

    2010-08-01

    High-spin states of the neutron-rich 152Nd nucleus have been reinvestigated by measuring the prompt γ -rays in the spontaneous fission of 252Cf . The ground-state band and a side negative-parity band have been updated. A new band based on the 2243.7keV isomeric state has been identified. The half-life for the isomeric state has been measured to be 63(7)ns. The projected shell model is employed to study the band structure of this nucleus. The results show that the calculated levels of the bands are in good agreement with the experimental ones, and the isomeric state and the negative-parity band are based on the proton π5/2-[532] ⊗ π9/2+[404] and neutron ν3/2-[521] ⊗ ν5/2+[642] two-quasiparticles configurations, respectively.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Unusual Anharmonicities in Isomerizing Systems: the S1 State of C2H2

    NASA Astrophysics Data System (ADS)

    Baraban, J. H.; Field, R. W.; Stanton, J. F.; Merer, A. J.

    2012-06-01

    Low-barrier {cis}-{trans} isomerization profoundly affects the tilde{A}-tilde{X} spectrum of acetylene. We present extensions of the usual effective Hamiltonian model that capture these effects, and thereby enable fits of the complete tilde{A} {}1Au state J=K=0 level structure up to 4300 cm-1 above the {trans} zero point level. The relationship between these new additions to the model and spectroscopic indicators of the transition state energy will also be discussed. One dimensional models will be used to illustrate both the effects of the isomerization dynamics on the spectrum and how they can be exploited to reveal the isomerization barrier height.

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

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

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

    SciTech Connect

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

    2007-08-15

    Four long-lived neutron-deficient Th isotopes with atomic mass numbers 211 to 218 and abundances of (1-10)x10{sup -11} relative to {sup 232}Th have been found in a study of naturally-occurring Th using inductively coupled plasma-sector field mass spectrometry. It is deduced that long-lived isomeric states exist in these isotopes. The hypothesis that they might belong to a new class of long-lived high spin super- and hyperdeformed isomeric states is discussed.

  13. No Evidence of Isomerism for the First Excited State of {sup 93}Rb

    SciTech Connect

    Miernik, K.; Gross, C.J.; Grzywacz, R.; Madurga, M.; Mendez, A.J.; Rykaczewski, K.P.; Stracener, D.W.; Zganjar, E.F.

    2014-06-15

    The 253.3–keV excited state located in {sup 93}Rb was studied at the Holifield Radioactive Ion Beam Facility in Oak Ridge. This state, described as isomeric in databases, was populated in the decay of {sup 93}Kr produced by proton–induced fission of {sup 238}U and isolated using the isotope separation on–line technique. We report that the 253.3–keV level does not reveal isomerism and the upper limit of the half-life from our measurement is 4 ns. Our findings are supported by previously reported results that were not taken into account in the latest nuclear databases.

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

    NASA Astrophysics Data System (ADS)

    Nishimura, D.; Fukuda, M.; Sakai, T.; Tanaka, M.; Abe, K.; Chiba, J.; Fukuda, S.; Furuki, H.; Homma, A.; Hotaka, H.; Ichihashi, N.; Inaba, N.; Iwamoto, K.; Izumikawa, T.; Kamisho, Y.; Kanbe, K.; Kikukawa, N.; Kitagawa, A.; Kouno, J.; Nagashima, M.; Nakamura, Y.; Nishizuka, I.; Matsuta, K.; Mihara, M.; Miyazawa, S.; Morita, Y.; Ono, J.; Ohtsubo, T.; Sato, K.; Sato, S.; Sera, D.; Suzuki, S.; Suzuki, S.; Suzuki, T.; Takechi, M.; Tashiro, K.; Wakabayashi, M.; Watanabe, D.; Yaguchi, M.; Yamaguchi, T.; Yamaki, S.; Yasumoto, S.; Yoshinaga, K.; Zhu, Y.

    2014-03-01

    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+.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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)

  17. High-K,t1/2=1.4(1) ms, isomeric state in Lr255

    NASA Astrophysics Data System (ADS)

    Hauschild, K.; Lopez-Martens, A.; Yeremin, A. V.; Dorvaux, O.; Antalic, S.; Belozerov, A. V.; Briançon, Ch.; Chelnokov, M. L.; Chepigin, V. I.; Curien, D.; Gall, B.; Görgen, A.; Gorshkov, V. A.; Guttormsen, M.; Hanappe, F.; Kabachenko, A. P.; Khalfallah, F.; Larsen, A. C.; Malyshev, O. N.; Minkova, A.; Popeko, A. G.; Rousseau, M.; Rowley, N.; Saro, S.; Shutov, A. V.; Siem, S.; Stuttgè, L.; Svirikhin, A. I.; Syed, N. U. H.; Theisen, Ch.; Venhart, M.

    2008-08-01

    An isomeric state in Lr255 with a half-life of t1/2=1.4(1) ms and Ex>720-keV has been observed for the first time using the GABRIELA setup at the focal plane of the VASSILISSA separator. Based on its K-forbiddeness, the configuration of the state is most probably formed by coupling the valence proton to a two quasiparticle neutron excitation. Possible three quasiparticle configurations are discussed.

  18. Discovery of a 10 {mu}s isomeric state in {sub 63}{sup 139}Eu

    SciTech Connect

    Cullen, D. M.; Mason, P. J. R; Kishada, A. M.; Procter, M. G.; Rigby, S. V.; Varley, B. J.; Scholey, C.; Eeckhaudt, S.; Grahn, T.; Greenlees, P. T.; Jakobsson, U.; Jones, P. M.; Julin, R.; Juutinen, S.; Ketelhut, S.; Leino, M.; Leppaenen, A.-P.; Maentyniemi, K.; Nieminen, P.; Nyman, M.

    2011-01-15

    Recoil-isomer tagging with the {sup 54}Fe+{sup 92}Mo reaction was used to establish a 10(2)-{mu}s isomeric state in {sup 139}Eu. Prompt versus delayed {gamma}-ray coincidence data have revealed the presence of a prompt rotational band built upon the isomer. The alignment properties of the states in this band show that the isomer is based upon a proton g{sub 7/2} configuration. The decay of the isomer takes place through a single 26-keV E1 transition. The {gamma}-ray transition strength for this decay is consistent with those established in the neighboring isomeric gamma-soft nuclei. In these nuclei, isomers are expected to form as a consequence of differences in nuclear shapes or configurations, and the natural hindrance associated with configuration-changing E1 transitions. The isomeric nature of the state in {sup 139}Eu is reasoned to be because of difference in shape of the proton g{sub 7/2} state and the proton h{sub 11/2} ground state to which it decays.

  19. Population of isomeric states in fusion and transfer reactions in beams of loosely bound nuclei near the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Skobelev, N. K.

    2015-07-01

    The influence of the mechanisms of nuclear reactions on the population of 195 m Hg and 197 m Hg(7/2-), 198 m Tl and 196 m Tl(7+), and 196 m Au and 198 m Au(12-) isomeric nuclear states obtained in reactions induced by beams of 3He, 6Li, and 6He weakly bound nuclei is studied. The behavior of excitation functions and high values of isomeric ratios ( δ m/ δ g) for products of nuclear reactions proceeding through a compound nucleus and involving neutron evaporation are explained within statistical models. Reactions in which the emission of charged particles occurs have various isomeric ratios depending on the reaction type. The isomeric ratio is lower in direct transfer reactions involving charged-particle emission than in reactions where the evaporation of charged particles occurs. Reactions accompanied by neutron transfer usually have a lower isomeric ratio, which behaves differently for different direct-reaction types (stripping versus pickup reactions).

  20. Spherical proton-neutron structure of isomeric states in {sup 128}Cd

    SciTech Connect

    Caceres, L.; Gorska, M.; Grawe, H.; Sieja, K.; Geissel, H.; Gerl, J.; Kojouharov, I.; Kurz, N.; Montes, F.; Martinez-Pinedo, G.; Prokopowicz, W.; Schaffner, H.; Tashenov, S.; Wollersheim, H. J.; Jungclaus, A.; Pfuetzner, M.; Werner-Malento, E.; Nowacki, F.

    2009-01-15

    The {gamma}-ray decay of isomeric states in the even-even nucleus {sup 128}Cd has been observed. The nucleus of interest was produced both by the fragmentation of {sup 136}Xe and the fission of {sup 238}U primary beams. The level scheme was unambiguously constructed based on {gamma}{gamma} 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 provide a consistent description of the experimental level scheme. The structure of the isomeric states and their decays exhibit coexistence of proton, neutron, and strongly mixed configurations due to {pi}{nu} interaction in overlapping orbitals for both proton and neutron holes.

  1. Delayed autoionization of recoil ions by the decay of high-spin isomeric states

    NASA Astrophysics Data System (ADS)

    Maidikov, V. Z.

    1985-12-01

    The time dependence of the ionization for isotopically different heavy ion fusion recoil ions has been observed. Delayed nuclear-induced autoionization of recoil ions caused by the decay of high-spin nuclear isomeric states by internal conversion was established. Internal conversion in isolated recoil atoms results in a drastic rearrangement in the atomic cloud with a loss of a great number of orbital electrons. Possibilities for the use of the observed phenomena in atomic and nuclear physics are discussed.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Study of Shape Isomeric States in Fission Fragments

    NASA Astrophysics Data System (ADS)

    Pyatkov, Yu. V.; Kamanin, D. V.; Alexandrov, A. A.; Alexandrova, I. A.; Kondtatyev, N. A.; Kuznetsova, , E. A.; Strekalovsky, A. O.; Strekalovsky, O. V.; Zhuchko, V. E.; Mkaza, N.

    2015-06-01

    For the first time the brake-up of the fission fragments crossing metal foil was observed. The effect takes place predominantly in front impacts. To treat the data we suppose the bulk of the fragments from the conventional binary fission to be borne in shape-isomer states which look like di-nuclear systems with magic cores.

  4. Nanostructure formation by self-assembled monolayers: influence of the isomerization state of azobenzene ligands on monolayer formation

    NASA Astrophysics Data System (ADS)

    Vogel, Florian; Bretthauer, Frauke; Siemeling, Ulrich; Träger, Frank

    2011-03-01

    The monolayer formation of photoswitchable self-assembled monolayers of azobenzene-functionalized molecules was studied in situ and in real time by optical second-harmonic generation. Especially the influence of the isomerization state during the adsorption process was measured in our experiments. As will be shown, the isomerization state has a significant influence on the adsorption process of the investigated molecules. Based on the results of the second-harmonic generation experiments the kinetics of the adsorption process was determined.

  5. Insights into excited-state and isomerization dynamics of bacteriorhodopsin from ultrafast transient UV absorption

    PubMed Central

    Schenkl, S.; van Mourik, F.; Friedman, N.; Sheves, M.; Schlesinger, R.; Haacke, S.; Chergui, M.

    2006-01-01

    A visible-pump/UV-probe transient absorption is used to characterize the ultrafast dynamics of bacteriorhodopsin with 80-fs time resolution. We identify three spectral components in the 265- to 310-nm region, related to the all-trans retinal, tryptophan (Trp)-86 and the isomerized photoproduct, allowing us to map the dynamics from reactants to products, along with the response of Trp amino acids. The signal of the photoproduct appears with a time delay of ≈250 fs and is characterized by a steep rise (≈150 fs), followed by additional rise and decay components, with time scales characteristic of the J intermediate. The delayed onset and the steep rise point to an impulsive formation of a transition state on the way to isomerization. We argue that this impulsive formation results from a splitting of a wave packet of torsional modes on the potential surface at the branching between the all-trans and the cis forms. Parallel to these dynamics, the signal caused by Trp response rises in ≈200 fs, because of the translocation of charge along the conjugate chain, and possible mechanisms are presented, which trigger isomerization. PMID:16537491

  6. Insights into excited-state and isomerization dynamics of bacteriorhodopsin from ultrafast transient UV absorption.

    PubMed

    Schenkl, S; van Mourik, F; Friedman, N; Sheves, M; Schlesinger, R; Haacke, S; Chergui, M

    2006-03-14

    A visible-pump/UV-probe transient absorption is used to characterize the ultrafast dynamics of bacteriorhodopsin with 80-fs time resolution. We identify three spectral components in the 265- to 310-nm region, related to the all-trans retinal, tryptophan (Trp)-86 and the isomerized photoproduct, allowing us to map the dynamics from reactants to products, along with the response of Trp amino acids. The signal of the photoproduct appears with a time delay of approximately 250 fs and is characterized by a steep rise ( approximately 150 fs), followed by additional rise and decay components, with time scales characteristic of the J intermediate. The delayed onset and the steep rise point to an impulsive formation of a transition state on the way to isomerization. We argue that this impulsive formation results from a splitting of a wave packet of torsional modes on the potential surface at the branching between the all-trans and the cis forms. Parallel to these dynamics, the signal caused by Trp response rises in approximately 200 fs, because of the translocation of charge along the conjugate chain, and possible mechanisms are presented, which trigger isomerization.

  7. Watching ultrafast barrierless excited-state isomerization of pseudocyanine in real time.

    PubMed

    Dietzek, Benjamin; Yartsev, Arkady; Tarnovsky, Alexander N

    2007-05-03

    The photoinduced excited-state processes in 1,1'-diethyl-2,2'-cyanine iodine are investigated using femtosecond time-resolved pump-probe spectroscopy. Using a broad range of probe wavelengths, the relaxation of the initially prepared excited-state wavepacket can be followed down to the sink region. The data directly visualize the directed downhill motion along the torsional reaction coordinate and suggest a barrierless excited-state isomerization in the short chain cyanine dye. Additionally, ultrafast ground-state hole and excited-state hole replica broadening is observed. While the narrow excited-state wavepacket broadens during pump-probe overlap, the ground-state hole burning dynamics takes place on a significantly longer time-scale. The experiment reported can be considered as a direct monitoring of the shape and the position of the photoprepared wavepacket on the excited-state potential energy surface.

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

    SciTech Connect

    Lachner, J.; Dillmann, I.; Faestermann, T.; Korschinek, G.; Poutivtsev, M.; Rugel, G.

    2008-12-15

    The discovery of naturally occurring long-lived isomeric states (t{sub 1/2}>10{sup 8} yr) in the neutron-deficient isotopes {sup 211,213,217,218}Th[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.

  9. 20 {mu}s isomeric state in doubly odd {sub 61}{sup 134}Pm

    SciTech Connect

    Cullen, D. M.; Mason, P. J. R; Rigby, S. V.; Kishada, A. M.; Varley, B. J.; Scholey, C.; Eeckhaudt, S.; Grahn, T.; Greenlees, P. T.; Jakobsson, U.; Jones, P. M.; Julin, R.; Juutinen, S.; Ketelhut, S.; Leino, M.; Leppaenen, A.-P.; Maentyniemi, K.; Nieminen, P.; Nyman, M.; Pakarinen, J.

    2009-08-15

    Recoil-isomer tagging at the Accelerator Laboratory of the University of Jyvaeskylae has been used to establish the isomeric nature of a known (7{sup -}) excited state in the doubly odd nucleus {sup 134}Pm. The isomeric state was determined to have a half-life of 20(1) {mu}s and was populated from the decay of a {pi}h{sub 11/2} x {nu}h{sub 11/2} band using the {sup 92}Mo({sup 54}Fe,2{alpha}3pn) reaction at 305 and 315 MeV. The isomer decays by a 71-keV transition that provides an intermediate step in linking the established {sup 134}Pm high-spin level scheme to the lower-spin states observed from the {beta} decay of {sup 134}Sm. Electron-conversion analysis for the 71-keV {gamma}-ray transition reveals that it is of E1 character and its small reduced-transition probability suggests that {sup 134}Pm may have a nuclear shape more rigid than that of the neighboring nuclei.

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

    NASA Astrophysics Data System (ADS)

    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.

  11. Partial Photoneutron Cross Sections for the Isomeric State {sup 180}Ta{sup m}

    SciTech Connect

    Goko, S.; Utsunomiya, H.; Makinaga, A.; Kaihori, T.; Hohara, S.; Akimune, H.; Yamagata, T.; Goriely, S.; Lui, Y.-W.; Toyokawa, H.; Koning, A.J.; Hilaire, S.

    2006-05-19

    Photoneutron cross sections for {sup 181}Ta({gamma},n){sup 180}Ta{sup m} were determined from simultaneous measurements of total cross sections ({sigma}{sup tot}) and ground-state cross sections ({sigma}{sup gs}) for {sup 180}Ta in photodisintegration of {sup 181}Ta with laser Compton-backscattered {gamma} rays. Techniques of direct neutron counting and photoactivation were used for the measurement of {sigma}{sup tot} and {sigma}{sup gs}, respectively. The partial cross sections for the isomeric state serves as a novel probe of the nuclear level density of {sup 180}Ta. Implications for the p- and s-process nucleosynthesis of {sup 180}Ta{sup m} are given.

  12. Population of isomeric states in fusion and transfer reactions in beams of loosely bound nuclei near the Coulomb barrier

    SciTech Connect

    Skobelev, N. K.

    2015-07-15

    The influence of the mechanisms of nuclear reactions on the population of {sup 195m}Hg and {sup 197m}Hg(7/2{sup −}), {sup 198m}Tl and {sup 196m}Tl(7{sup +}), and {sup 196m}Au and {sub 198m}Au(12{sup −}) isomeric nuclear states obtained in reactions induced by beams of {sup 3}He, {sup 6}Li, and {sup 6}He weakly bound nuclei is studied. The behavior of excitation functions and high values of isomeric ratios (δ{sub m}/δ{sub g}) for products of nuclear reactions proceeding through a compound nucleus and involving neutron evaporation are explained within statistical models. Reactions in which the emission of charged particles occurs have various isomeric ratios depending on the reaction type. The isomeric ratio is lower in direct transfer reactions involving charged-particle emission than in reactions where the evaporation of charged particles occurs. Reactions accompanied by neutron transfer usually have a lower isomeric ratio, which behaves differently for different direct-reaction types (stripping versus pickup reactions)

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Femtosecond study on the isomerization dynamics of NK88. II. Excited-state dynamics

    NASA Astrophysics Data System (ADS)

    Vogt, Gerhard; Nuernberger, Patrick; Gerber, Gustav; Improta, Roberto; Santoro, Fabrizio

    2006-07-01

    The molecule 3,3'-diethyl-2,2'-thiacyanine isomerizes after irradiation with light of the proper wavelength. After excitation, it undergoes a transition, in which one or more conical intersections are involved, back to the ground state to form different product photoisomers. The dynamics before and directly after the transition back to the ground state is investigated by transient absorption spectroscopy in a wavelength region of 360-950nm, as well as by fluorescence upconversion. It is shown that the excited-state dynamics are governed by two time scales: a short one with a decay time of less than 2ps and a long one with about 9ps. A thorough comparison of the experimental results with those of configuration interaction singles and time-dependent density functional theory calculations suggests that these dynamics are related to two competing pathways differing in the molecular twisting on the excited surface after photoexcitation. From the experimental point of view this picture arises taking into account the time scales for ground-state bleach, excited-state absorption, stimulated emission, fluorescence, and assumed hot ground-state absorption both in the solvent methanol and ethylene glycol.

  15. Isospin Symmetry at High Spin Studied via Nucleon Knockout from Isomeric States.

    PubMed

    Milne, S A; Bentley, M A; Simpson, E C; Baugher, T; Bazin, D; Berryman, J S; Bruce, A M; Davies, P J; Diget, C Aa; Gade, A; Henry, T W; Iwasaki, H; Lemasson, A; Lenzi, S M; McDaniel, S; Napoli, D R; Nichols, A J; Ratkiewicz, A; Scruton, L; Stroberg, S R; Tostevin, J A; Weisshaar, D; Wimmer, K; Winkler, R

    2016-08-19

    One-neutron knockout reactions have been performed on a beam of radioactive ^{53}Co in a high-spin isomeric state. The analysis is shown to yield a 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 reliable shell-model input is available. The work has resulted in a new level scheme, up to the 11^{+} band-termination state, of the proton-rich nucleus ^{52}Co (Z=27, N=25). This has in turn enabled a study of mirror energy differences in the A=52 odd-odd mirror nuclei, interpreted in terms of isospin-nonconserving (INC) forces in nuclei. The analysis demonstrates the importance of using a full set of J-dependent INC terms to explain the experimental observations.

  16. Identification of a millisecond isomeric state in Cd12981 via the detection of internal conversion and Compton electrons

    NASA Astrophysics Data System (ADS)

    Taprogge, J.; Jungclaus, A.; Grawe, H.; Nishimura, S.; Xu, Z. Y.; Doornenbal, P.; Lorusso, G.; Nácher, E.; Simpson, G. S.; Söderström, P.-A.; Sumikama, T.; 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.; 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.; Covello, A.; Daugas, J.-M.; Drouet, F.; Gadea, A.; Gargano, A.; Ilieva, S.; 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.

    2014-11-01

    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.

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

    SciTech Connect

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  19. Covalent isomeric state in {sup 12}Be induced by two-neutron transfers

    SciTech Connect

    Ito, M.; Itagaki, N.

    2008-07-15

    The {alpha}+{sup 8}He low-energy reactions and the exotic structures of {sup 12}Be are studied using the generalized two-center cluster ({alpha}+{alpha}+4N) model. In the two-neutron transfer reactions, {alpha}+{sup 8}He{sub g.s.}{yields}{sup 6}He{sub g.s.}+{sup 6}He{sub g.s.}, a resonant peak with J{sup {pi}}=0{sup +} appears around E {approx} 1.3 MeV above the {sup 6}He{sub g.s.}+{sup 6}He{sub g.s.} threshold as the result of the formation of the covalent superdeformation, which has a hybrid structure of covalent and ionic configurations for the valence neutrons. The covalent superdeformation gives rise to an isomeric state with a sharp width of {gamma}{approx}400 keV, which is smaller by about one order of magnitude than the typical width observed in molecular resonances above the Coulomb barrier. The energy-spin systematics for the two-neutron transfer reactions is investigated, and our calculation predicts a sequence of resonant structures in the range of 3-14 MeV in the center-of-mass energy with spins 0({Dirac_h}/2{pi})-8({Dirac_h}/2{pi})

  20. Femtosecond study on the isomerization dynamics of NK88. I. Ground-state dynamics after photoexcitation

    NASA Astrophysics Data System (ADS)

    Nuernberger, Patrick; Vogt, Gerhard; Gerber, Gustav; Improta, Roberto; Santoro, Fabrizio

    2006-07-01

    Recently, optimal control of a photoisomerization reaction in the liquid phase was demonstrated for the first time on the system 3,3'-diethyl-2,2'-thiacyanine (NK88). Additionally, the class of cyanines to which the molecule NK88 belongs draws a lot of attention in different recent theoretical publications. Therefore, a better understanding of the molecular dynamics of this molecular system is of special interest. Experiments using the femtosecond pump-supercontinuum probe technique with an excitation wavelength of 400nm and a spectral range from 370to620nm for the probe beam have been performed. In order to analyze the dynamics properly the time window has been chosen to comprise the characteristic times of the contributing processes, additionally we have employed two solvents, methanol and ethylene glycol, and have conducted anisotropy measurements. The spectroscopic data have been assigned to different molecular states with the help of density functional theory and second-order Möller-Plesset perturbation theory calculations. The analysis of the data has revealed in the most likely model that three different isomers exist with different lifetimes. On the basis of experimental and theoretical data, a conclusive scheme of the isomerization reaction is presented.

  1. Production and decay properties of the 1.9-s isomeric state in {sup 261}Rf

    SciTech Connect

    Haba, H.; Kaji, D.; Kikunaga, H.; Kudou, Y.; Morimoto, K.; Morita, K.; Ozeki, K.; Sumita, T.; Yoneda, A.; Kasamatsu, Y.; Komori, Y.; Ooe, K.; Shinohara, A.

    2011-03-15

    The 1.9-s isomeric state ({sup 261}Rf{sup b}) in {sup 261}Rf was directly populated in the {sup 248}Cm({sup 18}O,5n){sup 261}Rf{sup b} reaction. Alpha and spontaneous fission (SF) decays of {sup 261}Rf{sup b}, as well as the 68-s state {sup 261}Rf{sup a}, was investigated with a rotating wheel apparatus under low background conditions attained by a gas-jet transport system coupled to the RIKEN gas-filled recoil ion separator. An identification of {sup 261}Rf{sup b} was based on {alpha}-{alpha} correlations linking {alpha} decays of {sup 261}Rf{sup b} and its daughter {sup 257}No. The {alpha}-particle energy of {sup 261}Rf{sup b} was measured to be 8.52 {+-} 0.05 MeV. The half-life was determined to be 1.9 {+-} 0.4 s based on both 8.52-MeV {alpha} and SF decays. The {alpha} and SF branches are 0.27 {+-} 0.06 and 0.73 {+-} 0.06, respectively. The cross section for the {sup 248}Cm({sup 18}O,5n){sup 261}Rf{sup b} reaction is {sigma}({sup 261}Rf{sup b}) = 11 {+-} 2 nb at 95.1 MeV, which gives a cross-section ratio of {sigma}({sup 261}Rf{sup a})/{sigma}({sup 261}Rf{sup b}) = 1.1 {+-} 0.2.

  2. High-spin μs isomeric states in 96Ag

    NASA Astrophysics Data System (ADS)

    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.

  3. Nitrogen-15 NMR studies of tetrazole complexes of pentamminecobalt(III). Implications concerning the transition state for linkage isomerization

    SciTech Connect

    Hubinger, S.; Hall, J.H.; Purcell, W.L. Los Alamos National Lab., NM )

    1993-05-26

    Synthesis of the N1-bonded (5-methyltetrazolato)pentaamminecobalt(III) complex utilizing sodium azide enriched in [sup 1]N at the terminal nitrogen has produced a complex enriched specifically at the N2 and N4 ring positions. This has permitted the assignment of all four nitrogen signals in the natural-abundance NMR spectrum for a novel chelated amidine complex which is also N1 bonded is reported along with its synthesis and purification. Following the [sup 15]N NMR of the linkage isomerization of the enriched complex in solution to the N2-bonded form has also permitted an [eta][sup 5] and certain [eta][sup 3] transition-state structures to be eliminated from consideration for the isomerization process. The data suggest an [eta][sup 2] transition state is utilized. A subsequent N2-to-N3 isomerization of the N2-bonded complex has also been discovered from the [sup 15]N NMR study. The enrichment study also indicates that previous assignments of ring nitrogen signals N1 and N4 is similar N2-bonded tetrazolato complexes of cobalt(III) may be in error.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. High-K, t{sub 1/2} = 1.4(1) ms, isomeric state in {sup 255}Lr

    SciTech Connect

    Hauschild, K.; Lopez-Martens, A.; Briancon, Ch.; Yeremin, A. V.; Belozerov, A. V.; Chelnokov, M. L.; Chepigin, V. I.; Gorshkov, V. A.; Kabachenko, A. P.; Malyshev, O. N.; Popeko, A. G.; Shutov, A. V.; Svirikhin, A. I.; Dorvaux, O.; Curien, D.; Gall, B.; Khalfallah, F.; Rousseau, M.; Rowley, N.; Stuttge, L.

    2008-08-15

    An isomeric state in {sup 255}Lr with a half-life of t{sub 1/2} = 1.4(1) ms and E{sub x}>720-keV has been observed for the first time using the GABRIELA setup at the focal plane of the VASSILISSA separator. Based on its K-forbiddeness, the configuration of the state is most probably formed by coupling the valence proton to a two quasiparticle neutron excitation. Possible three quasiparticle configurations are discussed.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Decay of the Iπ=8- isomeric state in 134Nd and 184Pt studied by electron and γ spectroscopy

    NASA Astrophysics Data System (ADS)

    Perkowski, J.; Andrzejewski, J.; Droste, Ch.; Janiak, Ł.; Grodner, E.; Rohoziński, S. G.; Próchniak, L.; Srebrny, J.; Samorajczyk-Pyśk, J.; Abraham, T.; Hadyńska-KlÈ©k, K.; Kisieliński, M.; Komorowska, M.; Kowalczyk, M.; Kownacki, J.; Marchlewski, T.; Mierzejewski, J.; Napiorkowski, P.; Stolarz, A.; Korman, A.; Zielińska, M.

    2017-01-01

    The properties of the K -isomer decays in the 134Nd and 184Pt nuclei have been investigated. Measurements were carried out in e -γ and γ -γ coincidence modes using electron spectrometers coupled to the central European Array for Gamma Levels Evaluations at the Heavy Ion Laboratory of the University of Warsaw. Internal conversion coefficients were obtained for transitions relevant to the decay of the isomeric states, allowing the determination of multipolarities and mixing ratios as well as hindrance factors. Two possible causes of the weakening of the K forbiddenness, namely rotational K mixing (Coriolis interaction) and triaxiality, are briefly discussed using schematic theoretical models.

  8. A VUV detection system for the direct photonic identification of the first excited isomeric state of 229Th

    NASA Astrophysics Data System (ADS)

    Seiferle, Benedict; von der Wense, Lars; Laatiaoui, Mustapha; Thirolf, Peter G.

    2016-03-01

    With an expected energy of 7.6(5) eV, 229Th 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 229Th. 229(m)Th ions originating from a 233U α-recoil source are collected on a micro electrode that is placed in the focus of an annular parabolic mirror. The latter is used to parallelize the UV fluorescence that may emerge from the isomeric ground-state transition of 229Th. The parallelized light is then focused by a second annular parabolic mirror onto a CsI-coated position-sensitive MCP detector behind the mirror exit. To achieve a high signal-to-background ratio, a small spot size on the MCP detector needs to be achieved. Besides extensive ray-tracing simulations of the optical setup, we present a procedure for its alignment, as well as test measurements using a D2 lamp, where a focal-spot size of ≈100 μm has been achieved. Assuming a purely photonic decay, a signal-to-background ratio of ≈7000:1 could be achieved.

  9. Quantum optimal control pathways of ozone isomerization dynamics subject to competing dissociation: A two-state one-dimensional model

    SciTech Connect

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

    2014-02-28

    We construct a two-state one-dimensional reaction-path model for ozone open → cyclic isomerization dynamics. The model is based on the intrinsic reaction coordinate connecting the cyclic and open isomers with the O{sub 2} + O asymptote on the ground-state {sup 1}A{sup ′} potential energy surface obtained with the high-level ab initio method. Using this two-state model time-dependent wave packet optimal control simulations are carried out. Two possible pathways are identified along with their respective band-limited optimal control fields; for pathway 1 the wave packet initially associated with the open isomer is first pumped into a shallow well on the excited electronic state potential curve and then driven back to the ground electronic state to form the cyclic isomer, whereas for pathway 2 the corresponding wave packet is excited directly to the primary well of the excited state potential curve. The simulations reveal that the optimal field for pathway 1 produces a final yield of nearly 100% with substantially smaller intensity than that obtained in a previous study [Y. Kurosaki, M. Artamonov, T.-S. Ho, and H. Rabitz, J. Chem. Phys. 131, 044306 (2009)] using a single-state one-dimensional model. Pathway 2, due to its strong coupling to the dissociation channel, is less effective than pathway 1. The simulations also show that nonlinear field effects due to molecular polarizability and hyperpolarizability are small for pathway 1 but could become significant for pathway 2 because much higher field intensity is involved in the latter. The results suggest that a practical control may be feasible with the aid of a few lowly excited electronic states for ozone isomerization.

  10. Quantum optimal control pathways of ozone isomerization dynamics subject to competing dissociation: a two-state one-dimensional model.

    PubMed

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

    2014-02-28

    We construct a two-state one-dimensional reaction-path model for ozone open → cyclic isomerization dynamics. The model is based on the intrinsic reaction coordinate connecting the cyclic and open isomers with the O2 + O asymptote on the ground-state (1)A(') potential energy surface obtained with the high-level ab initio method. Using this two-state model time-dependent wave packet optimal control simulations are carried out. Two possible pathways are identified along with their respective band-limited optimal control fields; for pathway 1 the wave packet initially associated with the open isomer is first pumped into a shallow well on the excited electronic state potential curve and then driven back to the ground electronic state to form the cyclic isomer, whereas for pathway 2 the corresponding wave packet is excited directly to the primary well of the excited state potential curve. The simulations reveal that the optimal field for pathway 1 produces a final yield of nearly 100% with substantially smaller intensity than that obtained in a previous study [Y. Kurosaki, M. Artamonov, T.-S. Ho, and H. Rabitz, J. Chem. Phys. 131, 044306 (2009)] using a single-state one-dimensional model. Pathway 2, due to its strong coupling to the dissociation channel, is less effective than pathway 1. The simulations also show that nonlinear field effects due to molecular polarizability and hyperpolarizability are small for pathway 1 but could become significant for pathway 2 because much higher field intensity is involved in the latter. The results suggest that a practical control may be feasible with the aid of a few lowly excited electronic states for ozone isomerization.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Isomerization of HNO to HON in the singlet state assisted by amino acid residues and/or water molecules

    NASA Astrophysics Data System (ADS)

    Shi, Junyou; Li, Ping; Bu, Yuxiang; Wang, Weihua; Mou, Zhaoxia; Song, Rui

    The effects of amino acid residues in the presence or absence of water molecules on the isomerization of the singlet state of HNO/HON have been systematically investigated at the B3LYP/6-311++G** level of theory. The structural characteristics, proton transfer (PT) mechanisms, and the corresponding thermodynamic and kinetic parameters, have been discussed, respectively. All the optimized complexes have been characterized by the ring structures through the intermolecular H-bonds. The origin of the increase in N bond H stretching frequency (blue shifts) occurring in the reactants has also been investigated using the natural bonding orbital (NBO) analyses, which is mainly attributed to the decrease of the electron densities in the antibonding orbital of the N bond H bonds as well as the increase of the polarization of the N bond H bond. All the PTs proceed with the concerted mechanisms since no ionic intermediates have been located during PT processes. At the same time, the cooperative effects of amino acid residues and water molecules on the selected PT processes have been observed, where the PTs assisted solely by the selected residues cannot occur without the participation of the water molecule. Overall, the introductions of one or two water molecules are more favorable for the isomerization of HNO assisted by the amino acid residues.

  13. Effects of roaming trajectories on the transition state theory rates of a reduced-dimensional model of ketene isomerization.

    PubMed

    Ulusoy, Inga S; Stanton, John F; Hernandez, Rigoberto

    2013-08-15

    The rates of chemical reactions (or any activated process) are by definition determined by the flux of reactants (or initial states) that end up as products (or final states). The forward flux through any surface that divides reactants from products is a constant as long as only those trajectories that were reactants in the infinite past and products in the infinite future are included in the flux once and only once. Transition state theory (TST) ignores this last clause, thereby overestimating the rate if any of the trajectories recross the dividing surface. However, its advantage is that it replaces a dynamical calculation with a statistical integral over the TST geometry. The recent identification of roaming trajectories-those that persist for a long time as neither reactant nor product without ever visiting near the col on the energy landscape-apparently challenges the dogma that TST's only error lies in the omission of recrossing trajectories. This question is investigated using the isomerization reaction of ketene in which the experimental values are verified to be in reasonable agreement with both the exact and TST values. We have found two trajectories for the ketene isomerization that carry the signature of roaming, but their effect on the calculation of the reaction rate constant using classical transition state theory is small. Indeed, the existence of roaming trajectories is seen to impose a limitation on which dividing surfaces are appropriate for the calculation of either exact or approximate TST rates, but in this case, they do not unseat the existence of dividing surfaces that can be used safely to calculate TST rates.

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

    PubMed

    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.

  15. Photon induced isomerization in the first excited state of the 7-azaindole-(H2O)3 cluster.

    PubMed

    Pino, Gustavo A; Alata, Ivan; Dedonder, Claude; Jouvet, Christophe; Sakota, Kenji; Sekiya, Hiroshi

    2011-04-07

    A picosecond pump and probe experiment has been applied to study the excited state dynamics of 7-azaindole-water 1 ∶ 2 and 1 ∶ 3 clusters [7AI(H(2)O)(2,3)] in the gas phase. The vibrational-mode selective Excited-State-Triple-Proton Transfer (ESTPT) in 7AI(H(2)O)(2) proposed from the frequency-resolved study has been confirmed by picosecond decays. The decay times for the vibronic states involving the ESTPT promoting mode σ(1) (850-1000 ps) are much shorter than those for the other vibronic states (2100-4600 ps). In the (1 + 1) REMPI spectrum of 7AI(H(2)O)(3) measured by nanosecond laser pulses, the vibronic bands with an energy higher than 200 cm(-1) above the origin of the S(1) state become very weak. In contrast, the vibronic bands in the same region emerge in the (1 + 1') REMPI spectrum of 7AI(H(2)O)(3) with picosecond pulses. The decay times drastically decrease when increasing the vibrational energy above 200 cm(-1). Ab initio calculations show that a second stable "cyclic-nonplanar isomer" exists in addition to a "bridged-planar isomer", and that an isomerization from a bridged-planar isomer to a cyclic-nonplanar isomer is most probably responsible for the short lifetimes of the vibronic states of 7AI(H(2)O)(3).

  16. Monopole effects, isomeric states, and cross-shell excitations in the A =129 hole nuclei near 132Sn

    NASA Astrophysics Data System (ADS)

    Wang, Han-Kui; Kaneko, Kazunari; Sun, Yang; He, Yi-Qi; Li, Shao-Feng; Li, Jian

    2017-01-01

    We present results of large-scale shell-model calculations for the A =129 hole nuclei below 132Sn. We discuss structures of 129Sn, 129In, and 129Cd with emphasis on the monopole effects and excitations across the neutron N =82 shell gap, and further predict low-lying levels for the more exotic 129Ag. It is demonstrated that the monopole corrections in the Hamiltonian, which dynamically affect occupations of relevant orbits, can lead to interesting consequences for the shell evolution. It is found especially that the monopole terms, previously introduced to reproduce the cross-shell excitations of the 17 /2+ and 21 /2+ states in 131In, shows more pronounced effects on the A =129 nuclei. In 129In, the cross-shell excitations of 17 /2+ and 21 /2+ are pushed down significantly by the monopole terms, and in 129Cd, the same monopole terms reverse the order of the single-hole states of ν d3 /2 and ν h11 /2 , causing 11/2 - as the ground state for this nucleus. The structure of isomeric states in the A =129 nuclei is also discussed.

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

    PubMed

    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

  18. Strongly Enhanced Low Energy α-Particle Decay in Heavy Actinide Nuclei and Long-Lived Superdeformed and Hyperdeformed Isomeric States

    NASA Astrophysics Data System (ADS)

    Marinov, A.; Gelberg, S.; Kolb, D.; Weil, J. L.

    Unidentified low energy and very enhanced α-particle groups have been observed in various actinide fractions produced via secondary reactions in a CERN W target which had been irradiated with 24-GeV protons. In particular, 5.14, 5.27 and 5.53 MeV α-particle groups with corresponding half-lives of 3.8+/-1.0 y, 625+/-84 d and 26+/-7d, have been seen in Bk, Es and Lr-No sources, respectively. The measured energies are a few MeV lower than the known ground state to ground state α-decays in the corresponding neutron-deficient actinide nuclei. The half-lives are 104 to 107 shorter than expected from energy versus lifetime relationship for such low-energy α-particles in this region of nuclei. The deduced evaporation residue cross sections are in the mb region, about 104 times higher than expected. Not only is it impossible to identify these α-decays with any known activity in the whole nuclear chart, but they also could not be due to hypothetically unknown isomeric states in various conceivable neutron deficient nuclei, nor due to unknown isomeric states in the rare-earth region. Based on the fact that in other experiments we have found isomeric states in the second and third minima of the potential for other heavy ion reaction products, one can now understand in a quantitative way, both the unusual low energies, the unusual enhanced lifetimes and the unusual large production cross sections, in terms of production of similar isomeric states in appropriate actinide isotopes. Some consequences regarding the production of the long-lived superheavy elements are also discussed.

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

    NASA Astrophysics Data System (ADS)

    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.

  20. g-Factors of Isomeric States in the Neutron-Rich Nuclei

    SciTech Connect

    Georgiev, G.; Neyens, G.; Hass, M.; Balabanski, Dimiter Loukanov; Bingham, Carrol R; Borcea, C.; Coulier, N.; Coussenment, R.; Daugas, J. M.; De France, Gilles M; Gorska, M.; Grawe, Hubert H; Grzywacz, Robert Kazimierz; Lewitowicz, Marek; Mach, Henryk A; Matea, I.; de Oliveira Santos, F.; Page, R. D.; Pfutzner, Marek; Penionzhkevich, Yu. E.; Podolyak, Zsolt F; Regan, Patrick H; Rykaczewski, Krzysztof Piotr; Sawicka, M.; Smirnova, N. A.; Sobolev, Yu.; Stanoiu, M.; Teughels, S.; Vyvey, K.

    2004-02-01

    We report the results from the first experiment to measure gyromagnetic factors of {micro}s isomers in neutron-rich nuclei produced by intermediate-energy projectile-fragmentation reactions. The Time Dependent Perturbed Angular Distribution (TDPAD) method was applied in combination with the heavy-ion-gamma correlation technique. The nuclides in the vicinity of {sup 68}Ni were produced and spin-oriented following the fragmentation of a {sup 76}Ge, 61.4 MeV/ u beam at GANIL. The results obtained, |g|({sup 69 m}Cu) = 0.225(25) and |g|({sup 67 m}Ni) = 0.125(6) provide another indication of the importance of proton excitation across the Z = 28 shell gap for the description of these states.

  1. Magnetic moments of the isomeric states of /sup 141/Pr and /sup 143/Pm and the paramagnetism of promethium and praseodymium

    SciTech Connect

    Gorbachev, B.I.; Levon, A.I.; Nemets, O.F.; Fedotkin, S.N.; Stepanenko, V.A.

    1984-07-01

    The g-factors of the 11/2/sup -/ and 15/2/sup +/ isomeric states of the /sup 141/Pr and /sup 143/Pm nuclei (Tables I and II) have been measured by the method of differential and integrated perturbed angular distribution. The parametric corrections were determined for /sup 143/Pm from the measured temperature dependence g..beta..(T). The relaxation times have been measured for nuclear states aligned in beam reactions, metal targets, and targets made of La and Pr oxides. The results are analyzed in terms of the quasiparticle-phonon model with allowance for the spin-multipole interaction.

  2. Photoreactivity of a Push-Pull Merocyanine in Static Electric Fields: A Three-State Model of Isomerization Reactions Involving Conical Intersections

    NASA Astrophysics Data System (ADS)

    Xu, X. F.; Kahan, A.; Zilberg, S.; Haas, Y.

    2009-08-01

    The photochemistry of a prototype push-pull merocyanine is discussed using a simple three-state model. As a derivative of butadiene, the model focuses on two isomerization reactions around the two double bonds of the butadiene backbone. As a molecule substituted by an electron donor and electron acceptor at opposite ends, its structure as well as its photochemistry are expected to be strongly affected by the environment. In polar solvents, a zwitterion transition state for each of the isomerization reactions is stabilized, and its energy is on the same order as that of the biradical one; this leads to the symmetry allowed crossing (S0/S1 conical intersection). It is shown that applying an external electric field or varying the solvent polarity changes the relative energies of the different transition states as well as that of the conical intersection, and thus different photochemical products can be obtained. In particular, the very existence of conical intersections is found to depend on these external parameters. This work provides a theoretical foundation for ideas expressed by Squillacote et al. (J. Am. Chem. Soc. 2004, 126, 1940) concerning the electrostatic control of photochemical reactions.

  3. Isomerization of sugars

    SciTech Connect

    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.

  4. Conceptual Difficulties with Isomerism.

    ERIC Educational Resources Information Center

    Schmidt, Hans-Jurgen

    1992-01-01

    Reports descriptive study concerning student understanding of isomers. Sample of 7,441 senior high school students completed tests which contained 12 questions on isomerism. Results indicate students are inclined to restrict their concept of isomerism to compounds belonging to the same class. There was no evidence students expected molecular…

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

    SciTech Connect

    Hu, Bin; Geng, Jiao; Zhang, Lie; Huang, Wei

    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

  6. Magnetic dipole moments near 132Sn: Measurement on isomeric {11}/{2 -} states in odd- A131Te and 133Te by NMR/ON

    NASA Astrophysics Data System (ADS)

    White, G.; Rikovska, J.; Stone, N. J.; Copnell, J.; Towner, I. S.; Oros, A. M.; Heyde, K.; Fogelberg, B.; Jacobsson, L.; Gustavsson, F.

    1998-09-01

    On-line low temperature nuclear orientation (OLNO) experiments have been performed on the odd- A Te isotopes 131Te and 133Te using the technique of nuclear magnetic resonance on oriented nuclei (NMR/ON). The magnetic moments of the isomeric {11}/{2 -} states have been measured extending the known data on these states in the Te isotopes up to the neutron shell closure at N = 82. The contribution to the {11}/{2 -} magnetic moment in 133Te due to core polarisation is calculated using an RPA shell model as well as corrections to the magnetic dipole operator caused by mesonic exchange currents. The neutron number dependence of the magnetic moments of the {11}/{2 -} isomers in heavy Te isotopes is discussed in terms of particle-core coupling model (PCM) calculations.

  7. Analysis of isomeric ratios for medium-mass nuclei

    NASA Astrophysics Data System (ADS)

    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.

  8. Photo-Reactivity of a Push-Pull Merocyanine in a Static Electric Fields: a Three State Model of Isomerization Reactions Involving Conical Intersections

    NASA Astrophysics Data System (ADS)

    Zilberg, S.; Xu, X. F.; Kahan, A.; Haas, Y.

    2009-06-01

    The photochemistry of a prototype push-pull merocyanine is discussed using a simple three state model. As a derivative of butadiene, two isomerization reactions may take place, around the two double bonds of the butadiene backbone. As a molecule substituted by an electron donor and electron acceptor at opposite ends, its structure as well as its photochemistry are expected to be strongly affected by the environment. It is shown that varying the solvent polarity or the electric field, can lead to different photochemical products. In particular, the existence of conical intersections is found to depend on these external parameters. This work provides a theoretical foundation for ideas expressed by Squillacote et al.* concerning the electrostatic control of photochemical reactions. *Squillacote, M.; Wang, J.; Chen, J. J. Am. Chem. Soc. 2004, 126, 1940.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Reduced dimension rovibrational variational calculations of the S{sub 1} state of C{sub 2}H{sub 2}. II. The S{sub 1} rovibrational manifold and the effects of isomerization

    SciTech Connect

    Changala, P. Bryan Baraban, Joshua H.; Field, Robert W.; Stanton, John F.; Merer, Anthony J.

    2014-01-14

    Reduced dimension variational calculations have been performed for the rovibrational level structure of the S{sub 1} state of acetylene. The state exhibits an unusually complicated level structure, for various reasons. First, the potential energy surface has two accessible conformers, trans and cis. The cis conformer lies about 2700 cm{sup −1} above the trans, and the barrier to cis-trans isomerization lies about 5000 cm{sup −1} above the trans minimum. The trans vibrations ν{sub 4} (torsion) and ν{sub 6} (asym. bend) interact very strongly by Darling-Dennison and Coriolis resonances, such that their combination levels and overtones form polyads with unexpected structures. Both conformers exhibit very large x{sub 36} cross-anharmonicity since the pathway to isomerization is a combination of ν{sub 6} and ν{sub 3} (sym. bend). Near the isomerization barrier, the vibrational levels show an even-odd K-staggering of their rotational levels as a result of quantum mechanical tunneling through the barrier. The present calculations address all of these complications, and reproduce the observed K-structures of the bending and C–C stretching levels with good qualitative accuracy. It is expected that they will assist with the assignment of the irregular patterns near the isomerization barrier.

  11. Site-specific electronic couplings in dyads with MLCT excited states. Intramolecular energy transfer in isomeric Ru(II)-Ru(II) cyclometalated complexes.

    PubMed

    Polson, Matthew; Chiorboli, Claudio; Fracasso, Sandro; Scandola, Franco

    2007-04-01

    The rod-like binuclear complexes [(ttpy)Ru(tpy-ph(2)-phbpy)Ru(ttpy)](4+) and [(ttpy)Ru(tpy-ph(2)-tpy)Ru(phtbpy)](4+) (for abbreviations, see text) have been synthesized and characterized. In both complexes, the polypyridine Ru(II) centers have (N--N--N)Ru(N--N--N) and (N--N--N)Ru(C--N--N) coordination environment. The two isomeric species differ in whether the cyclometalating carbon resides on the bridging or on the terminal ligand. The two complexes have virtually identical energy levels, but MLCT excited states of different (bridging or terminal) ligand localization. They are thus ideally suited to investigate possible effects of excited-state localization on intramolecular energy transfer kinetics. In fact, ultrafast spectroscopic measurements yield different energy transfer time constants for the two isomers, with the bridge-cyclometalated complex (2.7 ps) being faster than the terminal-cyclometalated one (8.0 ps). This difference can be explained in terms of different electronic factors for Dexter energy transfer. The study highlights the peculiar intricacies of intramolecular energy transfer in inorganic dyads involving MLCT excited states.

  12. Experiments with isomeric beams

    NASA Astrophysics Data System (ADS)

    Pfützner, M.; Grzywacz, R.; Lewitowicz, M.; Rykaczewski, K.

    1997-02-01

    The results of the search for μs-isomers performed with 112Sn and 86Kr beams at 60 MeV/nucleon with the LISE3 spectrometer at GANIL are summarized. Planned extension of these studies to high energy fragmentation reactions with the FRS separator at GSI is described. Some perspectives for experiments with isomeric beams at GSI are mentioned.

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

    SciTech Connect

    LicA, R.; Marginean, N.; Ghita, D.G.; 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.

  14. Thermal Neutron Capture and Thermal Neutron Burn-up of K isomeric state of 177mLu: a way to the Neutron Super-Elastic Scattering cross section

    SciTech Connect

    Roig, O.; Belier, G.; Meot, V.; Daugas, J.-M.; Romain, P.

    2006-03-13

    Thermal neutron radiative capture and burn-up measurements of the K isomeric state in 177Lu form part of an original method to indirectly obtain the neutron super-elastic scattering cross section at thermal energy. Neutron super-elastic scattering, also called neutron inelastic acceleration, occurs during the neutron collisions with an excited nuclear level. In this reaction, the nucleus could partly transfer its excitation energy to the scattered neutron.

  15. Decay of 185Tl, 185m+gHg, 189m+gPb and energy location of the 13/2+ isomeric states in 185Hg, 189Pb, 193Po and 197Rn

    NASA Astrophysics Data System (ADS)

    Sauvage, J.; Roussière, B.; Genevey, J.; Franchoo, S.; Andreyev, A. N.; Barré, N.; Ben Braham, A.; Bourgeois, C.; Clavelin, J.-F.; De Witte, H.; Fedorov, D. V.; Fedoseyev, V. N.; Fraile, L. M.; Grave, X.; Huber, G.; Huyse, M.; Kilcher, P.; Köster, U.; Kunz, P.; Lesher, S. R.; Marsh, B. A.; Mukha, I.; Oms, J.; Porquet, M. G.; Seliverstov, M.; Stefanescu, I.; Van de Vel, K.; Van Duppen, P.; Volkov, YU. M.; Wojtasiewicz, A.

    2013-09-01

    The /EC decay of 185Tl was studied at the ISOLDE facility, the -rays belonging to 185Hg have been identified and a partial low-spin level scheme of 185Hg has been built. The decay of 185m+gHg was studied at the ISOCELE facility. Conversion electron lines of very low-energy transitions were observed for the first time. Electron data have been obtained for four transitions in 185Au and two transitions in 185Hg . From the analysis performed using an internal energy calibration procedure the energy location of the 185mHg has been determined to be keV. This value is consistent with that determined independently, keV, using 185m+gHg -decay data from literature. New particles emitted from 189m+gPb have been detected and their origins determined by in-source laser spectroscopy at the ISOLDE facility. - coincidence results have served to locate the isomeric state of 189Pb at keV. This latter value added to -decay data from literature have allowed the energy location of the isomeric states of 193Po and 197Rn at 95(7)keV and 194(12)keV, respectively. The nuclear structure of the isomeric and ground states in the nuclei of the three -emitter chains starting with 195m+g, 197m+g, 199m+gRn are discussed.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Neutron single-particle strengths at N=40 , 42: Neutron knockout from Ni68,70 ground and isomeric states

    DOE PAGES

    Recchia, F.; Weisshaar, D.; Gade, A.; ...

    2016-11-28

    The distribution of single-particle strength in 67,69Ni was characterized with one-neutron knockout reactions from intermediate-energy 68,70Ni 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, is used to identify and quantify neutron configurations in the wave functions. While 69Ni compares well to 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. Furthermore, these results suggest that our understanding of the low-lyingmore » states in the neutron-rich, semi-magic Ni isotopes may be incomplete and requires further investigation on both the experimental and theoretical sides.« less

  19. Conformational isomerism in the solid-state structures of tetracaine and tamoxifen with para-sulphonato-calix[4]arene

    NASA Astrophysics Data System (ADS)

    Danylyuk, Oksana; Monachino, Melany; Lazar, Adina N.; Suwinska, Kinga; Coleman, Anthony W.

    2010-02-01

    The solid-state complexes between para-sulphonato-calix[4]arene and the drugs tamoxifen and tetracaine show an unusual 4:1 guest-host stoichiometry with formation of hydrophobic layer of drug molecules held between bilayers of para-sulphonato-calix[4]arene. In both structures each of the four independent drug molecules adopts different conformation due to the different mode of interaction with the anionic host, the neighbouring drug cations and water molecules.

  20. Nuclear structure ''southeast'' of {sup 208}Pb: Isomeric states in {sup 208}Hg and {sup 209}Tl

    SciTech Connect

    Al-Dahan, N.; Podolyak, Zs.; Regan, P. H.; Alkhomashi, N.; Deo, A. Y.; Farrelly, G.; Steer, S. J.; Cullen, I. J.; Gelletly, W.; Swan, T.; Thomas, J. S.; Walker, P. M.; Gorska, M.; Grawe, H.; Gerl, J.; Pietri, S. B.; Wollersheim, H. J.; Boutachkov, P.; Domingo-Pardo, C.; Farinon, F.

    2009-12-15

    The nuclear structure of neutron-rich N>126 nuclei has been investigated following their production via relativistic projectile fragmentation of a E/A=1 GeV {sup 238}U beam. Metastable states in the N=128 isotones {sup 208}Hg and {sup 209}Tl have been identified. Delayed {gamma}-ray transitions are interpreted as arising from the decay of I{sup {pi}}=(8{sup +}) and (17/2{sup +}) isomers, respectively. The data allow for the so far most comprehensive verification of the shell-model approach in the region determined by magic numbers Z<82 and N>126.

  1. Prospects for isomeric energy release

    NASA Astrophysics Data System (ADS)

    Karamian, S. A.

    2008-07-01

    The state of experimental studies and promising proposals for the application of nuclear isomers presented as controlled energy or γ-ray sources are reviewed. The properties of isomeric states, methods of their production, and approaches to their efficient stimulation using various types of radiation are analyzed. The long-lived isomers, which can be accumulated in reactor irradiations or in other nuclear interactions with abundant yield, are listed. The isomers are estimated according to their specific energy accumulated per nucleus and the level of the cross section for their formation in reactions with neutrons. The nuclei are classified as promising either for obtaining controlled γ-ray pulses, for the enhanced release of the radioactive decay energy, or for experimental studies on detecting forbidden electromagnetic transitions from the ground to isomeric state. In all cases, the possibility of external-stimulus action on nuclear transitions has key significance, which should become the subject of investigations. The results of successful observation of stimulation of isomers are described at excitation energy E* > 1 MeV in the reactions with bremsstrahlung photons and Coulomb excitation in the ion beam. The essential increase in the K-hindered transitions with increasing energy and also the K-mixing at high rotational frequency for high-spin levels are discussed. The attention is focused on attempts to detect the triggering induced by the radiation in the x-ray range, in particular, that of the 178 m2Hf isomer with the help of x-ray sources and the synchrotron radiation. Proposals for experiments with other isomers are considered. The possibility of affecting the nuclear states by means of ionization of electron shells of a corresponding atom is discussed as promising, and various schemes of similar experiments are proposed. The atomic cross sections are eight orders of magnitude higher than the nuclear ones; therefore, the stimulation of an isomer can

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

    SciTech Connect

    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.

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

    PubMed

    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.

  4. Vibrational relaxation and isomerization kinetics of alcohols

    NASA Astrophysics Data System (ADS)

    Self-Medlin, Yehudi

    The vibrational dynamics of the O-H stretch was investigated for a series of alcohols in room temperature gas-phase and dilute solution. A set of alcohols with one stable conformer was measured to determine the intramolecular vibrational energy redistribution (IVR) timescales of basic alcohols for comparison of the isolated to solvated molecule dynamics. It was determined from these experiments the IVR rate of the O-H stretch is unaffected by the presence of solvent. Next, population transfer rates were measured from the initially excited O-H stretch through the molecule to the v = 1 acetylenic C-H bending mode of a series of alkynols. It was found that the IVR and population transfer rates were almost independent of molecule size, distance between the O-H and acetylene moiety, or branching size. However, the excited O-H stretch exhibits very little transfer to the C-H stretch or C-H bend overtone, indicating a mode-specific redistribution pathway. The data, as well as ab initio calculations, suggest non-statistical relaxation of the O-H stretch excited state population through a subset of C-H bending states. Determining the timescales of intramolecular relaxation and population transfer establishes a foundation for developing methods to enhance chemical reactions with lasers. A preliminary step towards this goal is the study of conformational isomerization. The IVR lifetime is the rate limiting step in vibrationally-induced isomerization kinetics. The conformational isomerization takes places so rapidly after IVR completion that it could not be detected with the available time resolution. However, excited state absorption signal was used as a molecular probe to measure the thermal isomerization created by collisions with solvent. The kinetic rate constants of the thermal isomerization were determined from the transient absorption spectra in combination with fixed time frequency scans of the entire absorption and bleach region. The experimentally determined values

  5. Rotational isomerism of vinylmethyltelluride

    SciTech Connect

    Keiko, V.V.; Sinegovskaya, L.M.; Gusarova, N.K.; Tatarinova, A.A.; Kalinina, N.A.; Trofimov, B.A.

    1987-08-10

    In the IR spectrum of solutions of vinylmethyltelluride in n-heptane the doublet form of the valence oscillation band of the double bond is due to rotational isomerism. By analyzing the temperature dependence of the doublet shape, the low-frequency component of the doublet was identified as the s-cis-rotamer. The differences in the enthalpies (4.6 +/- 0.2 kJ/mole) and entropies (-11.1 +/- 0.3 e.u.) of the vinylmethyltelluride rotamers have been calculated and it has been shown that the p,..pi..-conjugation in its molecule is weaker by a factor of 2 than in vinylmethylsulfide.

  6. a Reevaluation of Distortional Isomerism

    NASA Astrophysics Data System (ADS)

    Desrochers, Patrick John

    The blue and green forms of MoOCl_2 (PMe_2Ph)_3 and (LWOCl_2) PF _6 (L = 1,4,7-trimethyltriazacyclononane) are not examples of distortional isomerism. For both systems, the blue form is pure and the green form is a mixture of the blue complex and other components. Characterizations of the green material of each indicates that green "MoOCl _2(PMe_2Ph) _3" is a mixture of MoOCl _2(PMe_2Ph) _3 and MoCl_3(PMe _2Ph)_3 and that green "(LWOCl_2) PF _6" is a mixture of (LWOCl_2 ) PF_6 and two other species; one is a W(IV) and the other a W(VI) compound. Both solid state (XPS, Raman, infrared, powder X-ray diffraction) and solution phase (^1H NMR, UV -visible, EPR, cyclic voltammetry) measurements were applied to the respective green materials, presenting a consistent description of their composite nature. A single crystal X-ray structure determination of a crystal of green "MoOCl _2(PMe_2Ph) _3" allowed the compositional disorder to be partially resolved in this case, due to the high composition of MoOCl_3(PMe _2Ph)_3 in the sample (ca. 0.30 mole percent by XPS and visible spectroscopies). The single crystal X-ray diffraction data from the original single crystal study of green "(LWOCl_2 ) PF_6" were reinvestigated to ascertain whether compositional disorder could also be implicated in this system. Several composite models were applied to these data, resulting in improved fits to the observed data. This indicated that the original data collected for the crystal of green "(LWOCl _2) PF_6" could not support distortional isomerism in green "(LWOCl _2) PF_6". X-ray structure calculations on models of the compositional disorder in both systems illustrated the pronounced effect of disordering chlorine electron density on the derived metal-oxo bond lengths. A calibration curve of Mo-Cl bond length versus composition calculated from these models resulted in a favorable comparison of this present theoretical work with other experimental X-ray studies of the MoOCl_2 (PMe_2Ph)_3

  7. Isomeric oxydiphthalic anhydride polyimides

    NASA Technical Reports Server (NTRS)

    Gerber, Margaret K.; Pratt, J. Richard; Stclair, Terry L.

    1988-01-01

    Much of the polyimide research at Langley Research Center has focused on isomeric modification of the diamine component; polyimides having considerably improved processability and adhesion have resulted. The present structure-property study was designed to investigate how isomeric attachment of the three oxydiphthalic anhydride (ODPA) polyimides affects their properties. Each dianhydride, 3,4,3',4'-oxydiphthalic anhydride (4,4'-OPDA,I), 2,3,2',3'-oxydiphthalic anhydride (3,3'-ODPA,II), and 2,3,3',4'-oxydiphthalic anhydride (3,4'-OPDA,III), was reacted with p-phenylenediamine, 4,4'-oxydianiline, 3,3'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, and 4,4'-bis(3-aminophenoxy)benzophenone in DMAc. The inherent viscosities of the resulting poly(amic acids) were determined. Thermally imidized films were studied for their creasability and solubility, as well as by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and wide angle X-ray scattering (WAXS). A comparison of these properties will be made.

  8. Low-lying electronic states of FeNC and FeCN: A theoretical journey into isomerization and quartet/sextet competition

    NASA Astrophysics Data System (ADS)

    DeYonker, Nathan J.; Yamaguchi, Yukio; Allen, Wesley D.; Pak, Chaeho; Schaefer, Henry F.; Peterson, Kirk A.

    2004-03-01

    With several levels of multireference and restricted open-shell single-reference electronic structure theory, optimum structures, relative energetics, and spectroscopic properties of the low-lying 6Δ, 6Π, 4Δ, 4Π, and 4Σ- states of linear FeNC and FeCN have been investigated using five contracted Gaussian basis sets ranging from Fe[10s8p3d], C/N[4s2p1d] to Fe[6s8p6d3f2g1h], C/N[6s5p4d3f2g]. Based on multireference configuration interaction (MRCISD+Q) results with a correlation-consistent polarized valence quadruple-zeta (cc-pVQZ) basis set, appended with core correlation and relativistic corrections, we propose the relative energies: Te(FeNC), 6Δ(0)<6Π (2300 cm-1)<4Δ (2700 cm-1)<4Π (4200 cm-1)<4Σ-; and Te(FeCN), 6Δ(0)<6Π (1800 cm-1)<4Δ (2500 cm-1)<4Π (2900 cm-1)<4Σ-. The 4Δ and 4Π states have massive multireference character, arising mostly from 11σ→12σ promotions, whereas the sextet states are dominated by single electronic configurations. The single-reference CCSDT-3 (coupled cluster singles and doubles with iterative partial triples) method appears to significantly overshoot the stabilization of the quartet states provided by both static and dynamical correlation. The 4,6Δ and 4,6Π states of both isomers are rather ionic, and all have dipole moments near 5 D. On the ground 6Δ surface, FeNC is predicted to lie 0.6 kcal mol-1 below FeCN, and the classical barrier for isocyanide/cyanide isomerization is about 6.5 kcal mol-1. Our data support the recent spectroscopic characterization by Lei and Dagdigian [J. Chem. Phys. 114, 2137 (2000)] of linear 6Δ FeNC as the first experimentally observed transition-metal monoisocyanide. Their assignments for the ground term symbol, isotopomeric rotational constants, and the Fe-N ω3 stretching frequency are confirmed; however, we find rather different structural parameters for 6Δ FeNC:re(Fe-N)=1.940 Å and r(N-C)=1.182 Å at the cc-pVQZ MRCISD+Q level. Our results also reveal that the observed band of Fe

  9. 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

    SciTech Connect

    Changala, P. Bryan; Baraban, Joshua H.; Field, Robert W.; Merer, Anthony J.

    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.

  10. Exercises in anatomy: cardiac isomerism.

    PubMed

    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

  11. Conformational isomerism in solid state of AMG 853--structure studies using solid-state nuclear magnetic resonance and X-ray diffraction.

    PubMed

    Kiang, Y-H; Nagapudi, Karthik; Wu, Tian; Peterson, Matthew L; Jona, Janan; Staples, Richard J; Stephens, Peter W

    2015-07-01

    Investigation of an additional resonance peak in the (19) F solid-state nuclear magnetic resonance (NMR) spectrum of AMG 853, a dual antagonist of DP and CRTH2 previously in clinical development for asthma, has led to the identification of two conformational isomers coexisting in the crystal lattice in a continuous composition range between 89.7%:10.3% and 96.5%:3.5%. These two isomers differ in the chloro-flurorophenyl moiety orientation-the aromatic ring is flipped by 180° in these two isomers. The level of the minor isomer is directly measured through integration of the two peaks in the (19) F solid-state NMR spectrum. The values obtained from the NMR data are in excellent agreement with the degree of disorder of the fluorine atom in the crystal structure, refined using both single-crystal and high-resolution powder X-ray diffraction data.

  12. Synthesis of Positional Isomeric Phenylphenalenones.

    PubMed

    Ospina, Felipe; Ramirez, Adrian; Cano, Marisol; Hidalgo, William; Schneider, Bernd; Otálvaro, Felipe

    2017-03-27

    A series of isomeric phenylphenalenones in which the phenyl ring is located at all possible peripheral positions of the phenalenone nuclei was synthesized. The structural characteristics of the series, in which topological variation is permitted with minimal electronic disturbance, could, in principle, allow for easy pharmacophore recognition when the compounds are aligned in steroidomimetic conformations.

  13. Simple, Chemoselective, Catalytic Olefin Isomerization

    PubMed Central

    2015-01-01

    Catalytic amounts of Co(SaltBu,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. PMID:25398144

  14. Reinvestigation of the direct two-proton decay of the long-lived isomer 94Ag(m) [0.4 s, 6.7 MeV, (21+)].

    PubMed

    Cerny, J; Moltz, D M; Lee, D W; Peräjärvi, K; Barquest, B R; Grossman, L E; Jeong, W; Jewett, C C

    2009-10-09

    An attempt to confirm the reported direct one-proton and two-proton decays of the (21+) isomer at 6.7(5) MeV in 94Ag has been made. The 0.39(4) s half-life of the isomer permitted use of a helium-jet system to transport reaction products from the 40Ca + (nat)Ni reaction at 197 MeV to a low-background area; 24 gas DeltaE-(Si)E detector telescopes were used to identify emitted protons down to 0.4 MeV. No evidence was obtained for two-proton radioactivity with a summed energy of 1.9(1) MeV and a branching ratio of 0.5(3)%. Two groups of one-proton radioactivity from this isomer had also been reported; our data confirm the lower energy group at 0.79(3) MeV with its branching ratio of 1.9(5)%.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. The isomeric structure of 132Pr

    NASA Astrophysics Data System (ADS)

    Alharshan, G. A.; Cullen, D. M.; Taylor, M. J.; Procter, M. G.; Lumley, N. M.; Grahn, T.; Greenless, P. T.; Hauschild, K.; Herzon, A.; Jakobsson, U.; Jones, P. M.; Julin, R.; Juutinen, S.; Ketelhut, S.; Leino, M.; Lopez-Martens, A.; Nieminen, P.; Pantanen, J.; Peura, P.; Rahkila, P.; Rinta-Antilla, S.; Ruatsalainen, P.; Sandzelius, H. M.; Saren, J.; Scholey, C.; Sorri, J.; Stolze, S.; Uusitalo, J.

    2012-09-01

    The isomeric structure of the neutron deficient nucleus 132Pr, located in the rare-earth region of the nuclear chart, has been studied with the 98Mo(40Ar,5pn)132Pr reaction at beam energies of 150, 158 and 165 MeV. The experiment was performed at the University of Jyväskylä, Finland where the 40Ar beam was accelerated onto the target by the K130 cyclotron. The JUROGAM II HPGe detector array was employed in conjunction with the RITU gas-filled recoil separator. The focal-plane chamber housed a multi wire proportional counter and a position-sensitive silicon strip detector used for the implantation and identification of recoiling nuclei. The recoil-isomer tagging technique was used to correlate the delayed decays, measured in the Planar and Clover detectors of the GREAT spectrometer, with the known prompt transitions in 132Pr. Two new delayed transitions have been observed at energies of 102 and 118 keV. The corresponding X ray peaks are consistent with Pr Kα and Kβ X rays with energies of 35.63 and 40.91 keV, respectively. The half-life of the newly established isomeric state, from which the 102 and 118-keV transitions proceed, has been measured to be 2.5(3) μs.

  17. Trans-cis isomerization of lipophilic dyes probing membrane microviscosity in biological membranes and in live cells.

    PubMed

    Chmyrov, Volodymyr; Spielmann, Thiemo; Hevekerl, Heike; Widengren, Jerker

    2015-06-02

    Membrane environment and fluidity can modulate the dynamics and interactions of membrane proteins and can thereby strongly influence the function of cells and organisms in general. In this work, we demonstrate that trans-cis isomerization of lipophilic dyes is a useful parameter to monitor packaging and fluidity of biomembranes. Fluorescence fluctuations, generated by trans-cis isomerization of the thiocarbocyanine dye Merocyanine 540 (MC540), were first analyzed by fluorescence correlation spectroscopy (FCS) in different alcohol solutions. Similar isomerization kinetics of MC540 in lipid vesicles could then also be monitored, and the influence of lipid polarity, membrane curvature, and cholesterol content was investigated. While no influence of membrane curvature and lipid polarity could be observed, a clear decrease in the isomerization rates could be observed with increasing cholesterol contents in the vesicle membranes. Finally, procedures to spatially map photoinduced and thermal isomerization rates on live cells by transient state (TRAST) imaging were established. On the basis of these procedures, MC540 isomerization was studied on live MCF7 cells, and TRAST images of the cells at different temperatures were found to reliably detect differences in the isomerization parameters. Our studies indicate that trans-cis isomerization is a useful parameter for probing membrane dynamics and that the TRAST imaging technique can provide spatial maps of photoinduced isomerization as well as both photoinduced and thermal back-isomerization, resolving differences in local membrane microviscosity in live cells.

  18. Study of ground and excited state decays in N ≈ Z Ag nuclei

    NASA Astrophysics Data System (ADS)

    Moschner, K.; Blazhev, A.; Warr, N.; Boutachkov, P.; Davies, P.; Wadsworth, R.; Ameil, F.; Baba, H.; Bäck, T.; Dewald, M.; Doornenbal, P.; Faestermann, T.; Gengelbach, A.; Gerl, J.; Gernhäuser, R.; Go, S.; Górska, M.; Grawe, H.; Gregor, E.; Hotaka, H.; Isobe, T.; Jenkins, D. G.; Jolie, J.; Jung, H. S.; Kojouharov, I.; Kurz, N.; Lewitowicz, M.; Lorusso, G.; Merchan, E.; Naqvi, F.; Nishibata, H.; Nishimura, D.; Nishimura, S.; Pietralla, N.; Schaffner, H.; Söderström, P.-A.; Steiger, K.; Sumikama, T.; Taprogge, J.; Thöle, P.; Watanabe, H.; Werner, V.; Xu, Z. Y.; Yagi, A.; Yoshinaga, K.; Zhu, Y.

    2015-05-01

    A decay spectroscopy experiment was performed within the EURICA campaign at RIKEN in 2012. It aimed at the isomer and particle spectroscopy of excited states and ground states in the mass region below the doubly magic 100Sn. The N = Z nuclei 98In, 96Cd and 94Ag were of particular interest for the present study. Preliminary results on the neutron deficient nuclei 93Ag and 94Ag are presented. In 94Ag a more precise value for the half-life of the ground state's superallowed Fermi transition was deduced. In addition the energy spectra of the mentioned decay could be reproduced through precise Geant4 simulations of the used active stopper SIMBA. This will enable us to extract Qβ values from the measured data. The decay of 93Ag is discussed based on the observed implantation-decay correlation events.

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

    PubMed

    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.

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

    PubMed Central

    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

  1. Imaging the Predicted Isomerism of Oligo(aniline)s: A Scanning Tunneling Microscopy Study.

    PubMed

    Thomas, James O; Andrade, Hugo D; Mills, Benjamin M; Fox, Neil A; Hoerber, Heinrich J K; Faul, Charl F J

    2015-07-01

    The self-assembly of two emeraldine base tetra(aniline) derivatives is investigated using scanning tunneling microscopy. A combination of the scanning tunneling microscopy data and calculations reveals the presence of predicted cis/trans isomerism in this oxidation state. This isomerism is shown to hinder self-assembly into ordered structures, and provides indications as to why the properties of these materials, and their parent polymer, polyaniline, remain unfulfilled.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Ultrafast Extreme Ultraviolet Induced Isomerization of Acetylene Cations

    SciTech Connect

    Jiang, Y. H.; Kurka, M.; Kuehnel, K. U.; Schroeter, C. D.; Moshammer, R.; Rudenko, A.; Foucar, L.; Herrwerth, O.; Lezius, M.; Kling, M. F.; Tilborg, J. van; Belkacem, A.; Ueda, K.; Duesterer, S.; Treusch, R.; Ullrich, J.

    2010-12-31

    Ultrafast isomerization of acetylene cations ([HC=CH]{sup +}) in the low-lying excited A{sup 2}{Sigma}{sub g}{sup +} state, populated by the absorption of extreme ultraviolet (XUV) photons (38 eV), has been observed at the Free Electron Laser in Hamburg, (FLASH). Recording coincident fragments C{sup +}+CH{sub 2}{sup +} as a function of time between XUV-pump and -probe pulses, generated by a split-mirror device, we find an isomerization time of 52{+-}15 fs in a kinetic energy release (KER) window of 5.8

  4. Ultrafast Extreme Ultraviolet Induced Isomerization of Acetylene Cations

    SciTech Connect

    Jiang, Y.; Rudenko, Artem; Herrwerth, O.; Foucar, L.; Kurka, M.; Kuhnel, K.; Lezius, M.; Kling, Matthias; van Tilborg, Jeroen; Belkacem, Ali; Ueda, K.; Dusterer, S.; Treusch, R.; Schroter, Claus-Dieter; Moshammer, Robbert; Ullrich, Joachim

    2011-06-17

    Ultrafast isomerization of acetylene cations ([HC = CH]{sup +}) in the low-lying excited A{sup 2}{Sigma}{sub g}{sup +} state, populated by the absorption of extreme ultraviolet (XUV) photons (38 eV), has been observed at the Free Electron Laser in Hamburg, (FLASH). Recording coincident fragments C{sup +} + CH{sub 2}{sup +} as a function of time between XUV-pump and -probe pulses, generated by a split-mirror device, we find an isomerization time of 52 {+-} 15 fs in a kinetic energy release (KER) window of 5.8 < KER < 8 eV, providing clear evidence for the existence of a fast, nonradiative decay channel.

  5. Favored configurations for four-quasiparticle K isomerism in the heaviest nuclei

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    Configuration-constrained potential-energy-surface calculations are performed including β6 deformation to investigate high-K isomeric states in nuclei around 254No and 270Ds, the heaviest nuclei where there have been some observations of two-quasiparticle isomers, while data for four-quasiparticle isomers are scarce. We predict the prevalent occurrence of four-quasiparticle isomeric states in these nuclei, together with their favored configurations. The most notable examples, among others, are Kπ=20+ states in 266,268Ds and 268,270Cn having very high K value, relatively low excitation energy, and well-deformed axially symmetric shape. The predicted isomeric states, with hindered spontaneous fission and α decay, could play a significant role in the future study of superheavy nuclei.

  6. Rotational isomerism of molecules in condensed phases

    NASA Astrophysics Data System (ADS)

    Sakka, Tetsuo; Iwasaki, Matae; Ogata, Yukio

    1991-08-01

    A statistical mechanical model is developed for the description of the conformational distribution of organic molecules in the liquid and solid phases. In the model, they are assumed to have one internal freedom of rotation. The molecules are fixed to lattice sites and have two types of ordering, conformational and distributional. The latter is supposed to represent an ordering typical of solid state. The model is compared with the experimental results of the rotational-isomeric ratio of 1,2-dichloro-1,1-difluoroethane, in the temperature range from 77 to 300 K. It explains successfully the experimental results, especially the behavior near the melting point. From the point of view of melting, the present model is an extension of the Lennard-Jones and Devonshire model, because, when the distinctions between the two conformers are neglected, the parameter representing the distributional ordering of the molecules results in the same equation as that derived from the Lennard-Jones and Devonshire model.

  7. HCP CPH ISOMERIZATION: Caught in the Act

    NASA Astrophysics Data System (ADS)

    Ishikawa, H.; Field, R. W.; Farantos, S. C.; Joyeux, M.; Koput, J.; Beck, C.; Schinke, R.

    1999-10-01

    In this overview we discuss the vibrational spectrum of phosphaethyne, HCP, in its electronic ground state, as revealed by complementary experimental and theoretical examinations. The main focus is the evolution of specific spectral patterns from the bottom of the potential well up to excitation energies of approximately 25,000 cm-1, where large-amplitude, isomerization-type motion from H-CP to CP-H is prominent. Distinct structural and dynamical changes, caused by an abrupt transformation from essentially HC bonding to mainly PH bonding, set in around 13,000 cm-1. They reflect saddle-node bifurcations in the classical phase space-a phenomenon well known in the nonlinear dynamics literature-and result in characteristic patterns in the spectrum and the quantum-number dependence of the vibrational fine-structure constants. Two polar opposites are employed to elucidate the spectral patterns: the exact solution of the Schrodinger equation, using an accurate potential energy surface and an effective or resonance Hamiltonian (expressed in a harmonic oscillator basis set and block diagonalized into polyads), which is defined by parameters adjusted to fit either the measured or the calculated vibrational energies. The combination of both approaches-together with classical mechanics and semiclassical analyses-provides a detailed spectroscopic picture of the breaking of one bond and the formation of a new one.

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

    NASA Astrophysics Data System (ADS)

    Danagulyan, A. S.; Hovhannisyan, G. H.; Bakhshiyan, T. M.; Martirosyan, G. V.

    2016-05-01

    Calculations for ( p, n) and (α, p3 n) reactions were performed with the aid of the TALYS-1.4 code. Reactions in which the mass numbers of target and product nuclei were identical were examined in the range of A = 44-124. Excitation functions were obtained for product nuclei in ground and isomeric states, and isomeric ratios were calculated. The calculated data reflect well the dependence of the isomeric ratios on the projectile type. A comparison of the calculated and experimental data reveals, that, for some nuclei in a high-spin state, the calculated data fall greatly short of their experimental counterparts. These discrepancies may be due to the presence of high-spin yrast states and rotational bands in these nuclei. Calculations involving various level-density models included in the TALYS-1.4 code with allowance for the enhancement of collective effects do not remove the discrepancies in the majority of cases.

  9. Direct dynamics study of hydrogen-transfer isomerization of 1-pentyl and 1-hexyl radicals.

    PubMed

    Zheng, Jingjing; Truhlar, Donald G

    2009-10-29

    The rate constants of three intramolecular hydrogen-transfer isomerization reactions, namely, 1-4 isomerization of the 1-pentyl radical and 1-4 and 1-5 isomerizations of the 1-hexyl radical, are calculated using variational transition state theory with multidimensional tunneling, in particular by using canonical variational theory (CVT, which is the version of variational transition state theory in which the transition state dividing surface is optimized for a canonical ensemble) with small-curvature tunneling (SCT) for the transmission coefficient. The required potential energy surfaces were obtained implicitly by direct dynamics employing interpolated variational transition state theory with mapping (IVTST-M) and variational transition state theory with interpolated single-point energies (VTST-ISPE). Single-level direct dynamics calculations were performed for all of the reactions by IVTST-M using M06-2X/MG3S or M08-HX/cc-pVTZ+ potential energy surfaces or both. The stationary points of 1-4 isomerization of 1-pentyl and the stationary points for the forward reactions of 1-4 and 1-5 isomerizations of 1-hexyl were also optimized by BMC-CCSD, and for all three reactions we also performed dual-level direct dynamics calculations using VTST-ISPE in which MCG3-MPW single-point energies served as the higher level. The calculated MCG3-MPW//M06-2X/MG3S rate constants agree well with experimental values for 1-4 isomerization of the 1-pentyl radical at high temperature, and this validates the accuracy of this theoretical method for 1-4 isomerization. The MCG3-MPW//M06-2X/MG3S method was therefore used to make a reliable prediction for the rata constants of 1-4 isomerization of the 1-hexyl radical for which a direct experimental measurement is not available. The calculated CVT/SCT/M08-HX/cc-pVTZ+ rate constants agree well with experimental values for 1-5 isomerization of the 1-hexyl radical, and they show that the tunneling effect for these reactions was underestimated in

  10. Direct Dynamics Study of Hydrogen-Transfer Isomerization of 1-Pentyl and 1-Hexyl Radicals

    NASA Astrophysics Data System (ADS)

    Zheng, Jingjing; Truhlar, Donald G.

    2009-07-01

    The rate constants of three intramolecular hydrogen-transfer isomerization reactions, namely, 1-4 isomerization of the 1-pentyl radical and 1-4 and 1-5 isomerizations of the 1-hexyl radical, are calculated using variational transition state theory with multidimensional tunneling, in particular by using canonical variational theory (CVT, which is the version of variational transition state theory in which the transition state dividing surface is optimized for a canonical ensemble) with small-curvature tunneling (SCT) for the transmission coefficient. The required potential energy surfaces were obtained implicitly by direct dynamics employing interpolated variational transition state theory with mapping (IVTST-M) and variational transition state theory with interpolated single-point energies (VTST-ISPE). Single-level direct dynamics calculations were performed for all of the reactions by IVTST-M using M06-2X/MG3S or M08-HX/cc-pVTZ+ potential energy surfaces or both. The stationary points of 1-4 isomerization of 1-pentyl and the stationary points for the forward reactions of 1-4 and 1-5 isomerizations of 1-hexyl were also optimized by BMC-CCSD, and for all three reactions we also performed dual-level direct dynamics calculations using VTST-ISPE in which MCG3-MPW single-point energies served as the higher level. The calculated MCG3-MPW//M06-2X/MG3S rate constants agree well with experimental values for 1-4 isomerization of the 1-pentyl radical at high temperature, and this validates the accuracy of this theoretical method for 1-4 isomerization. The MCG3-MPW//M06-2X/MG3S method was therefore used to make a reliable prediction for the rata constants of 1-4 isomerization of the 1-hexyl radical for which a direct experimental measurement is not available. The calculated CVT/SCT/M08-HX/cc-pVTZ+ rate constants agree well with experimental values for 1-5 isomerization of the 1-hexyl radical, and they show that the tunneling effect for these reactions was underestimated in

  11. Global reaction route mapping of isomerization pathways of exotic C{sub 6}H molecular species

    SciTech Connect

    Vikas, E-mail: qlabspu@yahoo.com; Kaur, Gurpreet

    2013-12-14

    C{sub 6}H radical is known to exist in the astrophysical environment in linear form; however, it may originate from nonlinear isomeric forms. Potential energy surface of C{sub 6}H is explored to search isomers of C{sub 6}H and transition states connecting them. This work reports first-ever identification of reaction pathways for isomerization of C{sub 6}H. The reaction route search is performed through global reaction route mapping method, which utilizes an uphill walking technique based on an anharmonic downward distortion following approach to search intermediates and transition states. The computations performed at the CASSCF/aug-cc-pVTZ, CCSD(T)/6-311++G(d,p)//DFT/B3LYP/6-311++G(d,p), and DFT/B3LYP/aug-cc-pVTZ levels of the theory identified 14 isomers (including 8 new isomeric forms of C{sub 6}H) and 28 transition states. Most of the identified isomers are found to have significant multireference character. The kinetic stability and natural bond orbital analysis of the identified isomers is also investigated. The isomeric forms are further characterized using spectral analysis involving rotational constants, vibrational frequencies, and Raman scattering activities as well as analyzing the effect of isotopic substitution of hydrogen on the spectral features. This study proposes that the linear-C{sub 6}H can readily isomerize to a six-member ring isomer.

  12. Global reaction route mapping of isomerization pathways of exotic C6H molecular species

    NASA Astrophysics Data System (ADS)

    Vikas, Kaur, Gurpreet

    2013-12-01

    C6H radical is known to exist in the astrophysical environment in linear form; however, it may originate from nonlinear isomeric forms. Potential energy surface of C6H is explored to search isomers of C6H and transition states connecting them. This work reports first-ever identification of reaction pathways for isomerization of C6H. The reaction route search is performed through global reaction route mapping method, which utilizes an uphill walking technique based on an anharmonic downward distortion following approach to search intermediates and transition states. The computations performed at the CASSCF/aug-cc-pVTZ, CCSD(T)/6-311++G(d,p)//DFT/B3LYP/6-311++G(d,p), and DFT/B3LYP/aug-cc-pVTZ levels of the theory identified 14 isomers (including 8 new isomeric forms of C6H) and 28 transition states. Most of the identified isomers are found to have significant multireference character. The kinetic stability and natural bond orbital analysis of the identified isomers is also investigated. The isomeric forms are further characterized using spectral analysis involving rotational constants, vibrational frequencies, and Raman scattering activities as well as analyzing the effect of isotopic substitution of hydrogen on the spectral features. This study proposes that the linear-C6H can readily isomerize to a six-member ring isomer.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2009-05-13

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

  17. Ordering of azobenzenes by two-photon isomerization

    SciTech Connect

    Ishitobi, Hidekazu; Sekkat, Zouheir; Kawata, Satoshi

    2006-10-28

    We report on light induced orientation by two-photon isomerization of azobenzenes in films of polymer. The dynamics of isomerization and orientation by one-photon absorption and two-photon absorption (TPA) are similar, and TPA creates a degree of molecular orientation which is comparable to that achieved by single-photon isomerization, in agreement with the theoretical predictions of two-photon isomeric orientation.

  18. Internal electron conversion of the isomeric {sup 57}Fe nucleus state with an energy of 14.4 keV excited by the radiation of the plasma of a high-power femtosecond laser pulse

    SciTech Connect

    Golovin, G V; Savel'ev-Trofimov, Andrei B; Uryupina, D S; Volkov, Roman V

    2011-03-31

    We recorded the spectrum of delayed secondary electrons ejected from the target, which was coated with a layer of iron enriched with the {sup 57}Fe isotope to 98%, under its irradiation by fluxes of broadband X-ray radiation and fast electrons from the plasma produced by a femtosecond laser pulse at an intensity of 10{sup 17} W cm{sup -2}. Maxima were identified at energies of 5.6, 7.2, and 13.6 keV in the spectrum obtained for a delay of 90 - 120 ns. The two last-listed maxima owe their origin to the internal electron conversion of the isomeric level with an energy of 14.4 keV and a lifetime of 98 ns to the K and L shells of atomic iron, respectively; the first-named level arises from a cascade K - L{sub 2}L{sub 3} Auger process. Photoexcitaion by the X-ray plasma radiation is shown to be the principal channel of the isomeric level excitation. (interaction of laser radiation with matter)

  19. Coherence-enhanced optical determination of the 229Th isomeric transition.

    PubMed

    Liao, Wen-Te; Das, Sumanta; Keitel, Christoph H; Pálffy, Adriana

    2012-12-28

    The impact of coherent light propagation on the excitation and fluorescence of thorium nuclei in a crystal lattice environment is investigated theoretically. We find that in the forward direction, the fluorescence signal exhibits characteristic intensity modulations dominated by a sped-up initial decay signal that is orders of magnitude faster. This feature can be exploited for the optical determination of the isomeric transition energy. In order to obtain a unmistakable signature of the isomeric nuclear fluorescence, we put forward a novel scheme for the direct measurement of the transition energy via electromagnetically modified nuclear forward scattering involving two fields that couple to three nuclear states.

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

    NASA Astrophysics Data System (ADS)

    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.

  1. A theoretical examination of the isomerization of BrONO 2 to BrOONO

    NASA Astrophysics Data System (ADS)

    Kovačič, S.; Lesar, A.; Hodošček, M.; Koller, J.

    2006-04-01

    The structural properties of the BrONO2 ↔ BrOONO isomerization transition states are examined using density functional calculations in conjunction with different basis sets. The energy barriers for the isomerization pathways at the CBS-QB3 level of theory are large enough, from 34.2 up to 32.5 kcal mol -1, to prevent the isomerization of BrONO 2 to either cis-perp or trans-perp BrOONO. But, the energy barriers of only 8.3 and 4.7 kcal mol -1 make feasible an interconversion process of cis-perp BrOONO and trans-perp BrOONO, respectively, to BrONO 2.

  2. CRIS: A new method in isomeric beam production

    NASA Astrophysics Data System (ADS)

    Lynch, K. M.; Billowes, J.; Bissell, M. L.; Budincevic, I.; Cocolios, T. E.; De Groote, R. P.; De Schepper, S.; Fedosseev, V. N.; Flanagan, K. T.; Franchoo, S.; Garcia Ruiz, R. F.; Heylen, H.; Marsh, B. A.; Mason, P. J. R.; Neyens, G.; Procter, T. J.; Rossel, R. E.; Rothe, S.; Simpson, G. S.; Smith, A. J.; Strashnov, I.; Stroke, H. H.; Walker, P. M.; Wendt, K. D. A.; Wood, R. T.

    2013-12-01

    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.

  3. Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization.

    PubMed

    Heeb, Norbert V; Schweizer, W Bernd; Mattrel, Peter; Haag, Regula; Gerecke, Andreas C; Schmid, Peter; Zennegg, Markus; Vonmont, Heinz

    2008-11-01

    Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.

  4. Chemical Tools To Decipher Regulation of Phosphatases by Proline Isomerization on Eukaryotic RNA Polymerase II.

    PubMed

    Mayfield, Joshua E; Fan, Shuang; Wei, Shuo; Zhang, Mengmeng; Li, Bing; Ellington, Andrew D; Etzkorn, Felicia A; Zhang, Yan Jessie

    2015-10-16

    Proline isomerization greatly impacts biological signaling but is subtle and difficult to detect in proteins. We characterize this poorly understood regulatory mechanism for RNA polymerase II carboxyl terminal domain (CTD) phosphorylation state using novel, direct, and quantitative chemical tools. We determine the proline isomeric preference of three CTD phosphatases: Ssu72 as cis-proline specific, Scp1 and Fcp1 as strongly trans-preferred. Due to this inherent characteristic, these phosphatases respond differently to enzymes that catalyze the isomerization of proline, like Ess1/Pin1. We demonstrate that this selective regulation of RNA polymerase II phosphorylation state exists within human cells, consistent with in vitro assays. These results support a model in which, instead of a global enhancement of downstream enzymatic activities, proline isomerases selectively boost the activity of a subset of CTD regulatory factors specific for cis-proline. This leads to diversified phosphorylation states of CTD in vitro and in cells. We provide the chemical tools to investigate proline isomerization and its ability to selectively enhance signaling in transcription and other biological contexts.

  5. E/Z Isomers and Isomerization

    NASA Astrophysics Data System (ADS)

    Liaaen-Jensen, Synnøve; Lutnœes, Bjart Frode

    The natural occurrence of several carotenoid cis isomers and their biological significance were not anticipated in 1962, when the classical monograph on cis-trans isomeric carotenoids [1] was published. More recent research has demonstrated that various cis isomers occur naturally in bacteria plants, algae and invertebrate animals, and are present in human blood and tissues. The participation of cis isomers in the biosynthethic route to coloured carotenoids is well established (Volume 3, Chapter 2). Important biological functions of (15Z)-carotenoids in photosynthesis have been revealed [2]. In relation to health aspects of carotenoids, the bioavailability of cis isomers may be higher than that of the all-trans isomer [3], and accumulated evidence suggests that cis/trans isomerization may occur in biological tissues, particularly of lycopene (31) in human serum [4] (Volume 5, Chapter 7).

  6. Isomerization of one molecule observed through tip enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Yanxing; Lee, Joonhee; Apkarian, Vartkess A.; Wu, Ruqian; Ruqian Wu, Yanxing Zhang Team; Joonhee Lee, Vartkess A. Apkarian Team

    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 apparently heterogeneously photo-catalyzed reaction is assigned to cis-trans isomerization of an outlier, which is chemisorbed on the silver tip of the STM. In order to clarify the role of the silver tip of the STM, we perform systematic density functional theory (DFT) calculations. The results show that compared with the case on the flat Ag(111) surface, the energy difference between trans and cis states of ABT decrease as we add one silver atom or a tetrahedron silver cluster on Ag(111) surface which mimic the geometry of a silver tip. In particular, the trans stretches away from the surface on the tetrahedral silver cluster, and the energy difference between trans and cis decreases to 0.27 eV, from ~1 eV for ABT on the flat Ag(111) surface. This significantly increases the possibility of cis-trans isomerization, as observed in our experiments. Work was supported by the National Science Foundation Center for Chemical Innovation on Chemistry at the Space-Time Limit (CaSTL) under Grant No. CHE-1414466.

  7. Confirmed Assignments of Isomeric Dimethylbenzyl Radicals Generated by Corona Discharge

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Lee, Sang Kuk

    2012-06-01

    Polymethylbenzyl radicals, multi-methyl-substituted benzyl radicals, have been believed to be an ideal model for understanding the torsional effect of methyl group and substitution effect on electronic transition. These radicals are mainly generated from polymethylbenzenes by electric discharge for spectroscopic observation. However, the existence of several methyl groups on the benzene ring may produce several isomeric polymethylbenzyl radicals by removing one of the C-H bonds of each methyl group at different substitution position, which makes the assignment of spectrum ambiguous. In this work, the controversial vibronic assignments of isomeric dimethylbenzyl radicals were clearly resolved by using different precursors. By using corresponding dimethylbenzyl chlorides as precursors, we identified the origins of the vibronic bands of the dimethylbenzyl radicals generated by corona discharge of precursors 1,2,3- and 1,2,4-trimethylbenzenes. From the analysis of the spectra observed from the dimethylbenzyl chlorides in a corona excited supersonic expansion using a pinhole-type glass nozzle, we revised previous assignments of the 2,6- and 2,3-dimethylbenzyl radicals as well as the 3,4-, 2,4-, and 2,5-dimethylbenzyl radicals. In addition, spectroscopic data of electronic transition and vibrational mode frequencies in the ground electronic state of each isomer were accurately determined by comparing them with those obtained by an ab initio calculation and with the known vibrational data of precursors.

  8. Skeletal isomerization of n-butenes

    SciTech Connect

    Guisnet, M.; Andy, P.; Gnep, N.S.

    1996-02-01

    The transformation of n-butenes and of isobutene was carried out at 350{degrees}C on a fresh H-FER zeolite (Si/Al = 13.8) with various contact times so as to obtain a large range of conversion (from 5 to 65%). With both reactants the skeletal isomerization was accompanied by the formation of various products. The skeletal isomer, propene, pentenes, octenes (traces), and n-butane (from n-butenes) or isobutane (traces from isobutene) appeared as primary products. The simultaneous formation of the skeletal isomer and of propene and pentenes proved the presence of a dimerization-cracking process. Moreover, the low amount of octenes in the products showed that dimerization was the limiting step of the process. The dimerization step involved two secondary carbenium ions, which explained its slow rate. The dimer was rapidly isomerized through Type A (alkyl shift) or Type B (via protonated cyclopropanes) isomerization into the other octenes. Lastly octenes with a trimethylpentane or a dimethylhexane skeleton were rapidly cracked into isobutene, propene, and pentenes through Type A (involving two tertiary and one secondary carbenium ions) mechanisms. The transformation of n-pentenes and of n-octenes confirmed the high rate of the Type A and B isomerization and cracking steps. The slow rate of octene formation from butenes was also due to an inhibition of the diffusion of branched octenes in the narrow pores of H-FER. The shape selectivity of H-FER was also responsible for the very slow formation of isobutane by hydrogen transfer from coke precursors to isobutene and for the unexpected slow formation of propene and of pentenes from isobutene. 43 refs., 5 figs., 2 tabs.

  9. Isomerization of C[sub 4] alkenes

    DOEpatents

    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.

  10. Isomerization of C.sub.4 alkenes

    DOEpatents

    Smith, Jr., Lawrence A.

    1984-01-01

    A method 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 codimer, which comprieses 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 codimer of isobutene and n-butene, whereby an overhead fraction containing any unreacted isobutene and n-butene and a bottoms fraction containing codimer 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.

  11. Methods for suppressing isomerization of olefin metathesis products

    DOEpatents

    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.

  12. Dynamics of radiation induced isomerization for HCN-CNH

    SciTech Connect

    Na, Kyungsun; Jung, Christof; Reichl, L. E.

    2006-07-21

    We have analyzed the dynamics underlying the use of sequential radiation pulses to control the isomerization between the HCN and the CNH molecules. The appearance of avoided crossings among Floquet eigenphases as the molecule interacts with the radiation pulses is the key to understanding the isomerization dynamics, both in the adiabatic and nonadiabatic regimes. We find that small detunings of the incident pulses can have a significant effect on the outcome of the isomerization process for the model we consider.

  13. Amine-Catalyzed Isomerization of Diethylmaleate to Diethylfumarate.

    ERIC Educational Resources Information Center

    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)

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

    PubMed

    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.

  15. TD-DFT calculations of the potential energy curves for the trans-cis photo-isomerization of protonated Schiff base of retinal.

    PubMed

    Tachikawa, Hiroto; Iyama, Tetsuji

    2004-10-25

    One-dimensional potential energy curves for the isomerization of protonated Schiff base of retinal (PSBR) in bacteriorhodopsin (bR), i.e., isomerization from all-trans- to 13-cis-forms, have been calculated by means of time-dependent density functional theory (TD-DFT) calculations, in order to elucidate the mechanism of initial step in photo-absorption. The transition state of the isomerization in the first excited state is located at theta(13-14)=58 degrees , where theta(13-14) means twist angle around the C(13)=C(14) double bond of PSBR The potential barrier is formed by the avoided crossing between S(1) (B(u)-like) and S(2) (A(g)-like) states. The mechanism of the isomerization was discussed on the basis of theoretical results.

  16. Free-energy profile along an isomerization pathway: Conformational isomerization in alanine dipeptide

    NASA Astrophysics Data System (ADS)

    Lee, In-Ho

    2013-02-01

    The free-energy profile for the conformational isomerization process in alanine dipeptide is presented in atomistic detail by using an action-derived molecular dynamics (ADMD) method and replica-exchange molecular dynamics (REMD) method. First, by employing ADMD, a dynamic isomerization pathway model of the alanine dipeptide with two available low-energy conformations, C7 ax and C7 eq , is determined. The pathway model is chosen to be the reaction coordinate, so the isomerization process is characterized by the ADMD step index, which is not an a-priori reaction coordinate as found in conventional studies of molecular conformational changes. Second, by employing the REMD method, the free-energy profile is calculated as a function of temperature. This couple of procedures is a quite natural protocol for conformational isomerization process simulations, irrespective of the arbitrary selection of the reaction coordinate. The alliance between the two simulation methods, ADMD and REMD, is demonstrated to have a great synergy effect on understanding the conformational changes in molecules.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Proton NMR characterization of isomeric sulfmyoglobins: preparation, interconversion, reactivity patterns, and structural features

    SciTech Connect

    Chatfield, M.J.; La Mar, G.N.; Kauten, R.J.

    1987-11-03

    The preparations of sulfmyoglobin (sulf-Mb) by standard procedures have been found heterogeneous by /sup 1/H NMR spectroscopy. Presented here are the results of a comprehensive study of the factors that influence the selection among the three dominant isomeric forms of sperm whale sulf-Mb and their resulting detailed optical and /sup 1/H NMR properties as related to their detectability and structural properties of the heme pocket. A single isomer is formed initially in the deoxy state; further treatment in any desired oxidation/ligation state can yield two other major isomers. Acid catalysis and chromatography facilitate formation of a second isomer, particularly in the high-spin state. At neutral pH, a third isomer is formed by a first-order process. The processes that alter oxidation/ligation state are found to be reversible and are judged to affect only the metal center, but the three isomeric sulf-Mbs are found to exhibit significantly different ligand affinity and chemical stability. The present results allow, for the first time, a rational approach for preparing a given isomeric sulf-Mb in an optimally pure state for subsequent characterization by other techniques. While optical spectroscopy can distinguish the alkaline forms, only /sup 1/H NMR clearly distinguishes all three ferric isomers. The hyperfine shift patterns in the various oxidation/spin states of sulf-Mbs indicate relatively small structural alteration, and the proximal and distal sides of the heme suggest that peripheral electronic effects are responsible for the differentially reduced ligand affinities for the three isomeric sulf-Mbs. The first /sup 1/H NMR spectra of sulfhemoglobins are presented, which indicate a structure similar to that of the initially formed sulf-Mb isomer but also suggest the presence of a similar molecular heterogeneity as found for sulf-Mb, albiet to a smaller extent.

  19. Acid-Catalyzed Isomerization of Carvone to Carvacrol

    ERIC Educational Resources Information Center

    Kjonaas, Richard A.; Mattingly, Shawn P.

    2005-01-01

    The acid-catalyzed isomerization of carvone to carvacrol, first reported by Ritter and Ginsburg, is especially well suited with a permanent-magnet FT instrument. The acid-catalyzed isomerization of carvone to carvacrol produced a 61% yield after a three hour reflux with 30% aqueous sulfuric acid.

  20. Infrared-induced conformational isomerization and vibrational relaxation dynamics in melatonin and 5-methoxy-N-acetyl tryptophan methyl amide

    NASA Astrophysics Data System (ADS)

    Dian, Brian C.; Florio, Gina M.; Clarkson, Jasper R.; Longarte, Asier; Zwier, Timothy S.

    2004-05-01

    The conformational isomerization dynamics of melatonin and 5-methoxy N-acetyltryptophan methyl amide (5-methoxy NATMA) have been studied using the methods of IR-UV hole-filling spectroscopy and IR-induced population transfer spectroscopy. Using these techniques, single conformers of melatonin were excited via a well-defined NH stretch fundamental with an IR pump laser. This excess energy was used to drive conformational isomerization. By carrying out the infrared excitation early in a supersonic expansion, the excited molecules were re-cooled into their zero-point levels, partially re-filling the hole created in the ground state population of the excited conformer, and creating gains in population of the other conformers. These changes in population were detected using laser-induced fluorescence downstream in the expansion via an UV probe laser. The isomerization quantum yields for melatonin show some conformation specificity but no hint of vibrational mode specificity. In 5-methoxy NATMA, no isomerization was observed out of the single conformational well populated in the expansion in the absence of the infrared excitation. In order to study the dependence of the isomerization on the cooling rate, the experimental arrangement was modified so that faster cooling conditions could be studied. In this arrangement, the pump and probe lasers were overlapped in space in the high density region of the expansion, and the time dependence of the zero-point level populations of the conformers was probed following selective excitation of a single conformation. The analysis needed to extract isomerization quantum yields from the timing scans was developed and applied to the melatonin timing scans. Comparison between the frequency and time domain isomerization quantum yields under identical experimental conditions produced similar results. Under fast cooling conditions, the product quantum yields were shifted from their values under standard conditions. The results for melatonin

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

    SciTech Connect

    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.

  2. Ab initio kinetics for isomerization reaction of normal-chain hexadiene isomers

    NASA Astrophysics Data System (ADS)

    Yang, Feiyu; Deng, Fuquan; Pan, Youshun; Tian, Zemin; Zhang, Yingjia; Huang, Zuohua

    2016-10-01

    The ground-state potential energy surface (PES) of isomerization philosophy of ten normal-chain hexadiene isomers is computed by density functional methods using the geometries optimized at B3LYP/6-311++G (d, p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization reactions by transition state theory (TST) in the temperature range of 500-2500 K. Difference of rate constant between each hexadiene isomer is interpreted through the PES and Ḣ atom transfer, and only 2,4-hexadiene readily fulfills cis-cis to trans-trans conformation conversion. All the conversions are kinetically interpreted from the PES and ST geometry.

  3. Hoono Isomerization to HONO_2 Involving Conical Intersections

    NASA Astrophysics Data System (ADS)

    Kumar, T. J. Dhilip; Stanton, John F.; Barker, John R.

    2009-06-01

    The important atmospheric reactions HO_2 + NO and OH + NO_2 lead to formation and dissociation of the cis- and trans- isomers of the HOONO complex. In the present work, the global HNO_3 potential energy surface (PES) is being studied by using high-level ab initio electronic structure methods. This PES and others in the same class have been studied previously by others. In the F + NO_2 reaction system, UCCSD(T) calculations showed that FONO isomerizes to FNO_2 through a tight transition state involving a two-state avoided curve crossing. A similar mechanism has been invoked for HOONO, which is isoelectronic with FONO. CASSCF multi-configurational calculations on the CH_3O + NO_2 reaction located a conical intersection near where single-configurational DFT methods predict an intrinsic energy barrier; the barrier was suggested to be an artifact. In present work, the global HNO_3 PES is being investigated by both the UCCSD(T) and CASSCF methods in order to study the influence of low-lying excited electronic states on the ground state PES and reaction dynamics. L. P. Olsen, M. D. Bartberger and K. N. Houk, J. Am. Chem. Soc., 125, 3999 (2003) G. B. Ellison, J. M. Herbert, A. B. McCoy, J. F. Stanton and P. G. Szalay, J. Phys. Chem. A 108, 7639 (2004). J. F. Arenas, F. J. Avila, J. C. Otero, D. Peláez and J. Soto, J. Phys. Chem. A 112, 249 (2008).

  4. Identification of Sequence Similarities among Isomerization Hotspots in Crystallin Proteins

    PubMed Central

    2017-01-01

    The eye lens crystallins represent an ideal target for studying the effects of aging on protein structure. Herein we examine separately the water-soluble (WS) and water-insoluble (WI) crystallin fractions and identify sites of isomerization and epimerization. Both collision-induced dissociation and radical-directed dissociation are needed for detection of these non-mass-shifting post-translational modifications. Isomerization levels differ significantly between the WS and the WI fractions from sheep, pig, and cow eye lenses. Residues that are most susceptible to isomerization are identified site-specifically and are found to reside in structurally disordered regions. However, isomerization in structured domains, although less common, often yields more dramatic effects on solubility. Numerous isomerization hotspots were also identified and occur in regions with aspartic acid and serine repeats. For example, 128KMEIVDDDVPSLW140 in βB3 crystallin contains three sequential aspartic acid residues and is isomerized heavily in the WI fractions, while it is not modified at all in the WS fractions. Potential causes for enhanced isomerization at sites with acidic residue repeats are presented. The importance of acidic residue repeats extends beyond the lens, as they are found in many other long-lived proteins associated with disease. PMID:28234481

  5. Results of a direct search for the thorium-229 nuclear isomeric transition

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    The nucleus of thorium-229 has an exceptionally low-energy isomeric transition in the vacuum-ultraviolet spectrum around 7 . 8 +/- 0 . 5 eV. The prospects of a laser-accessible nuclear transition are manifold but require spectroscopically resolving the transition. Our approach is a direct search using thorium-doped crystals as samples and exciting the isomeric state with vacuum-ultraviolet synchrotron radiation. In a recent experiment, we were able to search for the transition at the Advanced Light Source synchrotron, LBNL, between 7 . 3 eV and 8 . 8 eV. We found no evidence for the transition within a lifetime range of 1-2s to 2000-5600s. This result excludes large parts of the theoretically expected region. We conclude reporting on our efforts of a search using laser-generated vacuum-ultraviolet light.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Spectroscopic Identification of Isomeric Trimethylbenzyl Radicals Generated in Corona Discharge of Tetramethylbenzene

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Lee, Sang Kuk; Lee, Gi Woo

    2011-06-01

    The visible vibronic emission spectra were recorded from the corona discharge of precursor tetramethylbenzene with a large amount of inert carrier gas helium using a pinhole-type glass nozzle coupled with corona excited supersonic expansion (CESE) well developed in this laboratory. The spectra showed a series of vibronic bands in the D_1 → D_0 electronic transition of jet-cooled benzyl-type radicals formed from the precursor in a corona excitation. The analysis confirmed that two isomeric radicals, 2,3,4- and 2,3,6-trimethylbenzyl radicals and three isomeric radicals, 3,4,5-, 2,3,5- and 2,4,6-trimethylbenzyl radicals were produced, respectively, from 1,2,3,4- and 1,2,3,5-tetramethylbenzenes as a result of removal of a hydrogen atom from the methyl group at different substitution position. For each isomeric trimethylbenzyl radical generated in the corona discharge of precursor, the electronic transition and a few vibrational mode frequencies were determined in the ground electronic state by comparing with those from both ab initio calculations and the known vibrational data of the precursor. The substitution effect that states the shift of electronic transition depends on the nature, the number, and the position of substituents on the ring has been qualitatively proved for the case of benzyl-type radicals.

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

    SciTech Connect

    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.

  9. Isomerization dynamics and thermodynamics of ionic argon clusters

    NASA Astrophysics Data System (ADS)

    Calvo, F.; Gadéa, F. X.; Lombardi, A.; Aquilanti, V.

    2006-09-01

    The dynamics and thermodynamics of small Arn+ clusters, n =3, 6, and 9, are investigated using molecular dynamics (MD) and exchange Monte Carlo (MC) simulations. A diatomic-in-molecule Hamiltonian provides an accurate model for the electronic ground state potential energy surface. The microcanonical caloric curves calculated from MD and MC methods are shown to agree with each other, provided that the rigorous conservation of angular momentum is accounted for in the phase space density of the MC simulations. The previously proposed projective partition of the kinetic energy is used to assist MD simulations in interpreting the cluster dynamics in terms of inertial, internal, and external modes. The thermal behavior is correlated with the nature of the charged core in the cluster by computing a dedicated charge localization order parameter. We also perform systematic quenches to establish a connection with the various isomers. We find that the Ar3+ cluster is very stable in its linear ground state geometry up to about 300K, and then isomerizes to a T-shaped isomer in which a quasineutral atom lies around a charged dimer. In Ar6+ and Ar9+, the covalent trimer core is solvated by neutral atoms, and the weakly bound solvent shell melts at much lower energies, occasionally leading to a tetramer or pentamer core with weakly charged extremities. At high energies the core itself becomes metastable and the cluster transforms into Ar2+ solvated by a fluid of neutral argon atoms.

  10. Methods for suppressing isomerization of olefin metathesis products

    DOEpatents

    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.

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

    PubMed

    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.

  12. HCP<=>CPH isomerization: caught in the act.

    PubMed

    Ishikawa, H; Field, R W; Farantos, S C; Joyeux, M; Koput, J; Beck, C; Schinke, R

    1999-01-01

    In this overview we discuss the vibrational spectrum of phosphaethyne, HCP, in its electronic ground state, as revealed by complementary experimental and theoretical examinations. The main focus is the evolution of specific spectral patterns from the bottom of the potential well up to excitation energies of approximately 25,000 cm(-1), where large-amplitude, isomerization-type motion from H-CP to CP-H is prominent. Distinct structural and dynamical changes, caused by an abrupt transformation from essentially HC bonding to mainly PH bonding, set in around 13,000 cm(-1). They reflect saddle-node bifurcations in the classical phase space--a phenomenon well known in the nonlinear dynamics literature--and result in characteristic patterns in the spectrum and the quantum-number dependence of the vibrational fine-structure constants. Two polar opposites are employed to elucidate the spectral patterns: the exact solution of the Schrödinger equation, using an accurate potential energy surface and an effective or resonance Hamiltonian (expressed in a harmonic oscillator basis set and block diagonalized into polyads), which is defined by parameters adjusted to fit either the measured or the calculated vibrational energies. The combination of both approaches--together with classical mechanics and semiclassical analyses--provides a detailed spectroscopic picture of the breaking of one bond and the formation of a new one.

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

    PubMed

    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.

  14. A review of drug isomerism and its significance

    PubMed Central

    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 levocetrizine is one of such examples, where effective and safer drug has been made available. In this article, we have attempted to review the basic concepts of stereochemistry and chirality and their significance in pharmacotherapeutics. Various pharmacological aspects such as pharmacokinetic and pharmacodynamic variations resulting out of chirality has been discussed in detail in this article. PMID:23776834

  15. Benzil-tethered precipitons for controlling solubility: a round-trip energy-transfer mechanism in the isomerization of extended stilbene analogues.

    PubMed

    Ams, Mark R; Wilcox, Craig S

    2007-04-04

    We are investigating photoresponsive molecules called "precipitons" that undergo a solubility change co-incident with isomerization. Isomerization can be induced by light or by catalytic reagents. Previous work demonstrated that covalent attachment of a metal complex, Ru(II)(bpy)3, greatly accelerates photoisomerization and influences the photostationary state. In this paper, we describe precipitons (1,2-biphenylethenes; analogous to stilbenes) that are activated by a covalently attached organic sensitizer (benzil). We find that isomerization of these stilbene analogues is little effected by the presence of benzil in solution but that the intramolecular benzil effect is to increase the rate of isomerization and to significantly change the photostationary state. What is most interesting about these observations is that the precipiton is the primary chromophore in this bichromophoric system (precipiton absorbance is many times greater than benzil absorbance in the 300-400 nm range), yet the neighboring benzil has a significant effect on the rate and the photostationary state. The effect of unattached benzil on the rate was small, about a 24% increase in rate as compared with 4-6-fold changes for an attached benzil. We speculate that the isomerization process occurs by a "round-trip" energy-transfer mechanism. Initial excitation of the precipiton chromophore initiates a sequence that includes (1) formation of the precipiton singlet state, (2) singlet excitation transfer from the precipiton unit to the benzil, (3) benzil-centered intersystem crossing to the localized benzil triplet state, (4) triplet energy transfer from the benzil moiety back to the precipiton, and (5) isomerization.

  16. Biventricular repair of right atrial isomerism with complex congenital anomalies.

    PubMed

    Kirali, Kaan; Sasmazel, Ahmet; Mataraci, Ilker; Erdem, Hasan; Guzelmeric, Fusun

    2010-01-01

    Biventricular repair is usually difficult to achieve in patients who have right atrial isomerism, which is typically associated with other complex cardiac anomalies. The procedure can be used in patients who have balanced ventricular structures. Herein, we report a successful surgical reconstruction, including biventricular repair, in a 4-year-old boy. The child's right atrial isomerism was associated with double-outlet right ventricle, a large atrial septal defect, a subaortic ventricular septal defect, valvular and infundibular pulmonary stenosis, left persistent superior vena cava, and hemiazygos continuation of an interrupted inferior vena cava. Balanced ventricles enabled biventricular repair, which we consider to be preferable to the Fontan procedure in such circumstances.

  17. Ethanol production from xylose by enzymic isomerization and yeast fermentation

    SciTech Connect

    Chiang, L.C.; Hsiao, H.Y.; Ueng, P.P.; Chen, L.F.; Tsao, G.T.

    1981-01-01

    Repetitive enzymic isomerization of xylose followed by yeast fermentation of xylulose, and simultaneous enzymic isomerization and yeast fermentation were proven to be methods capable of converting xylose to ethanol. The fermentation product, ethanol, xylitol, or glycerol, has little inhibitory or deactivation effect on the activity of isomerase. In a comparison of the ability of yeasts to ferment xylulose to ethanol, Schizosaccharomyces pombe was found to be superior to industrial bakers' yeast. Under optimal conditions (pH 6, temperature 30/sup 0/C), a final ethanol concentration of 6.3 wt.% was obtained from simulated hemicellulose hydrolysate using a simultaneous fermentation process. The ethanol yield was over 80% of the theoretical value.

  18. Catalytic Isomerization of Biomass‐Derived Aldoses: A Review

    PubMed Central

    Delidovich, Irina

    2016-01-01

    Abstract Selected aldohexoses (d‐glucose, d‐mannose, and d‐galactose) and aldopentoses (d‐xylose, l‐arabinose, and d‐ribose) are readily available components of biopolymers. Isomerization reactions of these substances are very attractive as carbon‐efficient processes to broaden the portfolio of abundant monosaccharides. This review focuses on the chemocatalytic isomerization of aldoses into the corresponding ketoses as well as epimerization of aldoses at C2. Recent advances in the fields of catalysis by bases and Lewis acids are considered. The emphasis is laid on newly uncovered catalytic systems and mechanisms of carbohydrate transformations. PMID:26948404

  19. Theoretical study of the isomerization mechanism of azobenzene and disubstituted azobenzene derivatives.

    PubMed

    Crecca, Christina R; Roitberg, Adrian E

    2006-07-06

    A series of azobenzenes was studied using ab initio methods to determine the substituent effects on the isomerization pathways. Energy barriers were determined from three-dimensional potential energy surfaces of the ground and electronically excited states. In the ground state (S(0)), the inversion pathway was found to be preferred. Our results show that electron donating substituents increase the isomerization barrier along the inversion pathway, whereas electron withdrawing substituents decrease it. The inversion pathway of the first excited state (S(1)) showed trans --> cis barriers with no curve crossing between S(0) and S(1). In contrast, a conical intersection was found between the ground and first excited states along the rotation pathway for each of the azobenzenes studied. No barriers were found in this pathway, and we therefore postulate that after n --> pi (S(1) <-- S(0)) excitation, the rotation mechanism dominates. Upon pi --> pi (S(2) <-- S(0)) excitation, there may be sufficient energy to open an additional pathway (concerted-inversion) as proposed by Diau. Our potential energy surface explains the experimentally observed difference in trans-to-cis quantum yields between S(1) and S(2) excitations. The concerted inversion channel is not available to the remaining azobenzenes, and so they must employ the rotation pathway for both n --> pi and pi --> pi excitations.

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

    SciTech Connect

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-12-28

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

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

    SciTech Connect

    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.

  2. Comparison of the isomerization mechanisms of human melanopsin and invertebrate and vertebrate rhodopsins

    PubMed Central

    Rinaldi, Silvia; Melaccio, Federico; Gozem, Samer; Fanelli, Francesca; Olivucci, Massimo

    2014-01-01

    Comparative modeling and ab initio multiconfigurational quantum chemistry are combined to investigate the reactivity of the human nonvisual photoreceptor melanopsin. It is found that both the thermal and photochemical isomerization of the melanopsin 11-cis retinal chromophore occur via a space-saving mechanism involving the unidirectional, counterclockwise twisting of the =C11H-C12H= moiety with respect to its Lys340-linked frame as proposed by Warshel for visual pigments [Warshel A (1976) Nature 260(5553):679–683]. A comparison with the mechanisms documented for vertebrate (bovine) and invertebrate (squid) visual photoreceptors shows that such a mechanism is not affected by the diversity of the three chromophore cavities. Despite such invariance, trajectory computations indicate that although all receptors display less than 100 fs excited state dynamics, human melanopsin decays from the excited state ∼40 fs earlier than bovine rhodopsin. Some diversity is also found in the energy barriers controlling thermal isomerization. Human melanopsin features the highest computed barrier which appears to be ∼2.5 kcal mol−1 higher than that of bovine rhodopsin. When assuming the validity of both the reaction speed/quantum yield correlation discussed by Warshel, Mathies and coworkers [Weiss RM, Warshel A (1979) J Am Chem Soc 101:6131–6133; Schoenlein RW, Peteanu LA, Mathies RA, Shank CV (1991) Science 254(5030):412–415] and of a relationship between thermal isomerization rate and thermal activation of the photocycle, melanopsin turns out to be a highly sensitive pigment consistent with the low number of melanopsin-containing cells found in the retina and with the extraretina location of melanopsin in nonmammalian vertebrates. PMID:24449866

  3. Rotational bands and isomeric states in 175Lu

    SciTech Connect

    Garrett, P E; Archer, D E; Becker, J A; Bernstein, L A; Hauschild, K; Henry, E A; McNabb, D P; Stoyer, M A; Younes, W; Johns, G D; Nelson, R O; Wilburn, W S

    2003-10-15

    Rotational bands in {sup 175}Lu have been extended through investigation with the (n,n{prime}{gamma}) reaction. Spallation neutrons bombarded Lu samples, and the resulting {gamma} rays were detected in a large-scale Compton-suppressed Ge detector array. Prompt- and delayed-{gamma}{gamma} coincidences have been used to extend most of the existing known bands, and to tentatively assign a new band, based on the 7/2{sup -}[523] configuration, from its band head to spin 13/2. The 3-quasiparticle K{sup {pi}} = 19/2{sup +} isomer is confirmed and its half life determined to be 984 {+-} 13(stat.) {+-} 30(sys.) {micro}s, in agreement with previous results.

  4. Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: dynamics using a multireference potential.

    PubMed

    Kalinowski, Jaroslaw; Räsänen, Markku; Heinonen, Petri; Kilpeläinen, Ilkka; Gerber, R Benny

    2014-01-03

    The isomerization and decomposition dynamics of the simplest Criegee intermediate CH2 OO have been studied by classical trajectory simulations using the multireference ab initio MR-PT2 potential on the fly. A new, accelerated algorithm for dynamics with MR-PT2 was used. For an initial temperature of 300 K, starting from the transition state from CH2 OO→CH2 O2  , the system reaches the dioxirane structure in around 50 fs, then isomerizes to formic acid (in ca. 2800 fs), and decomposes into CO+H2 O at around 2900 fs. The contributions of different configurations to the multiconfigurational total electronic wave function vary dramatically along the trajectory, with diradical contributions being important for transition states corresponding to H-atom transfers, while being only moderately significant for CH2 OO. The implications for reactions of Criegee intermediates are discussed.

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

    ERIC Educational Resources Information Center

    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)

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  9. Coherent control of the isomerization of retinal in bacteriorhodopsin in the high intensity regime.

    PubMed

    Prokhorenko, Valentyn I; Halpin, Alexei; Johnson, Philip J M; Miller, R J Dwayne; Brown, Leonid S

    2011-02-28

    Coherent control protocols provide a direct experimental determination of the relative importance of quantum interference or phase relationships of coupled states along a selected pathway. These effects are most readily observed in the high intensity regime where the field amplitude is sufficient to overcome decoherence effects. The coherent response of retinal photoisomerization in bacteriorhodopsin to the phase of the photoexcitation pulses was examined at fluences of 10(15) - 2.5 × 10(16) photons per square centimeter, comparable to or higher than the saturation excitation level of the S(0) - S(1) retinal electronic transition. At moderate excitation levels of ∼6 × 10(15) photons/cm(2) (<100 GW/cm(2)), chirping the excitation pulses increases the all-trans to 13-cis isomerization yield by up to 16% relative to transform limited pulses. The reported results extend previous weak-field studies [Prokhorenko et al., Science 313, 1257 (2006)] and further illustrate that quantum coherence effects persist along the reaction coordinate in strong fields even for systems as complex as biological molecules. However, for higher excitation levels of ∼200 GW/cm(2), there is a dramatic change in photophysics that leads to multiphoton generated photoproducts unrelated to the target isomerization reaction channel and drastically changes the observed isomerization kinetics that appears, in particular, as a red shift of the transient spectra. These results explain the apparent contradictions of the work by Florean et al. [Proc. Natl. Acad. Sci. U.S.A. 106, 10896 (2009)] in the high intensity regime. We are able to show that the difference in observations and interpretation is due to artifacts associated with additional multiphoton-induced photoproducts. At the proper monitoring wavelengths, coherent control in the high intensity regime is clearly observable. The present work highlights the importance of conducting coherent control experiments in the low intensity regime

  10. Taple-top imaging of the non-adiabatically driven isomerization in the acetylene cation

    NASA Astrophysics Data System (ADS)

    Beaulieu, Samuel; Ibrahim, Heide; Wales, Benji; Schmidt, Bruno E.; Thiré, Nicolas; Bisson, Éric; Hebeisen, Christoph T.; Wanie, Vincent; Giguere, Mathieu; Kieffer, Jean-Claude; Sanderson, Joe; Schuurman, Michael S.; Légaré, François

    2014-05-01

    One of the primary goals of modern ultrafast science is to follow nuclear and electronic evolution of molecules as they undergo a photo-chemical reaction. Most of the interesting dynamics phenomena in molecules occur when an electronically excited state is populated. When the energy difference between electronic ground and excited states is large, Free Electron Laser (FEL) and HHG-based VUV sources were, up to date, the only light sources able to efficiently initiate those non-adiabatic dynamics. We have developed a simple table-top approach to initiate those rich dynamics via multiphoton absorption. As a proof of principle, we studied the ultrafast isomerization of the acetylene cation. We have chosen this model system for isomerization since the internal conversion mechanism which leads to proton migration is still under debate since decades. Using 266 nm multiphoton absorption as a pump and 800 nm induced Coulomb Explosion as a probe, we have shoot the first high-resolution molecular movie of the non-adiabatically driven proton migration in the acetylene cation. The experimental results are in excellent agreement with high level ab initio trajectory simulations.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Femtosecond isomerization dynamics in the ethylene cation measured in an EUV-pump NIR-probe configuration

    SciTech Connect

    van Tilborg, Jeroen; Allison, Tom; Wright, Travis; Hertlein, Marc; Falcone, Roger; Liu, Yanwei; Merdji, Hamed; Belkacem, Ali

    2009-03-17

    Dynamics in the excited ethylene cation C{sub 2}H{sub 4}{sup +} lead to isomerization to the ethylidene configuration (HC-CH{sub 3}){sup +}, which is predicted to be a transient configuration for electronic relaxation. With an intense femtosecond EUV (extreme ultraviolet) pump pulse to populate the excited state, and an NIR (near infrared) probe pulse to produce the fragments CH{sup +} and CH{sub 3}{sup +} (which provides a direct signature of ethylidene), we measure optimum fragment yields at a probe delay of 80 fs. Also, an H{sub 2}-stretch transient configuration, yielding H{sub 2}{sup +} upon probing, is found to succeed the ethylidene configuration. We find that a simple single- or double-decay model does not match the data, and we present a modified model (introduction of an isomerization delay of 50 {+-} 25 fs) that does provide agreement.

  13. FAST TRACK COMMUNICATION: Femtosecond isomerization dynamics in the ethylene cation measured in an EUV-pump NIR-probe configuration

    NASA Astrophysics Data System (ADS)

    Tilborg, J. van; Allison, T. K.; Wright, T. W.; Hertlein, M. P.; Falcone, R. W.; Liu, Y.; Merdji, H.; Belkacem, A.

    2009-04-01

    Dynamics in the excited ethylene cation C2H+4 lead to isomerization to the ethylidene configuration (HC-CH3)+, which is predicted to be a transient configuration for electronic relaxation. With an intense femtosecond extreme ultraviolet pump pulse to populate the excited state, and a near infrared probe pulse to produce the fragments CH+ and CH+3 (which provides a direct signature of ethylidene), we measure optimum fragment yields at a probe delay of 80 fs. Also, an H2-stretch transient configuration, yielding H+2 upon probing, is found to succeed the ethylidene configuration. We find that a simple single- or double-decay model does not match the data, and we present a modified model (introduction of an isomerization delay of 50 ± 25 fs) that does provide agreement.

  14. Tryptophan-47 rotational isomerization in variant-3 scorpion neurotoxin. A combination thermodynamic perturbation and umbrella sampling study.

    PubMed Central

    Haydock, C; Sharp, J C; Prendergast, F G

    1990-01-01

    A combination thermodynamic perturbation and umbrella sampling study predicts two free energy wells for the rotational isomerization of the variant-3 scorpion neurotoxin tryptophan-47 indole side chain. One well has the indole side chain in the crystallographic orientation; the other has the indole rotated approximately 220 degrees to form a new conformation with a relative free energy of 3 +/- 2 kcal/mol. The activation barrier is 8.5 kcal/mol from the crystallographic well, from which transition state theory predicts a rate of escape of 2 x 10(5) s-1. Correlations in the displacements of side chains neighboring tryptophan-47 and the isomerization reaction coordinate last up to 20 ps. Favorable conditions of experimental verification are discussed. PMID:2393708

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    SciTech Connect

    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.

  18. Complementing ultrafast shape recognition with an optical isomerism descriptor.

    PubMed

    Zhou, Ting; Lafleur, Karine; Caflisch, Amedeo

    2010-11-01

    We introduce the mixed product of three vectors spanning four molecular locations as a descriptor of optical isomerism. This descriptor is very efficient as it does not require molecular superposition, and is very robust in discriminating between a given isomer and its mirror image. In particular, conformational isomers that are mirror images of each other, as well as optical isomers have opposite sign of the descriptor value. For efficient database searches, the optical isomerism descriptor can be used to complement an available ultrafast shape recognition (USR) method based solely on distances, which is not able to distinguish enantiomers. By an extensive comparison of the USR-based similarity score with an approach based on Gaussian molecular volume overlap, the accuracy and completeness of the former are discussed.

  19. Isomerization of meta-xylene over offretite catalysts

    SciTech Connect

    Sastre, E.; Corma, A.; Perez-Pariente, J. ); Fajula, F.; Figueras, F. )

    1990-12-01

    The conversion of meta-xylene has been investigated over offretites with different levels of ion exchange. The ratio isomerization/disproportionation increases with the degree of exchange, most probably due to an increased accessibility of the reactant to the internal surface and to a higher number and strength of acid sites. The addition of a hydrogenation function, in H{sub 2} atmosphere, slightly increases the activity and decreases the deactivation as a function of time. The conversion of 1-3-dimethylcyclohexene-1 yields experimental evidence that a bifunctional path exists for the reaction in these conditions. The supposed intermediate olefin isomerizes and disproportionates faster than meta-xylene, but the ortho/para selectivity remains unchanged.

  20. The isomerization barrier in cyanocyclobutadienes: an ab initio multireference average quadratic coupled cluster study.

    PubMed

    Eckert-Maksić, Mirjana; Lischka, Hans; Maksić, Zvonimir B; Vazdar, Mario

    2009-07-23

    The energy profiles of the isomerization of mono, di-, and tetracyano-substituted cyclobutadienes (CBDs) are computed at the multireference average quadratic coupled cluster/complete active space self-consistent field level of theory. It was found that the energy barrier heights for the automerization reaction are 2.6 (tetracyano-CBD), 5.1 (1,3-dicyano-CBD), and 6.4 (cyano-CBD) kcal mol(-1), implying that they are lowered relative to that in the parent CBD (6.4 kcal mol(-1)), the monosubstituted derivative being an exception. Since the free CBD shuttles between two equivalent structures even at low temperature of 10 K, it follows that bond-stretch isomerism does not take place in cyanocyclobutadienes. Instead, these compounds exhibit rapid fluxional interconversion at room temperature between two bond-stretch isomers by the double bond flipping mechanism. The reason behind the decrease in the barrier heights is identified as a slightly enhanced resonance effect at the saddle points separating two (equivalent) bond-stretch isomers, compared to that in the equilibrium structures, predominantly due to the diradical character of the former. It is also shown that the energy gap between the singlet ground state saddle point structure and the first triplet equilibrium geometry decreases upon multiple substitution by the cyano groups. The splitting of the S and T energy is small being within the range of 6.5-8.2 kcal mol(-1).

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

    PubMed

    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.

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

    PubMed

    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.

  3. Photoinduced isomerization of lycopene and application to tomato cultivation.

    PubMed

    Heymann, Thomas; Raeke, Julia; Glomb, Marcus A

    2013-11-20

    The present study aimed to investigate if growth conditions have an impact on the isomeric composition of lycopene in tomatoes. First a model system for photoinduced isomerization was established. Tomato extracts were irradiated with a halogen lamp, whose wavelength spectrum is close to the spectrum of daylight and thus mimics field-grown cultivation. Different optical filters were interposed between lamp and samples to simulate greenhouse conditions. 5-cis-Lycopene was formed preferentially while the concentration of 7-cis-lycopene decreased in field-grown model systems. The change of isomerization in greenhouse model systems led to a significantly different ratio. Consequently 5-cis- and 7-cis-lycopene were identified as potent markers for the differentiation of various lighting conditions during cultivation. This result was verified in biological samples. Authentic field-grown tomatoes (var. Lycopersicon esculentum Mill. var. commune L. H. Bailey "Harzfeuer") showed a significantly higher content of 5-cis-lycopene 5.90 ± 0.45% compared to tomatoes of the same variety grown under electric lighting 4.11 ± 0.10%. Additionally, the ratio of 7-cis-lycopene was significantly lower under field-grown conditions.

  4. Photochemical isomerization in solution. Photophysics of diphenyl butadiene

    NASA Astrophysics Data System (ADS)

    Velsko, Stephan P.; Fleming, Graham R.

    1982-04-01

    We have examined the radiative and nonradiative decay rates of diphenyl butadiene in hydrocarbon and polar solvents as a function of temperature and pressure. We demonstrate that the radiative rate constant has a small dependence on solvent polarizability, in contrast to what is observed for diphenylhexatriene. We make an explicit separation of the internal molecular barrier to isomerization and the barrier due to frictional forces in the solvent. The energy of the internal barrier to isomerization is less than the activation energy observed in solution, and depends on the polarizability and polarity of the solvent. In contrast to diphenylhexatriene, it decreases, in more polar solvents. We compare the viscosity dependence of the barrier crossing process with Kramers' theory, the recent kinetic theory result of Skinner and Wolynes [J. Chem. Phys. 69, 2143 (1978)], and the free volume theory of Gegiou, Muzkat, and Fischer, [J. Amer. Chem. Soc. 90, 12 (1968)]. Our data clearly show that the isomerization process is in the intermediate friction limit and we obtain experimental values for the parameters of the three theories. Over the viscosity region studied, Kramers' and Skinner and Wolynes' equations coincide exactly and do not reproduce the functional dependence of the radiationless rate pre-exponential factor as well as the free volume theory. We speculate that it may be necessary to consider the frequency dependence of medium viscosity.

  5. Industrial application of catalytic systems for n-heptane isomerization.

    PubMed

    Alemán-Vázquez, Laura Olivia; Cano-Domínguez, José Luis; Torres-García, Enelio; Villagómez-Ibarra, José Roberto

    2011-07-14

    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.

  6. Interstellar isomeric species: Energy, stability and abundance relationship

    NASA Astrophysics Data System (ADS)

    Etim, Emmanuel E.; Arunan, Elangannan

    2016-12-01

    Accurate enthalpies of formation are reported for known and potential interstellar isomeric species using high-level ab initio quantum-chemical calculations. A total of 130 molecules comprising of 31 isomeric groups and 24 cyanide/isocyanide pairs with molecules ranging from 3 to 12 atoms have been considered. The results show an interesting relationship between energy, stability and abundance (ESA) existing among these molecules. Among the isomeric species, isomers with lower enthalpies of formation are more easily observed in the interstellar medium compared to their counterparts with higher enthalpies of formation. Available data in the literature confirm the high abundance of the most stable isomer over other isomers in the different groups considered. Potential for interstellar hydrogen bonding accounts for the few exceptions observed. Thus, in general, it suffices to say that the interstellar abundances of related species could be linked to their stabilities if other factors do not dominate. The immediate consequences of this relationship in addressing some of the whys and wherefores among interstellar molecules and in predicting some possible candidates for future astronomical observations are discussed.

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

    PubMed

    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).

  8. Shape-Asymmetry Supramolecular Isomerism in Asymmetrical Ligand PCPs and the Expression Method of Three-Level Isomerism.

    PubMed

    Gao, Xiaonan; Fu, Ai-Yun; Wang, Yao-Yu

    2016-05-02

    We show here the supramolecular isomerism, with respect to shape-asymmetry of ligand and the new hierarchical classification for supramolecular isomerism, the three-level isomerism, which was advanced based on a thorough investigation for the four new Ni/dpt24 polymorphs [Hdpt24 = 3-(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole)]. Compounds 1, 2, and 3 are three-dimensional twofold interpenetrated porous coordination polymers with NbO topology, while 4 with two-dimensional grid structure is termed as the primary isomer of 1/2/3 due to the difference of dimensionality. Complex 3 possessing different shape-asymmetry of single networks from 1 and 2, is called as the secondary isomer of 1 and 2. Complexes 1 and 2 possess the same topology, single shape-asymmetry networks, but different interpenetration-orientation and interpenetration-asymmetry, and are defined as the tertiary isomers. Distinct differences in H2 and CO2 adsorption capacity were observed among each level of isomers. In addition, the hierarchical classification's relationship with characteristic classifications has been discussed.

  9. Refolding additive, dimethylbenzylammonium propane sulfonate (NDSB- 256), accelerates gly-pro cis-trans isomerization.

    PubMed

    Wang, Haimei; Hosoda, Kazuo; Terawaki, Shin-Ichi; Wakamatsu, Kaori

    2014-01-01

    Proline cis-trans isomerization plays a key role in the rate-determining steps of protein folding, and many different peptide-proline cis-trans isomerases (PPIases) catalyze this reaction. The acceleration of isomerization would be beneficial for in vitro refolding of protein preparations for industrial and research purposes. So we analyzed whether low-molecular-weight compounds that have been reported to enhance protein refolding have the activity to accelerate the isomerization. To evaluate the effects of chemicals on the isomerization rate, we set up a new NMR (EXSY) method that is invulnerable to their inhibitory activity, if any, and to their large NMR signals. With this method, we found that dimethylbenzylammonium propane sulfonate (NDSB-256) increase the isomerization rate in a concentration-dependent manner for the first time. Acceleration by imidazole (suggested but not experimentally confirmed) was also demonstrated. Arginine, a most popular refolding additive, did not show any significant effects on the isomerization reaction as expected.

  10. Direct measurement of the isomerization barrier of the isolated retinal chromophore.

    PubMed

    Dilger, Jonathan; Musbat, Lihi; Sheves, Mordechai; Bochenkova, Anastasia V; Clemmer, David E; Toker, Yoni

    2015-04-13

    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 activation voltages for isomerization for each of the reaction pathways, and by measuring the threshold activation voltage for fragmentation, the relative energies of the isomers as well as the energy barriers for isomerization were determined. The energy barrier for a single cis-trans isomerization is (0.64±0.05) eV, which is significantly lower than that observed for the reaction within opsin proteins.

  11. Characteristics of Hospitalizations for the Glenn Procedure in Those With Isomerism Compared to Those Without.

    PubMed

    Loomba, Rohit S; Kouretas, Peter C; Anderson, Robert H

    2016-12-01

    Isomerism, also known as heterotaxy, is a unique clinical entity in which there are mirror imaged findings in the thoracic. In the abdomen, the arrangement of organs can be random. The anatomic findings also have functional consequences. Isomerism has been known to increase morbidity and mortality in those with functionally univentricular hearts. The aim of this study was to determine the impact of isomerism on the Glenn hospitalization. Data from the 1997 to 2012 Kids' Inpatient Database were utilized for this cross-sectional study. Admissions during which a Glenn procedure was done were identified. Next, these admissions were separated into those with and without isomerism. Admission characteristics were then compared in a univariate fashion as well as by regression analysis. Length of hospitalization, cost of hospitalization, extracorporeal membrane oxygenation, and inpatient mortality were the outcomes of interest. A total of 4959 admissions with a Glenn procedure were identified. Of these, 450 were associated with isomerism. The median age at which the Glenn procedure was done was 10 and 13 months in those without and with isomerism, respectively. Neither univariate nor regression analysis demonstrated any significant difference in length of hospitalization, cost of hospitalization, need for extracorporeal membrane oxygenation, and inpatient mortality between those with and without isomerism. Isomerism does not impact the characteristics of the Glenn hospitalization. Those with isomerism did tend to be older when they underwent the Glenn procedure.

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

    NASA Astrophysics Data System (ADS)

    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. Carotene Degradation and Isomerization during Thermal Processing: A Review on the Kinetic Aspects.

    PubMed

    Colle, Ines J P; Lemmens, Lien; Knockaert, Griet; Van Loey, Ann; Hendrickx, Marc

    2016-08-17

    Kinetic models are important tools for process design and optimization to balance desired and undesired reactions taking place in complex food systems during food processing and preservation. This review covers the state of the art on kinetic models available to describe heat-induced conversion of carotenoids, in particular lycopene and β-carotene. First, relevant properties of these carotenoids are discussed. Second, some general aspects of kinetic modeling are introduced, including both empirical single-response modeling and mechanism-based multi-response modeling. The merits of multi-response modeling to simultaneously describe carotene degradation and isomerization are demonstrated. The future challenge in this research field lies in the extension of the current multi-response models to better approach the real reaction pathway and in the integration of kinetic models with mass transfer models in case of reaction in multi-phase food systems.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  16. Isomerization of Internal Alkynes to Iridium(III) Allene Complexes via C-H Bond Activation: Expanded Substrate Scope, and Progress towards a Catalytic Methodology.

    PubMed

    Phadke, Neha; Findlater, Michael

    2015-11-10

    The synthesis of a series of allene complexes (POCOP)Ir(η²-RC=(.)=CR') 1b-4b (POCOP = 2,6-bis(di-tert-butylphosphonito)benzene) 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.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. How is the anionic tetrahedral intermediate involved in the isomerization of aspartyl peptides to iso-aspartyl ones? A DFT study on the tetra-peptide.

    PubMed

    Yamabe, Shinichi; Guan, Wei; Sakaki, Shigeyoshi

    2012-10-21

    An isomerization reaction of a tetra-peptide, Ac-Gly-Asp-Gly-Gly-NHMe → Ac-Gly-isoAsp-Gly-Gly-NHMe, was investigated by DFT calculations. Thirteen water molecules were added to the peptide for simulating proton transfers during the isomerization. As a starting analysis, the number (m) of water molecules participating in ready proton transfers was examined by the use of a small model system, H(3)C-NH-C(=O)-CH(2)-CH(2)-COOH and (H(2)O)(m). The m = 2 stepwise path was found to be of the smallest activation free energy. On the basis of this result, the first isomerization path of the tetra-peptide was obtained with four elementary processes. The m = 2 proton-transfer pattern is involved in them. A different proton transfer gives the second isomerization path with six elementary processes. The second path (with ionization) is more likely than the first one (without ionization). Formation of the five membered rings of the aminosuccinimidyl-residue and anionic tetrahedral intermediates enhances the encapsulation of H(3)O(+) through the wound tetra-peptide ring. The role of the hydrogen bonds on the encapsulation was discussed in terms of the optimized geometries of proton-transfer transition states and intermediates.

  19. Competing intermolecular interactions in some 'bridge-flipped' isomeric phenylhydrazones.

    PubMed

    Ojala, William H; Arola, Trina M; Brigino, Ann M; Leavell, Jeremy D; Ojala, Charles R

    2012-07-01

    To examine the roles of competing intermolecular interactions in differentiating the molecular packing arrangements of some isomeric phenylhydrazones from each other, the crystal structures of five nitrile-halogen substituted phenylhydrazones and two nitro-halogen substituted phenylhydrazones have been determined and are described here: (E)-4-cyanobenzaldehyde 4-chlorophenylhydrazone, C(14)H(10)ClN(3), (Ia); (E)-4-cyanobenzaldehyde 4-bromophenylhydrazone, C(14)H(10)BrN(3), (Ib); (E)-4-cyanobenzaldehyde 4-iodophenylhydrazone, C(14)H(10)IN(3), (Ic); (E)-4-bromobenzaldehyde 4-cyanophenylhydrazone, C(14)H(10)BrN(3), (IIb); (E)-4-iodobenzaldehyde 4-cyanophenylhydrazone, C(14)H(10)IN(3), (IIc); (E)-4-chlorobenzaldehyde 4-nitrophenylhydrazone, C(13)H(10)ClN(3)O(2), (III); and (E)-4-nitrobenzaldehyde 4-chlorophenylhydrazone, C(13)H(10)ClN(3)O(2), (IV). Both (Ia) and (Ib) are disordered (less than 7% of the molecules have the minor orientation in each structure). Pairs (Ia)/(Ib) and (IIb)/(IIc), related by a halogen exchange, are isomorphous, but none of the 'bridge-flipped' isomeric pairs, viz. (Ib)/(IIb), (Ic)/(IIc) or (III)/(IV), is isomorphous. In the nitrile-halogen structures (Ia)-(Ic) and (IIb)-(IIc), only the bridge N-H group and not the bridge C-H group acts as a hydrogen-bond donor to the nitrile group, but in the nitro-halogen structures (III) (with Z' = 2) and (IV), both the bridge N-H group and the bridge C-H group interact with the nitro group as hydrogen-bond donors, albeit via different motifs. The occurrence here of the bridge C-H contact with a hydrogen-bond acceptor suggests the possibility that other pairs of `bridge-flipped' isomeric phenylhydrazones may prove to be isomorphous, regardless of the change from isomer to isomer in the position of the N-H group within the bridge.

  20. Asymmetric synthesis and cytotoxic activity of isomeric phytosphingosine derivatives.

    PubMed

    Rives, Arnaud; Baudoin-Dehoux, Cécile; Saffon, Nathalie; Andrieu-Abadie, Nathalie; Génisson, Yves

    2011-12-07

    New phytosphingosine analogues have been conceived, synthesised and their cytotoxicity in B16 murine melanoma cells tested. These compounds embed an isomeric substitution pattern resulting from a formal permutation of the C-2 and C-4 substituents along the aliphatic skeleton of the original sphingoid base. Five different stereoisomers have been accessed through regio- and stereocontrolled opening of the oxirane of long chain epoxyamine precursors. The corresponding N-hexyl and N-octanoyl derivatives have also been prepared. In cell viability experiments all the primary amines were found to be more active than the natural phytosphingosine with IC(50) in the low μM range for the most potent compounds.

  1. Comparison of the interaction between lactoferrin and isomeric drugs

    NASA Astrophysics Data System (ADS)

    Guo, Ming; Lu, Xiaowang; Wang, Yan; Brodelius, Peter E.

    2017-02-01

    The binding properties of pentacyclic triterpenoid isomeric drugs, i.e. ursolic acid (UA) and oleanolic acid (OA), to bovine lactoferrin (BLF) have been studied by molecule modeling, fluorescence spectroscopy, UV-visible absorbance spectroscopy and infrared spectroscopy (IR). Molecular docking, performed to reveal the possible binding mode or mechanism, suggested that hydrophobic interaction and hydrogen bonding play important roles to stabilize the complex. The results of spectroscopic measurements showed that the two isomeric drugs both strongly quenched the intrinsic fluorescence of BLF through a static quenching procedure although some differences between UA and OA binding strength and non-radiation energy transfer occurred within the molecules. The number of binding sites was 3.44 and 3.10 for UA and OA, respectively, and the efficiency of Förster energy transfer provided a distance of 0.77 and 1.21 nm for UA and OA, respectively. The conformation transformation of BLF affected by the drugs conformed to the "all-or-none" pattern. In addition, the changes of the ratios of α-helices, β-sheets and β-turns of BLF during the process of the interaction were obtained. The results of the experiments in combination with the calculations showed that there are two modes of pentacyclic triterpenoid binding to BLF instead of one binding mode only governed by the principle of the lowest bonding energy.

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

    PubMed

    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. Comparison of the interaction between lactoferrin and isomeric drugs.

    PubMed

    Guo, Ming; Lu, Xiaowang; Wang, Yan; Brodelius, Peter E

    2017-02-15

    The binding properties of pentacyclic triterpenoid isomeric drugs, i.e. ursolic acid (UA) and oleanolic acid (OA), to bovine lactoferrin (BLF) have been studied by molecule modeling, fluorescence spectroscopy, UV-visible absorbance spectroscopy and infrared spectroscopy (IR). Molecular docking, performed to reveal the possible binding mode or mechanism, suggested that hydrophobic interaction and hydrogen bonding play important roles to stabilize the complex. The results of spectroscopic measurements showed that the two isomeric drugs both strongly quenched the intrinsic fluorescence of BLF through a static quenching procedure although some differences between UA and OA binding strength and non-radiation energy transfer occurred within the molecules. The number of binding sites was 3.44 and 3.10 for UA and OA, respectively, and the efficiency of Förster energy transfer provided a distance of 0.77 and 1.21nm for UA and OA, respectively. The conformation transformation of BLF affected by the drugs conformed to the "all-or-none" pattern. In addition, the changes of the ratios of α-helices, β-sheets and β-turns of BLF during the process of the interaction were obtained. The results of the experiments in combination with the calculations showed that there are two modes of pentacyclic triterpenoid binding to BLF instead of one binding mode only governed by the principle of the lowest bonding energy.

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

    PubMed

    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.

  5. Isomerization of Secondary Phosphirane into Terminal Phosphinidene Complexes: An Analogy between Monovalent Phosphorus and Transition Metals.

    PubMed

    Wong, Jonathan; Li, Yongxin; Hao, Yanwei; Tian, Rongqiang; Mathey, François

    2015-10-26

    Secondary phosphirane complexes isomerize above 100 °C to give the corresponding terminal phosphinidene complexes, which can be trapped by alkenes and alkynes. This reaction is a rare instance of the isomerization of a P(III) derivative into a P(I) derivative. It appears to mimic the reductive elimination of alkanes from transition-alkylmetal hydrides.

  6. NMR and GC Analyses of 3-Carene Isomerization Products over Activated Glauconite

    NASA Astrophysics Data System (ADS)

    Utenkova, D. B.; Skakovskii, E. D.; Senkov, G. M.; Agabekov, V. E.; Baranovskii, A. V.; Bogushevich, S. E.; Sidorenko, A. Yu.

    2017-01-01

    The qualitative and quantitative compositions of isomerization products of 3-carene over acid-treated glauconite were established using NMR and GC methods. Chemical shifts of 1H and 13C nuclei of identified compounds were assigned. A possible mechanism of the isomerization transformations was proposed.

  7. Communication: One-photon phase control of cis-trans isomerization in retinal

    SciTech Connect

    Arango, Carlos A.; Brumer, Paul

    2013-02-21

    We computationally demonstrate the one-photon phase control of retinal isomerization under conditions of low laser intensity. The calculations, utilizing the multiconfigurational time dependent Hartree method, include coupling between the two modes that are active in isomerization and the background molecular vibrational environment. Noting previously unsuccessful computations highlights the significance of this result.

  8. Using ruthenium-based isomerization to improve properties of bio-based materials

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new method that combines isomerization with other reactions has been shown to produce a family of isomeric materials. The chemistry involves the addition of a phosphorous-containing group to produce dibutyl-phosphono-octadecanoates. A low level of [Ru(CO)2(EtCO2)]n is first used for the isomerizat...

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

    PubMed

    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.

  10. Communication: One-photon phase control of cis-trans isomerization in retinal

    NASA Astrophysics Data System (ADS)

    Arango, Carlos A.; Brumer, Paul

    2013-02-01

    We computationally demonstrate the one-photon phase control of retinal isomerization under conditions of low laser intensity. The calculations, utilizing the multiconfigurational time dependent Hartree method, include coupling between the two modes that are active in isomerization and the background molecular vibrational environment. Noting previously unsuccessful computations highlights the significance of this result.

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

    PubMed

    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.

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

    PubMed

    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

    DOEpatents

    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. Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of beta-HBCD racemization.

    PubMed

    Heeb, Norbert V; Schweizer, W Bernd; Mattrel, Peter; Haag, Regula; Kohler, Martin; Schmid, Peter; Zennegg, Markus; Wolfensberger, Max

    2008-04-01

    Hexabromocyclododecanes (HBCDs) are high production volume chemicals currently produced in quantities exceeding 20000ty(-1). They are used as flame retardants for plastics and textiles. HBCDs are thermally labile compounds, rapidly decomposing at temperatures above 250 degrees C to form bromine radicals, which scavenge other radicals formed during pyrolysis. But certain HBCD stereoisomers must reach the environment without decomposition, because their levels in soils, sediments, and biota are increasing worldwide. The fate of individual HBCD stereoisomers during production, product use, disposal, and transformation in the environment remains unclear. Herein we report on the thermally induced, highly selective isomerization of (+) and (-)beta-HBCD. Regio- and stereoselective migration of only two of the six bromine atoms resulted in the racemization of both beta-HBCDs. First order rate constants (k(rac)) increased from 0.005, 0.011, 0.021, to 0.055min(-1) at 130, 140, 150, and 160 degrees C, corresponding to half life times tau(1/2) of 143, 63, 29, and 14min, respectively. From the deduced kinetic model, we conclude that any thermal treatment of enantiomerically enriched beta-HBCDs in the range of 100-160 degrees C will result in a loss of most optical activity within few hours. The simultaneous inversion of two asymmetric centers occurred with perfect stereocontrol. Selectively, vicinal dibromides with the RR- and the SS-configurations migrated at these temperatures. An intramolecular reaction mechanism with a four-center transition state is postulated, based on the obtained stereoisomer pattern and the observed reaction kinetics. Crystal structure analysis revealed that all vicinal dibromides in beta-HBCDs prefer synclinal (gauche) conformations. However, an antiperiplanar (staggered) conformation is assumed to facilitate the concerted 1.2-shifts of both bromine atoms, resulting in an inversion of both neighboring carbon atoms. First experiments with other HBCD

  15. Aborted double bicycle-pedal isomerization with hydrogen bond breaking is the primary event of bacteriorhodopsin proton pumping.

    PubMed

    Altoè, Piero; Cembran, Alessandro; Olivucci, Massimo; Garavelli, Marco

    2010-11-23

    Quantum mechanics/molecular mechanics calculations based on ab initio multiconfigurational second order perturbation theory are employed to construct a computer model of Bacteriorhodopsin that reproduces the observed static and transient electronic spectra, the dipole moment changes, and the energy stored in the photocycle intermediate K. The computed reaction coordinate indicates that the isomerization of the retinal chromophore occurs via a complex motion accounting for three distinct regimes: (i) production of the excited state intermediate I, (ii) evolution of I toward a conical intersection between the excited state and the ground state, and (iii) formation of K. We show that, during stage ii, a space-saving mechanism dominated by an asynchronous double bicycle-pedal deformation of the C10═C11─C12═C13─C14═N moiety of the chromophore dominates the isomerization. On this same stage a N─H/water hydrogen bond is weakened and initiates a breaking process that is completed during stage iii.

  16. Optical Pumping and Laser Induced Nuclear Orientation of a Microsecond Isomeric Level in BARIUM-134

    NASA Astrophysics Data System (ADS)

    Bell, Curtis John

    Using optical pumping techniques, on and off-line experiments were performed on a microsecond nuclear isomer (('134m)Ba 10('+) ). Shifts in atomic resonances detected by changes in the angular distribution of characteristic nuclear radiations (expressed as changes in shape and size) yield information on changes in nuclear structure. The 10('+) isomeric state was produced using a 49 MeV pulsed beam of ('13)C on an isotopically enriched ('124)Sn target. The reaction products recoil out of the target and are slowed to thermal velocities in 10 torr of xenon in a region illuminated with circularly polarized light (553.5 nm) from a Coherent 699-21 dye laser. Nuclear parameters measured were the lifetime (3.8(2)(mu)s) and g-factor (g = -.20(1)) of the 10('+) state. Atomic parameters measured for barium were the depolarization cross sections of the ('1)P(,1) atomic level (6.0(6) nm('2)) in xenon, the quenching cross section for hydrogen (0.042(4) nm('2)), and the branching ratio of the metastable (('1,3)D(,1,2,3)) atomic states (0.011(1)). A possible anisotropy signal and the cumulative results (no measurable anisotropy) are presented. Difficulties encountered were insufficient neutralization, and unexpectedly large spatial distribution, and 'trapping' in metastable atomic states.

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

    PubMed

    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.

  18. Direct observation of disulfide isomerization in a single protein

    NASA Astrophysics Data System (ADS)

    Alegre-Cebollada, Jorge; Kosuri, Pallav; Rivas-Pardo, Jaime Andrés; Fernández, Julio M.

    2011-11-01

    Photochemical uncaging techniques use light to release active molecules from otherwise inert compounds. Here we expand this class of techniques by demonstrating the mechanical uncaging of a reactive species within a single protein. We proved this novel technique by capturing the regiospecific reaction between a thiol and a vicinal disulfide bond. We designed a protein that includes a caged cysteine and a buried disulfide. The mechanical unfolding of this protein in the presence of an external nucleophile frees the single reactive cysteine residue, which now can cleave the target disulfide via a nucleophilic attack on either one of its two sulfur atoms. This produces two different and competing reaction pathways. We used single-molecule force spectroscopy to monitor the cleavage of the disulfides, which extends the polypeptide by a magnitude unambiguously associated with each reaction pathway. This allowed us to measure, for the first time, the kinetics of disulfide-bond isomerization in a protein.

  19. Epoxidation of propylene dimers and isomerization of mixtures obtained

    SciTech Connect

    Dobrev, D.M.; Kurtev, K.S.

    1988-05-10

    Mixtures of hexenes are obtained in the dimerization of propylene on a Ziegler catalyst. By the epoxidation of this mixture by organic peroxides, followed by isomerization of the oxides, C/sub 6/ ketones, which are used as solvents, can be obtained. The hexenes were obtained by dimerization of propylene in the presence of a Ni(C/sub 5/H/sub 7/O/sub 2/)/sub 2/-P(C/sub 6/H/sub 5/)/sub 3/-(C/sub 3/H/sub 5/)/sub 2/AlCl catalytic system. The epoxidation was carried with technical grade isopropylbenzyl hydroperoxide (IPBHP). MoO/sub 2/(C/sub 5/H/sub 7/O/sub 2/)/sub 2/ was used as the catalyst. The relative rates of epoxidation of different isomers contained in the dimeric fraction, with respect to 2-methyl-1-pentene, was determined by means of competing reactions.

  20. Ultrafast isomerization initiated by X-ray core ionization

    NASA Astrophysics Data System (ADS)

    Liekhus-Schmaltz, Chelsea E.; Tenney, Ian; Osipov, Timur; Sanchez-Gonzalez, Alvaro; Berrah, Nora; Boll, Rebecca; Bomme, Cedric; Bostedt, Christoph; Bozek, John D.; Carron, Sebastian; Coffee, Ryan; Devin, Julien; Erk, Benjamin; Ferguson, Ken R.; Field, Robert W.; Foucar, Lutz; Frasinski, Leszek J.; Glownia, James M.; Gühr, Markus; Kamalov, Andrei; Krzywinski, Jacek; Li, Heng; Marangos, Jonathan P.; Martinez, Todd J.; McFarland, Brian K.; Miyabe, Shungo; Murphy, Brendan; Natan, Adi; Rolles, Daniel; Rudenko, Artem; Siano, Marco; Simpson, Emma R.; Spector, Limor; Swiggers, Michele; Walke, Daniel; Wang, Song; Weber, Thorsten; Bucksbaum, Philip H.; Petrovic, Vladimir S.

    2015-09-01

    Rapid proton migration is a key process in hydrocarbon photochemistry. Charge migration and subsequent proton motion can mitigate radiation damage when heavier atoms absorb X-rays. If rapid enough, this can improve the fidelity of diffract-before-destroy measurements of biomolecular structure at X-ray-free electron lasers. Here we study X-ray-initiated isomerization of acetylene, a model for proton dynamics in hydrocarbons. Our time-resolved measurements capture the transient motion of protons following X-ray ionization of carbon K-shell electrons. We Coulomb-explode the molecule with a second precisely delayed X-ray pulse and then record all the fragment momenta. These snapshots at different delays are combined into a `molecular movie' of the evolving molecule, which shows substantial proton redistribution within the first 12 fs. We conclude that significant proton motion occurs on a timescale comparable to the Auger relaxation that refills the K-shell vacancy.

  1. Isomeric separation of methamphetamine by HPLC chiral column.

    PubMed

    Lekskulchai, V

    2001-11-01

    Methamphetamine and its active metabolite, amphetamine, are optically active compounds which, based upon synthetic routes, can be found in two forms; pure d-form and racemic mixture. Analysis of their isomers can help to identify which precursor is currently spreading widely in a given region. Since there are many drugs that can be metabolized to amphetamine/methamphetamine, isomeric separation can be a useful tool for evaluation of these drugs, as well. Indirect method by using N-trifluoroacetyl-1-prolyl chloride (1-TPC) was found to have limited accuracy due to the contribution effect. In this presentation a direct method using HPLC Chirex chiral column 3022 was studied. Although the method gave no base-line separation of two different isomer peaks, it gave good sensitivity, reliability, and linearity. No contribution effect was found in the method presented. It also gave excellent correlation with the 1-TPC method.

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

    NASA Astrophysics Data System (ADS)

    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

  3. Mass spectrometric profiling of flavonoid glycoconjugates possessing isomeric aglycones.

    PubMed

    Abrankó, László; Szilvássy, Blanka

    2015-01-01

    In fields such as food and nutrition science or plant physiology, interest in untargeted profiling of flavonoids continues to expand. The group of flavonoids encompasses several thousands of chemically distinguishable compounds, among which are a number of isobaric compounds with the same elemental composition. Thus, the mass spectrometric identification of these compounds is challenging, especially when reference standards are not available to support their identification. Many different types of isomers of flavonoid glycoconjugates are known, i.e. compounds that differ in their glycosylation position, glycan sequence or type of interglycosidic linkage. This work focuses on the mass spectrometric identification of flavonoid glycoconjugate isomers possessing the same glycan mass and differing only in their aglycone core. A non-targeted HPLC-ESI-MS/MS profiling method using a triple quadrupole MS is presented herein, which utilizes in-source fragmentation and a pseudo-MS(3) approach for the selective analysis of flavonoid glycoconjugates with isomeric/isobaric aglycones. A selective MRM-based identification of the in-source formed isobaric aglycone fragments was established. Additionally, utilizing the precursor scanning capability of the employed triple quadrupole instrument, the developed method enabled the determination of the molecular weight of the studied intact flavonoid glycoconjugate. The versatility of the method was proven with various types of flavonoid aglycones, i.e. anthocyanins, flavonols, flavones, flavanones and isoflavones, along with their representative glycoconjugates. The developed method was also successfully applied to a commercially available sour cherry sample, in which 16 different glycoconjugates of pelargonidin, genistein, cyanidin, kaempferol and quercetin could be tentatively identified, including a number of compounds containing isomeric/isobaric aglycones.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. cis-trans-Isomerization of unsaturated fatty acids during /γ-irradiation of barley grains

    NASA Astrophysics Data System (ADS)

    Geißler, Christian; Brede, Ortwin; Reinhardt, Jürgen

    2003-06-01

    Gamma-irradiating barley grains with doses of 10-100 kGy, a dose dependent isomerization of the naturally occurring cis-unsaturated fatty acids such as oleic, cis-vaccenic, linoleic and also of linolenic acid was found. Whereas the effect was negligible up to 10 kGy, at 50 kGy the trans-fatty acid level became comparable to that of other natural products like butter fat which means that there is no essential nutrition danger. The cis-trans-isomerization found in barley grains is explained mainly by a thiyl radical driven process rather than direct isomerization.

  7. Observation of Isomeric Decays in the r-Process Waiting-Point Nucleus {sup 130}Cd{sub 82}

    SciTech Connect

    Jungclaus, A.; Poves, A.; Modamio, V.; Walker, J.; Caceres, L.; Gorska, M.; Grawe, H.; Langanke, K.; Martinez-Pinedo, G.; Cuenca-Garcia, J. J.; Doornenbal, P.; Geissel, H.; Gerl, J.; Kojouharov, I.; Kurz, N.; Prokopowicz, W.; Schaffner, H.; Wollersheim, H. J.; Montes, F.; Tashenov, S.

    2007-09-28

    The {gamma} decay of excited states in the waiting-point nucleus {sup 130}Cd{sub 82} has been observed for the first time. An 8{sup +} two-quasiparticle isomer has been populated both in the fragmentation of a {sup 136}Xe beam as well as in projectile fission of {sup 238}U, making {sup 130}Cd the most neutron-rich N=82 isotone for which information about excited states is available. The results, interpreted using state-of-the-art nuclear shell-model calculations, show no evidence of an N=82 shell quenching at Z=48. They allow us to follow nuclear isomerism throughout a full major neutron shell from {sup 98}Cd{sub 50} to {sup 130}Cd{sub 82} and reveal, in comparison with {sup 76}Ni{sub 48} one major proton shell below, an apparently abnormal scaling of nuclear two-body interactions.

  8. Radiative lifetime and energy of the low-energy isomeric level in 229Th

    NASA Astrophysics Data System (ADS)

    Tkalya, E. V.; Schneider, Christian; Jeet, Justin; Hudson, Eric R.

    2015-11-01

    We estimate the range of the radiative lifetime and energy of the anomalous, low-energy 3 /2+(7.8 ±0.5 eV) state in the 229Th nucleus. Our phenomenological calculations are based on the available experimental data for the intensities of M 1 and E 2 transitions between excited levels of the 229Th nucleus in the Kπ[N nZΛ ] =5 /2+[633 ] and 3 /2+[631 ] rotational bands. We also discuss the influence of certain branching coefficients, which affect the currently accepted measured energy of the isomeric state. From this work, we establish a favored region, 0.66 ×106seV3/ω3≤τ ≤2.2 ×106seV3/ω3 , where the transition lifetime τ as a function of transition energy ω should lie at roughly the 95% confidence level. Together with the result of Beck et al. [LLNL-PROC-415170 (2009)], we establish a favored area where transition lifetime and energy should lie at roughly the 90% confidence level. We also suggest new nuclear physics measurements, which would significantly reduce the ambiguity in the present data.

  9. "W-X-M" transformations in isomerization of B39- borospherenes

    NASA Astrophysics Data System (ADS)

    Gao, Ting-Ting; Chen, Qiang; Mu, Yue-Wen; Lu, Haigang; Li, Si-Dian

    2016-06-01

    The Stone-Wales transformation plays an important role in the isomerization of fullerenes and graphenic systems. The continuous conversions between neighboring six- and seven-membered rings in the borospherene (all-boron fullerene) B40 had been discovered (Martínez-Guajardo et al. Sci. Rep. 5, 11287 (2015)). In the first axially chiral borospherenes C3 B39- and C2 B39-, we identify three active boron atoms which are located at the center of three alternative sites involving five boron atoms denoted as "W", "X", and "M", respectively. The concerted movements of these active boron atoms and their close neighbors between neighboring six- and seven-membered rings define the "W-X-M" transformation of borospherenes. Extensive first-principles molecular dynamics simulations and quadratic synchronous transit transition-state searches indicate that, via three transition states (TS1, TS2, and TS3) and two intermediate species (M1 and M2), the three-step "W-X-M" transformations convert the C3 B39- global minimum into its C2 isomer at room temperature (300 K) and vice versa. The maximum barriers are only 3.89 kcal/mol from C3 to C2 B39- and 2.1 kcal/mol from C2 to C3 B39-, rendering dynamic fluxionalities to these borospherenes. Therefore, the "W-X-M" transformation plays an important role in the borospherenes and borospherene-based nanostructures.

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

    NASA Astrophysics Data System (ADS)

    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.

  11. Vibrational predissociation and vibrationally induced isomerization of 3-aminophenol-ammonia

    SciTech Connect

    Heid, Cornelia G.; Merrill, Wyatt G.; Case, Amanda S. Crim, F. Fleming

    2015-01-07

    We investigate the vibrational predissociation dynamics of the hydrogen-bonded 3-aminophenol-ammonia cluster (3-AP-NH{sub 3}) in the OH and NH stretching regions. Vibrational excitation provides enough energy to dissociate the cluster into its constituent 3-AP and NH{sub 3} monomers, and we detect the 3-AP fragments via (1 + 1) resonance-enhanced multiphoton ionization (REMPI). The distribution of vibrational states of the 3-AP fragment suggests the presence of two distinct dissociation pathways. The first dissociation channel produces a broad, unstructured feature in the REMPI-action spectrum after excitation of any of the OH or NH stretching vibrations, pointing to a nearly statistical dissociation pathway with extensive coupling among the vibrations in the cluster during the vibrational predissociation. The second dissociation channel produces distinct, resolved features on top of the broad feature but only following excitation of the OH or symmetric NH{sub 3} stretch in the cluster. This striking mode-specificity is consistent with strong coupling of these two modes to the dissociation coordinate (the O–H⋯N bond). The presence of clearly resolved transitions to the electronic origin and to the 10a{sup 2} + 10b{sup 2} state of the cis-3-AP isomer shows that vibrational excitation is driving the isomerization of the trans-3-AP-NH{sub 3} isomer to the cis-3-AP-NH{sub 3} isomer in the course of the dissociation.

  12. Molecular driving forces for Z/E isomerization mediated by heteroatoms: the example hemithioindigo.

    PubMed

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

    2010-12-23

    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 multiexponential reaction dynamics on the few picoseconds time scale, which are interpreted by quantum chemical calculations at the CASSCF/CASPT2 level of theory. Detailed insight into the processes governing the ultrafast decay from the first excited state, mediated by a number of conical intersections, is provided. Charge separation and charge balance recovery on the reaction pathway play the leading role and are controlled by the electron-donating or -withdrawing character of the heteroatoms. The electronic and geometric structures of the individual minimum energy conical intersections governing the reaction are rationalized, and an extended energetically low lying conical intersection seam is extracted. Comparison to the experimental results permits linking the observed time constants to molecular intermediates and pathways. An explanation is provided for the pronounced differences of Z → E and the E → Z photoreactions upon excitation to the first excited singlet state.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  14. Metal-centred azaphosphatriptycene gear with a photo- and thermally driven mechanical switching function based on coordination isomerism

    NASA Astrophysics Data System (ADS)

    Ube, Hitoshi; Yasuda, Yoshihiro; Sato, Hiroyasu; Shionoya, Mitsuhiko

    2017-02-01

    Metal ions can serve as a centre of molecular motions due to their coordination geometry, reversible bonding nature and external stimuli responsiveness. Such essential features of metal ions have been utilized for metal-mediated molecular machines with the ability to motion switch via metallation/demetallation or coordination number variation at the metal centre; however, motion switching based on the change in coordination geometry remain largely unexplored. Herein, we report a PtII-centred molecular gear that demonstrates control of rotor engagement and disengagement based on photo- and thermally driven cis-trans isomerization at the PtII centre. This molecular rotary motion transmitter has been constructed from two coordinating azaphosphatriptycene rotators and one PtII ion as a stator. Isomerization between an engaged cis-form and a disengaged trans-form is reversibly driven by ultraviolet irradiation and heating. Such a photo- and thermally triggered motional interconversion between engaged/disengaged states on a metal ion would provide a selector switch for more complex interlocking systems.

  15. Metal-centred azaphosphatriptycene gear with a photo- and thermally driven mechanical switching function based on coordination isomerism

    PubMed Central

    Ube, Hitoshi; Yasuda, Yoshihiro; Sato, Hiroyasu; Shionoya, Mitsuhiko

    2017-01-01

    Metal ions can serve as a centre of molecular motions due to their coordination geometry, reversible bonding nature and external stimuli responsiveness. Such essential features of metal ions have been utilized for metal-mediated molecular machines with the ability to motion switch via metallation/demetallation or coordination number variation at the metal centre; however, motion switching based on the change in coordination geometry remain largely unexplored. Herein, we report a PtII-centred molecular gear that demonstrates control of rotor engagement and disengagement based on photo- and thermally driven cis–trans isomerization at the PtII centre. This molecular rotary motion transmitter has been constructed from two coordinating azaphosphatriptycene rotators and one PtII ion as a stator. Isomerization between an engaged cis-form and a disengaged trans-form is reversibly driven by ultraviolet irradiation and heating. Such a photo- and thermally triggered motional interconversion between engaged/disengaged states on a metal ion would provide a selector switch for more complex interlocking systems. PMID:28176770

  16. Metal-centred azaphosphatriptycene gear with a photo- and thermally driven mechanical switching function based on coordination isomerism.

    PubMed

    Ube, Hitoshi; Yasuda, Yoshihiro; Sato, Hiroyasu; Shionoya, Mitsuhiko

    2017-02-08

    Metal ions can serve as a centre of molecular motions due to their coordination geometry, reversible bonding nature and external stimuli responsiveness. Such essential features of metal ions have been utilized for metal-mediated molecular machines with the ability to motion switch via metallation/demetallation or coordination number variation at the metal centre; however, motion switching based on the change in coordination geometry remain largely unexplored. Herein, we report a Pt(II)-centred molecular gear that demonstrates control of rotor engagement and disengagement based on photo- and thermally driven cis-trans isomerization at the Pt(II) centre. This molecular rotary motion transmitter has been constructed from two coordinating azaphosphatriptycene rotators and one Pt(II) ion as a stator. Isomerization between an engaged cis-form and a disengaged trans-form is reversibly driven by ultraviolet irradiation and heating. Such a photo- and thermally triggered motional interconversion between engaged/disengaged states on a metal ion would provide a selector switch for more complex interlocking systems.

  17. 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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    Wu, Yunlong; Zhao, Yanqing; Yang, Guo-Ping Guo, Yanjun; Wang, Yao-Yu 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

  19. Ion Mobility Mass Spectrometry Analysis of Isomeric Disaccharide Precursor, Product and Cluster Ions

    PubMed Central

    Li, Hongli; Bendiak, Brad; Siems, William F.; Gang, David R.; Hill, Herbert H.

    2015-01-01

    RATIONALE Carbohydrates are highly variable in structure owing to differences in their anomeric configurations, monomer stereochemistry, inter-residue linkage positions and general branching features. The separation of carbohydrate isomers poses a great challenge for current analytical techniques. METHODS The isomeric heterogeneity of disaccharide ions and monosaccharideglycolaldehyde product ions evaluated using electrospray traveling wave ion mobility mass spectrometry (Synapt G2 high definition mass spectrometer) in both positive and negative ion modes investigation. RESULTS The separation of isomeric disaccharide ions was observed but not fully achieved based on their mobility profiles. The mobilities of isomeric product ions, the monosaccharide-glycolaldehydes, derived from different disaccharide isomers were measured. Multiple mobility peaks were observed for both monosaccharide-glycolaldehyde cations and anions, indicating that there was more than one structural configuration in the gas phase as verified by NMR in solution. More importantly, the mobility patterns for isomeric monosaccharide-glycolaldehyde product ions were different, which enabled partial characterization of their respective disaccharide ions. Abundant disaccharide cluster ions were also observed. The Results showed that a majority of isomeric cluster ions had different drift times and, moreover, more than one mobility peak was detected for a number of specific cluster ions. CONCLUSIONS It is demonstrated that ion mobility mass spectrometry is an advantageous method to assess the isomeric heterogeneity of carbohydrate compounds. It is capable of differentiating different types of carbohydrate ions having identical m/z values as well as multiple structural configurations of single compounds. PMID:24591031

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

    SciTech Connect

    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.

  1. Randomized Subspace Learning for Proline Cis-Trans Isomerization Prediction.

    PubMed

    Al-Jarrah, Omar Y; Yoo, Paul D; Taha, Kamal; Muhaidat, Sami; Shami, Abdallah; Zaki, Nazar

    2015-01-01

    Proline residues are common source of kinetic complications during folding. The X-Pro peptide bond is the only peptide bond for which the stability of the cis and trans conformations is comparable. The cis-trans isomerization (CTI) of X-Pro peptide bonds is a widely recognized rate-limiting factor, which can not only induces additional slow phases in protein folding but also modifies the millisecond and sub-millisecond dynamics of the protein. An accurate computational prediction of proline CTI is of great importance for the understanding of protein folding, splicing, cell signaling, and transmembrane active transport in both the human body and animals. In our earlier work, we successfully developed a biophysically motivated proline CTI predictor utilizing a novel tree-based consensus model with a powerful metalearning technique and achieved 86.58 percent Q2 accuracy and 0.74 Mcc, which is a better result than the results (70-73 percent Q2 accuracies) reported in the literature on the well-referenced benchmark dataset. In this paper, we describe experiments with novel randomized subspace learning and bootstrap seeding techniques as an extension to our earlier work, the consensus models as well as entropy-based learning methods, to obtain better accuracy through a precise and robust learning scheme for proline CTI prediction.

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

    PubMed Central

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

    2016-01-01

    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. PMID:27339163

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

  8. Photofragmentation of I2-ṡArn clusters: Observation of metastable isomeric ionic fragments

    NASA Astrophysics Data System (ADS)

    Vorsa, Vasil; Campagnola, Paul J.; Nandi, Sreela; Larsson, Mats; Lineberger, W. C.

    1996-08-01

    We report the 790 nm photofragmentation of mass-selected I-2ṡArn clusters, n=1 to 27. We determine the I-+I caging efficiency as a function of the number of solvent Ar atoms and compare these results with I-2 in CO2 clusters. Caging is much less effective with Ar. In addition to ``normal'' caged photoproducts (I-2ṡArm, where mstate or as a solvent-separated pair at an internuclear separation of ˜5.5 Å. The photofragmentation data also exhibit the existence of two distinct isomeric forms of the precursor I-2ṡArn, for n≤14. These forms are evaporatively distinct in that one isomer displays highly nonstatistical fragmentation, probably arising from a cluster in which the I-2 resides on the surface, rather than in the interior. The photofragmentation distribution of the other form exhibits statistical behavior, consistent with the evaporation of an I-2 solvated inside the cluster.

  9. Extrapolating potential energy surfaces by scaling electron correlation: Isomerization of bicyclobutane to butadiene

    NASA Astrophysics Data System (ADS)

    Lutz, Jesse J.; Piecuch, Piotr

    2008-04-01

    The recently proposed potential energy surface (PES) extrapolation scheme, which predicts smooth molecular PESs corresponding to larger basis sets from the relatively inexpensive calculations using smaller basis sets by scaling electron correlation energies [A. J. C. Varandas and P. Piecuch, Chem. Phys. Lett. 430, 448 (2006)], is applied to the PESs associated with the conrotatory and disrotatory isomerization pathways of bicyclo[1.1.0]butane to buta-1,3-diene. The relevant electronic structure calculations are performed using the completely renormalized coupled-cluster method with singly and doubly excited clusters and a noniterative treatment of connected triply excited clusters, termed CR-CC(2,3), which is known to provide a highly accurate description of chemical reaction profiles involving biradical transition states and intermediates. A comparison with the explicit CR-CC(2,3) calculations using the large correlation-consistent basis set of the cc-pVQZ quality shows that the cc-pVQZ PESs obtained by the extrapolation from the smaller basis set calculations employing the cc-pVDZ and cc-pVTZ basis sets are practically identical, to within fractions of a millihartree, to the true cc-pVQZ PESs. It is also demonstrated that one can use a similar extrapolation procedure to accurately predict the complete basis set (CBS) limits of the calculated PESs from the results of smaller basis set calculations at a fraction of the effort required by the conventional pointwise CBS extrapolations.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

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

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

  13. Formation, isomerization, and dissociation of alpha-carbon-centered and pi-centered glycylglycyltryptophan radical cations

    SciTech Connect

    Ng, Dominic C.; Song, Tao; Siu, Shiu On; Siu, Chi-Kit; Laskin, Julia; Chu, Ivan K.

    2010-02-11

    Gas phase fragmentations of two isomeric radical cationic tripeptides of glycylglycyltryptophan-G•GW+ and [GGW]•+—with well-defined initial radical sites at the α-carbon atom and the 3-methylindole ring, respectively, have been studied using collision-induced dissociation (CID), density functional theory (DFT), and Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Substantially different low-energy CID spectra were obtained for these two isomeric GGW structures, suggesting that they did not interconvert on the time scale of these experiments. DFT and RRKM calculations were used to investigate the influence of the kinetics, stabilities, and locations of the radicals on the competition between the isomerization and dissociation channels. The calculated isomerization barrier between the GGW radical cations (>35.4 kcal/mol) was slightly higher than the barrier for competitive dissociation of these species (<30.5 kcal/mol); the corresponding microcanonical rate constants for isomerization obtained from RRKM calculations were all considerably lower than the dissociation rates at all internal energies. Thus, interconversion between the GGW isomers examined in this study cannot compete with their fragmentations.

  14. Quantum chemical and master equation simulations of the oxidation and isomerization of vinoxy radicals.

    PubMed

    Kuwata, Keith T; Hasson, Alam S; Dickinson, Ray V; Petersen, Erin B; Valin, Lukas C

    2005-03-24

    The vinoxy radical, a common intermediate in gas-phase alkene ozonolysis, reacts with O2 to form a chemically activated alpha-oxoperoxy species. We report CBS-QB3 energetics for O2 addition to the parent (*CH2CHO, 1a), 1-methylvinoxy (*CH2COCH3, 1b), and 2-methylvinoxy (CH3*CHCHO, 1c) radicals. CBS-QB3 predictions for peroxy radical formation agree with experimental data, while the G2 method systematically overestimates peroxy radical stability. RRKM/master equation simulations based on CBS-QB3 data are used to estimate the competition between prompt isomerization and thermalization for the peroxy radicals derived from 1a, 1b, and 1c. The lowest energy isomerization pathway for radicals 4a and 4c (derived from 1a and 1c, respectively) is a 1,4-shift of the acyl hydrogen requiring 19-20 kcal/mol. The resulting hydroperoxyacyl radical decomposes quantitatively to form *OH. The lowest energy isomerization pathway for radical 4b (derived from 1b) is a 1,5-shift of a methyl hydrogen requiring 26 kcal/mol. About 25% of 4a, but only approximately 5% of 4c, isomerizes promptly at 1 atm pressure. Isomerization of 4b is negligible at all pressures studied.

  15. Stability and isomerization of complexes formed by metal ions and cytosine isomers in aqueous phase.

    PubMed

    Ai, Hongqi; Liu, Jingjing; Chan, Kwaichow

    2013-08-01

    We present a systematic study of the stability of the formation of complexes produced by four metal ions (M(+/2+)) and 14 cytosine isomers (Cn). This work predicts theoretically that predominant product complexes are associated with higher-energy C4M(+/2+) and C5M(+/2+) rather than the most stable C1M(+/2+). The prediction resolves successfully several experimental facts puzzling two research groups. Meanwhile, in-depth studies further reveal that direct isomerization of C1↔C4 is almost impossible, and also that the isomerization induced by either metalation or hydration, or by a combination of the two unfavorable. It is the single water molecule locating between the H1(-N1) and O2 of the cytosine that plays the dual roles of being a bridge and an activator that consequently improves the isomerization greatly. Moreover, the cooperation of divalent metal ion and such a monohydration actually leads to an energy-free C1←C4 isomerization in the gas phase. Henceforth, we are able to propose schemes inhibiting the free C1←C4 isomerization, based purely on extended hydration at the divalent metal ion.

  16. Isomeric yield ratios and excitation functions in α-induced reactions on 107,109Ag

    NASA Astrophysics Data System (ADS)

    Guin, R.; Saha, S. K.; Prakash, Satya; Uhl, M.

    1992-07-01

    Isomeric yield ratios for the reactions 107Ag(α,3n)108In, 107Ag(α,α3n)104Ag, 109Ag(α,2n)111In, and 109Ag(α,3n)110In are determined in the energy range of 20-63 MeV α particles. Excitation functions for the above reactions as well as for the 107Ag(α,2n)109In, 107Ag(α,α2n)105Ag, 109Ag(α,4n)109In, 109Ag(α,5n)108In, and 109Ag(α,α4n)105Ag reactions are also presented. Experimental excitation functions are compared with statistical model calculations taking into account precompound particle emission. Isomeric yield ratios are found to depend strongly on the root mean square orbital angular momentum in the entrance channel. A semiempirical method for the prediction of isomeric yield ratios failed to reproduce experimental data even for compoundlike reactions. Isomeric yield ratios were also calculated in the frame of a statistical model under consideration of angular momentum effects in the preequilibrium and the equilibrium stage. Overall agreement between the theory and the experiment for isomeric yield ratios was found to be satisfactory especially at low bombarding energy when compound nucleus reaction channel is dominant. The discrepancy observed at higher bombarding energies needs to be theoretically investigated in greater detail.

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

    PubMed

    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.

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

    PubMed

    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.

  19. Ab initio studies of isomerization and dissociation reactions of peroxyacetyl nitrate (PAN)

    NASA Astrophysics Data System (ADS)

    Wei, Wen-Mei; Tan, Wei; Zheng, Ren-Hui; He, Tian-Jing; Chen, Dong-Ming; Liu, Fan-Chen

    2005-06-01

    The complex potential energy surface for the unimolecular isomerization and decomposition of peroxyacetyl nitrate (PAN, CH3C(O)OONO2), including 11 isomers, 45 interconversion transition states and 18 major dissociation products, is probed theoretically at the G2MP2//B3LYP/6-311G(2d,2p) level of theory. The geometries and relative energies for various stationary points are determined. Based on the calculated G2MP2 potential energy surface, the possible unimolecular decomposition mechanism of PAN is proposed. It is shown that the most feasible decomposition channels of PAN are those leading to 2CH3C(O)OO + NO2, 2CH3C(O)O + 2NO3, and 2CH3 + CO2 + 2NO3, respectively. Among them, the formations of the products of the first two channels are produced by the homolytic O-N and O-O bond ruptures of PAN with the bond dissociation energies of 32.3 and 33.9 kcal/mol, respectively, while the last one is initiated by the concerted C-C and O-O bond fissions via a barrier of 36.5 kcal/mol. Our results suggest that besides the first two decomposition pathways which have been reported by the literature, the last concerted bond fission dissociation channel via a well-defined transition state is also feasible, which has been confirmed by using CBS-Q and CBS-QB3 methods. Therefore, PAN dissociation occurs mainly via the homolytic O-N or O-O bond ruptures or via the concerted C-C and O-O bond fissions while the first channel is more favorable than the last two channels.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Experimental and DFT studies of initiation processes for butane isomerization over sulfated-zirconia catalysts

    SciTech Connect

    Hong, Z.; Watwe, R.M.; Natal-Santiago, M.A.; Hill, J.M.; Dumesic, J.A.; Fogash, K.B.; Kim, B.; Masqueda-Jimenez, B.I.

    1998-09-10

    Reaction kinetics studies were conducted of isobutane and n-butane isomerization at 423 K over sulfated-zirconia, with the butane feeds purified of olefins. Dihydrogen evolution was observed during butane isomerization over fresh catalysts, as well as over catalysts selectively poisoned by preadsorbed ammonia. Butane isomerization over sulfated-zirconia can be viewed as a surface chain reaction comprised of initiation, propagation, and termination steps. The primary initiation step in the absence of feed olefins is considered to be the dehydrogenation of butane over sulfated-zirconia, generating butenes which adsorb onto acid sites to form protonated olefinic species associated with the conjugate base form of the acid sites. Quantum-chemical calculations, employing density-functional theory, suggest that the dissociative adsorption of dihydrogen, isobutylene hydrogenation, and dissociative adsorption of isobutane are feasible over the sulfated-zirconia cluster, and these reactions take place over Zr-O sites.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Evidence from Chlamydomonas on the photoactivation of rhodopsins without isomerization of their chromophore

    PubMed Central

    Foster, Kenneth W.; Saranak, Jureepan; Krane, Sonja; Johnson, Randy L.; Nakanishi, Koji

    2011-01-01

    SUMMARY Attachment of retinal to opsin forms the chromophore N-retinylidene which isomerizes during photoactivation of rhodopsins. To test whether isomerization is crucial, custom-tailored chromophores lacking the β-ionone ring and any isomerizable bonds were incorporated in vivo into the opsin of a blind mutant of the eukaryote Chlamydomonas reinhardtii. The analogues restored phototaxis with the anticipated action spectra, ruling out the need for isomerization in photoactivation. To further elucidate photoactivation, responses to chromophores formed from naphthalene aldehydes were studied. The resulting action spectral shifts suggest that charge separation within the excited chromophore leads to electric field induced polarization of nearby amino-acid residues and altered hydrogen bonding. This redistribution of charge faciliates the reported multiple bond rotations and protein rearrangements of rhodopsin activation. These results provide new insight into the activation of rhodopsins and related GPCRs. PMID:21700209

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

    PubMed

    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.

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

    PubMed

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

    2015-01-01

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

  7. Isomerization of Cyclooctadiene to Cyclooctyne with a Zinc/Zirconium Heterobimetallic Complex

    PubMed Central

    Butler, Michael J.; White, Andrew J. P.

    2016-01-01

    Abstract Reaction of a zinc/zirconium heterobimetallic complex with 1,5‐cyclooctadiene (1,5‐COD) results in slow isomerization to 1,3‐cyclooctadiene (1,3‐COD), along with the formation of a new complex that includes a cyclooctyne ligand bridging two metal centers. While analogous magnesium/zirconium and aluminum/zirconium heterobimetallic complexes are competent for the catalytic isomerization of 1,5‐COD to 1,3‐COD, only in the case of the zinc species is the cyclooctyne adduct observed. PMID:27071992

  8. Pump-Probe Spectroscopy of Thermal Cis-Trans Isomerization Process of Methyl Red in 1-Octanol

    NASA Astrophysics Data System (ADS)

    Joukai, Tatsuya; Kita, Kenji; Yano, Ryuzi

    Thermal cis-trans isomerization process of Methyl Red in 1-Octanol at room temperature was studied by pump-probe spectroscopy. The isomerization rate increased as the dye concentration was increased. However, at concentrations above ~ 3 × 10-5 mol/L, the isomerization rate became almost constant regardless of the dye concentration. We interpreted that the concentration dependence of the thermal isomerization rate was caused by the creation of hydrogen-bonded dimer molecules. When a dimer is formed, one of the dye molecules which form the dimer easily changes its form from the cis isomer to the trans isomer. As the dye concentration is increased, the ratio of dyes which form dimer molecules will increase. When the dye concentration is high enough, most dye molecules form dimer molecules. Thus the isomerization rate averaged over the dye molecules is constant.

  9. A search for thermal isomerization of olefins to carbenes: Thermal generations of the silicon-nitrogen double bond

    SciTech Connect

    Zhang, Xianping.

    1990-09-21

    The first part of this thesis will search for the thermal isomerization of olefins to carbenes which is predicted to be a high energy process by calculations and has only been observed in a few strained olefins. The possibility of thermal isomerization of simple olefins to carbenes will be explored. Substitution of a silyl group on the double bond of an olefin allows a potential intermediate which has a {beta}-radical to the silyl group during the cis-trans isomerization. The effects of a trimethylsilyl group on this isomerization are the subject of this study. The second part of this thesis will include the generation and chemistry of intermediates containing a silicon-nitrogen double bond. The isomerization of parent silanimine to the aminosilylene was calculated to be a high energy process. New approaches to the silicon-nitrogen double bond will also be presented. 92 refs., 12 figs., 11 tabs.

  10. Linkage Isomerization in Heme–NOx Compounds: Understanding NO, Nitrite, and Hyponitrite Interactions with Iron Porphyrins

    PubMed Central

    Xu, Nan; Yi, Jun

    2011-01-01

    Nitric oxide (NO) and its derivatives such as nitrite and hyponitrite are biologically important species of relevance to human health. Much of their physiological relevance stems from their interactions with the iron centers in heme proteins. The chemical reactivities displayed by the heme-NOx species (NOx = NO, nitrite, hyponitrite) are a function of the binding modes of the NOx ligands. Hence, an understanding of the types of binding modes extant in heme-NOx compounds is important if we are to unravel the inherent chemical properties of these NOx metabolites. In this Forum article, the experimentally characterized linkage isomers of heme-NOx models and proteins are presented and reviewed. Nitrosyl linkage isomers of synthetic Fe and Ru porphyrins have been generated by photolysis at low temperatures and characterized by spectroscopy and DFT calculations. Nitrite linkage isomers in synthetic metalloporphyrin derivatives have been generated from photolysis experiments and in low-temperature matrices. In the case of nitrite adducts of heme proteins, both N-binding and O-binding have been determined crystallographically, and the role of the distal Hbonding residue in myoglobin in directing the O-binding mode of nitrite has been explored using mutagenesis. To date, only one synthetic metalloporphyrin complex containing a hyponitrite ligand (displaying an O-binding mode) has been characterized by crystallography. This is contrasted with other hyponitrite binding modes experimentally determined for coordination compounds and computationally for NO reductase enzymes. Although linkage isomerism in heme-NOx derivatives is still in its infancy, opportunities now exist for a detailed exploration of the existence and stabilities of the metastable states in both heme models and heme proteins. PMID:20666385

  11. Proline cis-trans isomerization in staphylococcal nuclease: multi-substrate free energy perturbation calculations.

    PubMed Central

    Hodel, A.; Rice, L. M.; Simonson, T.; Fox, R. O.; Brünger, A. T.

    1995-01-01

    Staphylococcal nuclease A exists in two folded forms that differ in the isomerization state of the Lys 116-Pro 117 peptide bond. The dominant form (90% occupancy) adopts a cis peptide bond, which is observed in the crystal structure. NMR studies show that the relatively small difference in free energy between the cis and trans forms (delta Gcis-->trans approximately 1.2 kcal/mol) results from large and nearly compensating differences in enthalpy and entropy (delta Hcis-->trans approximately delta TScis-->trans approximately 10 kcal/mol). There is evidence from X-ray crystal structures that the structural differences between the cis and the trans forms of nuclease are confined to the conformation of residues 112-117, a solvated protein loop. Here, we obtain a thermodynamic and structural description of the conformational equilibrium of this protein loop through an exhaustive conformational search that identified several substates followed by free energy simulations between the substrates. By partitioning the search into conformational substates, we overcame the multiple minima problem in this particular case and obtained precise and reproducible free energy values. The protein and water environment was implicitly modeled by appropriately chosen nonbonded terms between the explicitly treated loop and the rest of the protein. These simulations correctly predicted a small free energy difference between the cis and trans forms composed of larger, compensating differences in enthalpy and entropy. The structural predictions of these simulations were qualitatively consistent with known X-ray structures of nuclease variants and yield a model of the unknown minor trans conformation. PMID:7613463

  12. How Accurate Are the Minnesota Density Functionals for Noncovalent Interactions, Isomerization Energies, Thermochemistry, and Barrier Heights Involving Molecules Composed of Main-Group Elements?

    PubMed

    Mardirossian, Narbe; Head-Gordon, Martin

    2016-09-13

    The 14 Minnesota density functionals published between the years 2005 and early 2016 are benchmarked on a comprehensive database of 4986 data points (84 data sets) involving molecules composed of main-group elements. The database includes noncovalent interactions, isomerization energies, thermochemistry, and barrier heights, as well as equilibrium bond lengths and equilibrium binding energies of noncovalent dimers. Additionally, the sensitivity of the Minnesota density functionals to the choice of basis set and integration grid is explored for both noncovalent interactions and thermochemistry. Overall, the main strength of the hybrid Minnesota density functionals is that the best ones provide very good performance for thermochemistry (e.g., M06-2X), barrier heights (e.g., M08-HX, M08-SO, MN15), and systems heavily characterized by self-interaction error (e.g., M06-2X, M08-HX, M08-SO, MN15), while the main weakness is that none of them are state-of-the-art for the full spectrum of noncovalent interactions and isomerization energies (although M06-2X is recommended from the 10 hybrid Minnesota functionals). Similarly, the main strength of the local Minnesota density functionals is that the best ones provide very good performance for thermochemistry (e.g., MN15-L), barrier heights (e.g., MN12-L), and systems heavily characterized by self-interaction error (e.g., MN12-L and MN15-L), while the main weakness is that none of them are state-of-the-art for the full spectrum of noncovalent interactions and isomerization energies (although M06-L is clearly the best from the four local Minnesota functionals). As an overall guide, M06-2X and MN15 are perhaps the most broadly useful hybrid Minnesota functionals, while M06-L and MN15-L are perhaps the most broadly useful local Minnesota functionals, although each has different strengths and weaknesses.

  13. 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,

    NASA Astrophysics Data System (ADS)

    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.

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

    DTIC Science & Technology

    2015-11-03

    retinal protonated Schiff base (RPSB). Photoisomerization of the RPSB is the primary in animal vision. We find that the energy barrier for a single...determine in- ternal energy barrier for isomerization [1]. Here we apply the technique to the important case of the retinal protonated Schiff base

  15. The phytohormone precursor OPDA is isomerized in the insect gut by a single, specific glutathione transferase

    PubMed Central

    Dąbrowska, Paulina; Freitak, Dalial; Vogel, Heiko; Heckel, David G.; Boland, Wilhelm

    2009-01-01

    Oxylipins play important roles in stress signaling in plants. The compound 12-oxophytodienoic acid (cis-OPDA) is an early biosynthetic precursor of jasmonic acid (JA), the key phytohormone orchestrating the plant anti-herbivore defense. When consumed by feeding Lepidopteran larvae, plant-derived cis-OPDA suffers rapid isomerization to iso-OPDA in the midgut and is excreted in the frass. Unlike OPDA epimerization (yielding trans-OPDA), the formation of iso-OPDA is enzyme-dependent, and is catalyzed by an inducible glutathione transferase (GSTs) from the larval gut. Purified GST fractions from the gut of Egyptian cotton leafworm (Spodoptera littoralis) and cotton bollworm (Helicoverpa armigera) both exhibited strong OPDA isomerization activity, most likely via transient formation of a glutathione-OPDA conjugate. Out of 16 cytosolic GST proteins cloned from the gut of cotton bollworm larvae and expressed in E. coli, only one catalyzed the OPDA isomerization. The biological function of the double bond shift might be seen in an inactivation of cis-OPDA, similar to the inactivation of prostaglandin A1 to prostaglandin B1 in mammalian tissue. The enzymatic isomerization is particularly widespread among generalist herbivores that have to cope with various amounts of cis-OPDA in their spectrum of host plants. PMID:19805297

  16. Retardation of the orientation relaxation of azo-dye doped amorphous polymers upon photoinduced isomerization

    NASA Astrophysics Data System (ADS)

    Chan, S. W.; Quatela, A.; Casalboni, M.; Nunzi, J.-M.

    2006-08-01

    The orientation relaxation upon photo-induced isomerization of azo-dyes was studied. All-optical poling (AOP) and photo-induced birefringence, which are based on the mechanism of angular selective photo-isomerization, were employed to manipulate the angular distribution of azo-dyes (Disperse-red 1) doped in three different amorphous polymers: (poly(methyl methacrylate) PMMA, poly(carbonate) PC and poly(sulfone) PSU), with different glass transition temperature (T g). In the case of AOP, quasi-permanent macroscopic second-order nonlinear optical susceptibility χ (2) was inscribed in the dye-doped centro-symmetric polymer systems, while in the case of photo-induced birefringence, quasi-permanent birefringence Δn was inscribed in the dye-doped isotropic polymer systems. Relaxation of χ (2) and Δn were monitored upon different duration of AOP and photo-induced birefringence preparation. Experimental results show that azo-dye orientation relaxation follows the duration of the photo-nduced isomerization process: the longer the photo-induced isomerization process, the slower the relaxation of the inscribed χ (2) and Δn. In addition, retardation of the orientation relaxation does not follow a simple relation with hardness (T g) of the polymer host. Causes of the orientation relaxation retardation are discussed.

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

    PubMed

    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.

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

    PubMed

    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.

  19. Competitive Adsorption of Substrate and Solvent in Sn‐Beta Zeolite During Sugar Isomerization

    PubMed Central

    van der Graaff, William N. P.; Tempelman, Christiaan H. L.; Li, Guanna; Mezari, Brahim; Kosinov, Nikolay

    2016-01-01

    Abstract The isomerization of 1,3‐dihydroxyactone and d‐glucose over Sn‐Beta zeolite was investigated by in situ 13C NMR spectroscopy. The conversion rate at room temperature is higher when the zeolite is dehydrated before exposure to the aqueous sugar solution. Mass transfer limitations in the zeolite micropores were excluded by comparing Sn‐Beta samples with different crystal sizes. Periodic density functional theory (DFT) calculations show that sugar and water molecules compete for adsorption on the active framework Sn centers. Careful solvent selection may thus increase the rate of sugar isomerization. Consistent with this prediction, batch catalytic experiments show that the use of a co‐solvent, such as tetrahydrofuran, that strongly interacts with the Sn centers suppresses glucose isomerization. On the other hand, the use of ethanol as cosolvent results in significantly higher isomerization activity in comparison with pure water because of decreased competition with glucose adsorption on zeolitic Sn sites. PMID:27791334

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

    PubMed

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

    2013-08-26

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

  1. Isomerization of 4-vinylcyclohexene radical cation. A tandem mass spectrometry study

    SciTech Connect

    Vollmer, D.; Rempel, D.L.; Gross, M. L. ); Williams, F. )

    1995-02-08

    Investigation by matrix-isolation ESR has shown that 4-vinylcyclohexene, 1, surprisingly undergoes isomerization to the bicyclo[3.2.1]oct-2-ene ion, 3. Here we demonstrate the occurrence of this isomerization in the gas phase by use of tandem (MS/MS) sector and Fourier transform (FT) mass spectrometries. The radical cations of 4-vinylcyclohexene (IE = 8.93 eV) or bicyclo[3.2.1]oct-2-ene (approximately 14 kcal/mol more stable than that of 4-vinylcyclohexene) were formed, in separate trials, in a chemical ionization (CI) source by electron ionization (EI). The radical cations were then studied by obtaining their collisionally activated decomposition (CAD) spectra. The CAD spectra are similar, indicating that the isomerization has occurred. Both the sector and the FT mass spectrometer results reflect those obtained in the matrix-isolation ESR investigation. That is isomerizes to 3 at high internal energy, but is stable at low internal energy. Two mechanisms explain this rearrangement. The second mechanism is questionable because the most stable olefin radical cation formed from 5 is that of bicyclo[2.2.2]-2-octene, which gives different ESR and CAD spectra than those of 1 or 3. The CAD spectrum of bicyclo[2.2.2]-2-octene radical cation indicates that the retro-Diels-Alder loss of ethylene is more facile than that from 1 or 3. 18 refs., 3 figs.

  2. Surprising photochemical and thermal isomerizations of a cyclic 1,2,3-butatriene

    SciTech Connect

    Chen, Yiyuan; Ma, Zhongxin; Ijadi-Maghsoodi, Sina; Barton, T.J. |

    1997-12-31

    Photolysis of cyclic 1,2,3-butatriene 1 exclusively affords cyclopropane 2 for which an unprecedented initial isomerization to a methylenecyclopropanylidene is proposed. Thermolysis of 1 produces butadiene 3 in 83% yield. Formation of 3 is an apparent disallowed S, A [2+2] cycloaddition but we will argue that it is actually an allowed [4+2] cycloaddition.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    PubMed

    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.

  5. Synthesis and thermocatalytic isomerization of 1,2,3-triphenyl-3-(diacylmethyl)cyclopropenes

    SciTech Connect

    Plotkin, V.N.; Domnin, I.N.; Dmitrieva, E.F.; Komendantov, M.I.

    1987-10-20

    The authors investigate the thermocatalytic isomerization of the title compounds to the corresponding substituted cyclopentadienes with high yields under the action of an organic copper carbonyl catalyst. Kinetics are established for reaction pathways and times. Infrared spectra, determined in potassium bromide and carbon tetrachloride, and NMR spectra, determined in deuterated chloroform and carbon tetrachloride, are analyzed.

  6. Tandem isomerization-decarboxylation for converting alkenoic fatty acids into alkenes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We report a facile Ru-catalyzed route to alkenes from alkenoic fatty acids via a readily accessible pre-catalyst [Ru(CO)2RCO2]n. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds in an aliphatic chain and, subsequently, decarboxylating specif...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

    ERIC Educational Resources Information Center

    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…

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Ab initio reaction pathways for photodissociation and isomerization of nitromethane on four singlet potential energy surfaces with three roaming paths

    SciTech Connect

    Isegawa, Miho; Liu, Fengyi; Morokuma, Keiji; Maeda, Satoshi

    2014-06-28

    Photodissociation pathways of nitromethane following π → π{sup *} electronic excitation are reported. The potential energy surfaces for four lowest singlet states are explored, and structures of many intermediates, dissociation limits, transition states, and minimum energy conical intersections were determined using the automated searching algorism called the global reaction route mapping strategy. Geometries are finally optimized at CASSCF(14e,11o) level and energies are computed at CAS(14o,11e)PT2 level. The calculated preferable pathways and important products qualitatively explain experimental observations. The major photodissociation product CH{sub 3} and NO{sub 2} ({sup 2}B{sub 2}) is formed by direct dissociation from the S{sub 1} state. Important pathways involving S{sub 1} and S{sub 0} states for production of various dissociation products CH{sub 3}NO + O ({sup 1}D), CH{sub 3}O(X{sup 2}E) + NO (X{sup 2}Π), CH{sub 2}NO + OH, and CH{sub 2}O + HNO, as well as various isomerization pathways have been identified. Three roaming processes also have been identified: the O atom roaming in O dissociation from CH{sub 3}NO{sub 2}, the OH radical roaming in OH dissociation from CH{sub 2}N(O)(OH), and the NO roaming in NO dissociation from CH{sub 3}ONO.

  11. A classical trajectory study of the intramolecular dynamics, isomerization, and unimolecular dissociation of HO2

    NASA Astrophysics Data System (ADS)

    Perry, Jamin W.; Dawes, Richard; Wagner, Albert F.; Thompson, Donald L.

    2013-08-01

    The classical dynamics and rates of isomerization and dissociation of HO2 have been studied using two potential energy surfaces (PESs) based on interpolative fittings of ab initio data: An interpolative moving least-squares (IMLS) surface [A. Li, D. Xie, R. Dawes, A. W. Jasper, J. Ma, and H. Guo, J. Chem. Phys. 133, 144306 (2010)] and the cubic-spline-fitted PES reported by Xu, Xie, Zhang, Lin, and Guo (XXZLG) [J. Chem. Phys. 127, 024304 (2007)]. Both PESs are based on similar, though not identical, internally contracted multi-reference configuration interaction with Davidson correction (icMRCI+Q) electronic structure calculations; the IMLS PES includes complete basis set (CBS) extrapolation. The coordinate range of the IMLS PES is limited to non-reactive processes. Surfaces-of-section show similar generally regular phase space structures for the IMLS and XXZLG PESs with increasing energy. The intramolecular vibrational energy redistribution (IVR) at energies above and below the threshold of isomerization is slow, especially for O-O stretch excitations, consistent with the regularity in the surfaces-of-section. The slow IVR rates lead to mode-specific effects that are prominent for isomerization (on both the IMLS and XXZLG) and modest for unimolecular dissociation to H + O2 (accessible only on the XXZLG PES). Even with statistical distributions of initial energy, slow IVR rates result in double exponential decay for isomerization, with the slower rate correlated with slow IVR rates for O-O vibrational excitation. The IVR and isomerization rates computed for the IMLS and XXZLG PESs are quantitatively, but not qualitatively, different from one another with the largest differences ascribed to the ˜2 kcal/mol difference in the isomerization barrier heights. The IMLS and XXZLG results are compared with those obtained using the global, semi-empirical double-many-body expansion DMBE-IV PES [M. R. Pastrana, L. A. M. Quintales, J. Brandão, and A. J. C. Varandas, J. Chem

  12. Ibuprofen Impairs Allosterically Peroxynitrite Isomerization by Ferric Human Serum Heme-Albumin*

    PubMed Central

    Ascenzi, Paolo; di Masi, Alessandra; Coletta, Massimo; Ciaccio, Chiara; Fanali, Gabriella; Nicoletti, Francesco P.; Smulevich, Giulietta; Fasano, Mauro

    2009-01-01

    Human serum albumin (HSA) participates in heme scavenging; in turn, heme endows HSA with myoglobin-like reactivity and spectroscopic properties. Here, the allosteric effect of ibuprofen on peroxynitrite isomerization to NO3− catalyzed by ferric human serum heme-albumin (HSA-heme-Fe(III)) is reported. Data were obtained at 22.0 °C. HSA-heme-Fe(III) catalyzes peroxynitrite isomerization in the absence and presence of CO2; the values of the second order catalytic rate constant (kon) are 4.1 × 105 and 4.5 × 105 m−1 s−1, respectively. Moreover, HSA-heme-Fe(III) prevents peroxynitrite-mediated nitration of free added l-tyrosine. The pH dependence of kon (pKa = 6.9) suggests that peroxynitrous acid reacts preferentially with the heme-Fe(III) atom, in the absence and presence of CO2. The HSA-heme-Fe(III)-catalyzed isomerization of peroxynitrite has been ascribed to the reactive pentacoordinated heme-Fe(III) atom. In the absence and presence of CO2, ibuprofen impairs dose-dependently peroxynitrite isomerization by HSA-heme-Fe(III) and facilitates the nitration of free added l-tyrosine; the value of the dissociation equilibrium constant for ibuprofen binding to HSA-heme-Fe(III) (L) ranges between 7.7 × 10−4 and 9.7 × 10−4 m. Under conditions where [ibuprofen] is ≫L, the kinetics of HSA-heme-Fe(III)-catalyzed isomerization of peroxynitrite is superimposable to that obtained in the absence of HSA-heme-Fe(III) or in the presence of non-catalytic HSA-heme-Fe(III)-cyanide complex and HSA. Ibuprofen binding impairs allosterically peroxynitrite isomerization by HSA-heme-Fe(III), inducing the hexacoordination of the heme-Fe(III) atom. These results represent the first evidence for peroxynitrite isomerization by HSA-heme-Fe(III), highlighting the allosteric modulation of HSA-heme-Fe(III) reactivity by heterotropic interaction(s), and outlining the role of drugs in modulating HSA functions. The present results could be relevant for the drug-dependent protective role

  13. Neutron single-particle strengths at N=40 , 42: Neutron knockout from Ni68,70 ground and isomeric states

    SciTech Connect

    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.; Lauritsen, T.; Liddick, S. N.; Lunderberg, E.; Noji, S.; Prokop, C.; Stroberg, S. R.; Suchyta, S.; Wimmer, K.; Zhu, S.

    2016-11-28

    The distribution of single-particle strength in 67,69Ni was characterized with one-neutron knockout reactions from intermediate-energy 68,70Ni 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, is used to identify and quantify neutron configurations in the wave functions. While 69Ni compares well to 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. Furthermore, these results suggest that our understanding of the low-lying states in the neutron-rich, semi-magic Ni isotopes may be incomplete and requires further investigation on both the experimental and theoretical sides.

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

    PubMed

    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.

  15. Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH2OH and CD2OH). I. A theoretical study

    NASA Astrophysics Data System (ADS)

    Kamarchik, E.; Rodrigo, C.; Bowman, J. M.; Reisler, H.; Krylov, A. I.

    2012-02-01

    The dissociation of the hydroxymethyl radical, CH2OH, and its isotopolog, CD2OH, following the excitation of high OH stretch overtones is studied by quasi-classical molecular dynamics calculations using a global potential energy surface (PES) fitted to ab initio calculations. The PES includes CH2OH and CH3O minima, dissociation products, and all relevant barriers. Its analysis shows that the transition states for OH bond fission and isomerization are both very close in energy to the excited vibrational levels reached in recent experiments and involve significant geometry changes relative to the CH2OH equilibrium structure. The energies of key stationary points are refined using high-level electronic structure calculations. Vibrational energies and wavefunctions are computed by coupled anharmonic vibrational calculations. They show that high OH-stretch overtones are mixed with other modes. Consequently, trajectory calculations carried out at energies about ˜3000 cm-1 above the barriers reveal that despite initial excitation of the OH stretch, the direct OH bond fission is relatively slow (10 ps) and a considerable fraction of the radicals undergoes isomerization to the methoxy radical. The computed dissociation energies are: D0(CH2OH → CH2O + H) = 10 188 cm-1, D0(CD2OH → CD2O + H) = 10 167 cm-1, D0(CD2OH → CHDO + D) = 10 787 cm-1. All are in excellent agreement with the experimental results. For CH2OH, the barriers for the direct OH bond fission and isomerization are: 14 205 and 13 839 cm-1, respectively.

  16. Proline isomerism leads to multiple folded conformations of calbindin D9k: direct evidence from two-dimensional 1H NMR spectroscopy.

    PubMed Central

    Chazin, W J; Kördel, J; Drakenberg, T; Thulin, E; Brodin, P; Grundström, T; Forsén, S

    1989-01-01

    A complete analysis of calbindin D9k by two-dimensional 1H nuclear magnetic resonance spectroscopy has established the existence of two conformations for the folded protein in solution. Well-resolved major and minor resonances in a ratio of 3:1 are observed throughout the 1H NMR spectrum. Two-dimensional exchange experiments show that the major and minor species are related by an equilibrium process. Analysis of short proton-proton distances along the peptide backbone, identified by two-dimensional nuclear Overhauser effect spectroscopy, provides unambiguous evidence that the two forms of the folded protein differ only in the isomerization state of the peptide bond between Gly-42 and Pro-43. Cis-trans isomerism of Pro-43 is thereby directly identified as the cause of multiple conformations for the folded protein in solution. In addition, when Pro-43 is mutated to a glycine residue there is no indication of multiple conformations. These results provide evidence for the possibility of conformational heterogeneity in the native state of globular proteins. PMID:2928325

  17. 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

    NASA Astrophysics Data System (ADS)

    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.

  18. Energetics of the all-trans{yields}13-cis isomerization of the retinal chromophore of bacteriorhodopsin: Electronic structure calculations for a simple model system

    SciTech Connect

    Woywod, Clemens; Vallet, Valerie; Li, Jingrui; Goerling, Andreas

    2008-12-08

    Understanding the molecular mechanism for the photoinduced transmembrane proton pump in the bacteriorhodopsin system is of fundamental importance. This study attempts to investigate the energetics of the initial step of the proton transport cycle, the photoisomerization of the retinal chromophore. The exact reaction pathway and the question of how many excited electronic states are involved in the internal conversion process are still unresolved. The problem is approached by constructing a reaction coordinate suggested by crystallographic studies for a simplified chromophore model system. The CASSCF and CASPT2 electronic structure methods are employed to calculate the energies of the four lowest lying singlet states as a function of the reaction coordinate. The effect of negatively charged protein residues on the reaction is simulated by inclusion of a negative point charge in the model. The results indicate that trans{yields}cis isomerization around the C{sub {beta}} = C{sub {gamma}} bond may be accompanied by twisting around the C{sub {alpha}}-C{sub {beta}} bond in order to drive the proton pump. The presence of a counterion does not seem to reduce the barrier for isomerization or the S{sub 0}-S{sub 1} energy difference but clearly stabilizes the cis--product. At first sight the results appear to support the idea of a participation of no other electronic states beyond S{sub 0} and first singly {pi}{pi}* excited state in the photoreaction. However, the relevance of this prediction is rather limited because of the small size of the model system. Other states of retinal, corresponding in particular to the partly doubly {pi}{pi}* excited S{sub 2} state of the model, are likely to have a vertical excitation energy similar to the first singly {pi}{pi}* excited state or even below.

  19. 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.

    PubMed

    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.

  20. Coulomb excitation of a Am242 isomeric target: E2 and E3 strengths, rotational alignment, and collective enhancement

    NASA Astrophysics Data System (ADS)

    Hayes, A. B.; Cline, D.; Moody, K. J.; Ragnarsson, I.; Wu, C. Y.; Becker, J. A.; Carpenter, M. P.; Carroll, J. J.; Gohlke, D.; Greene, J. P.; Hecht, A. A.; Janssens, R. V. F.; Karamian, S. A.; Lauritsen, T.; Lister, C. J.; Macri, R. A.; Propri, R.; Seweryniak, D.; Wang, X.; Wheeler, R.; Zhu, S.

    2010-10-01

    A 98% pure 242mAm (K=5-, t1/2=141 years) isomeric target was Coulomb excited with a 170.5-MeV Ar40 beam. The selectivity of Coulomb excitation, coupled with the sensitivity of Gammasphere plus CHICO, was sufficient to identify 46 new states up to spin 18ℏ in at least four rotational bands; 11 of these new states lie in the isomer band, 13 in a previously unknown yrast Kπ=6- rotational band, and 13 in a band tentatively identified as the predicted yrast Kπ=5+ band. The rotational bands based on the Kπ=5- isomer and the 6- bandhead were populated by Coulomb excitation with unexpectedly equal cross sections. The γ-ray yields are reproduced by Coulomb excitation calculations using a two-particle plus rotor model (PRM), implying nearly complete ΔK=1 mixing of the two almost-degenerate rotational bands, but recovering the Alaga rule for the unperturbed states. The degeneracy of the 5- and 6- bands allows for precise determination of the mixing interaction strength V, which approaches the strong-mixing limit; this agrees with the 50% attenuation of the Coriolis matrix element assumed in the model calculations. The fractional admixture of the IKπ=66- state in the nominal 65- isomer band state is measured within the PRM as 45.6-1.1+0.3%. The E2 and M1 strengths coupling the 5- and 6- bands are enhanced significantly by the mixing, while E1 and E2 couplings to other low-K bands are not measurably enhanced. The yields of the 5+ band are reproduced by an E3 strength of ≈15 W.u., competitive with the interband E2 strength. Alignments of the identified two-particle Nilsson states in Am242 are compared with the single-particle alignments in Am241.

  1. Hydroboration/amination of N-trimethylsilyl protected olefinic amines and diolefins: Synthesis of isomerically pure diamines

    SciTech Connect

    Kabalka, G.W.; Zhe Wang )

    1990-01-01

    N-Trimethylsilyl protected olefinic amines and terminal diolefins were hydroborated with dimethylborane and the resulting organoboranes were treated with in situ generated chloramine or chloralkylamines to produce isomerically pure diamines or N-substituted diamines in good yields.

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

    EPA Science Inventory

    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...

  3. Structural and dynamic implications of an effector-induced backbone amide cis-trans isomerization in cytochrome P450cam

    PubMed Central

    Asciutto, Eliana K.; Madura, Jeffry D.; Pochapsky, Susan Sondej; OuYang, Bo; Pochapsky, Thomas C.

    2009-01-01

    Experimental evidence has been provided for a functionally relevant cis-trans isomerization of the Ile 88-Pro 89 peptide bond in cytochrome P450cam (CYP101). The isomerization is proposed to be a key element of the structural reorganization leading to the catalytically competent form of CYP101 upon binding of the effector protein putidaredoxin (Pdx). A detailed comparison of the results of molecular dynamics simulations on the cis and trans conformations of substrate- and carbonmonoxy-bound ferrous CYP101 with sequence-specific Pdx-induced structural perturbations identified by nuclear magnetic resonance is presented, providing insight into the structural and dynamic consequences of the isomerization. The mechanical coupling between the Pdx binding site on the proximal face of CYP101 and the site of isomerization is described. PMID:19327368

  4. Application of Δ- and Λ-Isomerism of Octahedral Metal Complexes for Inducing Chiral Nematic Phases

    PubMed Central

    Sato, Hisako; Yamagishi, Akihiko

    2009-01-01

    The Δ- and Λ-isomerism of octahedral metal complexes is employed as a source of chirality for inducing chiral nematic phases. By applying a wide range of chiral metal complexes as a dopant, it has been found that tris(β-diketonato)metal(III) complexes exhibit an extremely high value of helical twisting power. The mechanism of induction of the chiral nematic phase is postulated on the basis of a surface chirality model. The strategy for designing an efficient dopant is described, together with the results using a number of examples of Co(III), Cr(III) and Ru(III) complexes with C2 symmetry. The development of photo-responsive dopants to achieve the photo-induced structural change of liquid crystal by use of photo-isomerization of chiral metal complexes is also described. PMID:20057959

  5. Ultrashort IR Laser Pulse Isomerization Of All-Trans Retinal To 11 CIS Retinal

    NASA Astrophysics Data System (ADS)

    Taboada, J.; Liegner, J.; Tsin, A. T.

    1987-01-01

    The mammalian ocular system possesses a significant IR transmission window between the longest visually detectable light wavelength at 700 nm and the cut off water absorption band at 1400 nm. This near IR optical band may provide a channel for controlling vision processes. Of particular interest is the regeneration process which involves the re -Wmerization of all-trans retinal to 11-cis retinal and the molecular recoupling of retinal with opsin.". This re-isomerization, moving against potential energy gradient, is the rate limiting step is assumed to involve either a vitamin A intermediate or a directly applied enzyme, "isomerase"). The concept investigated in this study concerns the possibility of directly influencing the isomerization process by ultrashort IR laser pulses.

  6. Synthesis and optical properties of isomeric branched pi-conjugated systems.

    PubMed

    Nierengarten, Jean-François; Zhang, Sheng; Gégout, Aline; Urbani, Maxence; Armaroli, Nicola; Marconi, Giancarlo; Rio, Yannick

    2005-09-16

    [structure: see text] Branched conjugated systems with a terminal alkyne function have been prepared starting from 4-(triisopropylsilylethynyl) phenylacetylene by applying the following iterative reaction sequence: (i) metal-catalyzed cross-coupling reaction of the terminal alkyne with 3,4-dibromobenzaldehyde or 2,5- dibromobenzaldehyde; (ii) Corey-Fuchs dibromoolefination and treatment with an excess of LDA. The building blocks thus prepared have been subjected to a Pd-catalyzed cross-coupling reaction with 1,4-diiodobenzene to yield isomeric branched pi-conjugated systems containing 7 (first generation) or 15 (second generation) phenyl units connected by ethynyl spacers. The different pi-conjugation patterns in those isomeric derivatives have a dramatic effect on their electronic properties, as attested by the differences observed in their absorption and emission spectra. Finally, theoretical calculations have been performed to rationalize the optical properties of these compounds.

  7. Ethanol production from xylose by enzymic isomerization and yeast fermentation. [Schizosaccharomyces pombe

    SciTech Connect

    Chiang, L.C.; Hsiao, H.Y.; Ueng, P.P.; Chen, L.F.; Tsao, G.T.

    1981-01-01

    Repetitive enzymic isomerization of xylose followed by yeast fermentation of xylulose, and simultaneous enzymic isomerization and yeast fermentation, were proven to be methods capable of converting xylose to EtOH. The fermentation product (EtOH, xylitol, or glycerol) has little inhibitory or deactivation effect on the activity of isomerase. In a comparison of the ability of yeasts to ferment xylulose to EtOH, Schizosaccharomyces pombe was found to be superior to industrial bakers' yeast. Under optimal conditions (pH 6, temperature 30 degrees), a final EtOH concentration of 6.3% was obtained from simulated hemicellulose hydrolyzate using a simultaneous fermentation process. The EtOH yield was more than 80% of theoretical.

  8. A kinetic study on the isomerization of hop alpha-acids.

    PubMed

    Jaskula, Barbara; Kafarski, Pawel; Aerts, Guido; De Cooman, Luc

    2008-08-13

    In this article, a detailed study on hop alpha-acid isomerization kinetics is presented. Because of the complex wort matrix and interfering interactions occurring during real wort boiling (i.e., trub formation and alpha-acids/iso-alpha-acids complexation), this investigation on alpha-acid isomerization kinetics was performed in aqueous buffer solution as a function of time (0-90 min) and heating temperature (80-100 degrees C). Rate constants and activation energies for the formation of individual iso-alpha-acids were determined. It was found that iso-alpha-acid formation follows first-order kinetics and Arrhenius behavior. Differences in activation energies for the formation of trans- and cis-isomers were noticed, the activation energy for the formation of trans-iso-alpha-acids being approximately 9 kJmol (-1) lower.

  9. Experimental study of water-ice catalyzed thermal isomerization of cyanamide into carbodiimide: implication for prebiotic chemistry.

    PubMed

    Duvernay, Fabrice; Chiavassa, Thierry; Borget, Fabien; Aycard, Jean-Pierre

    2004-06-30

    Cyanamide (NH2CN) is a molecule of interstellar interest which can be implied in prebiotic chemistry. We showed, by FTIR spectroscopy, that cyanamide can be isomerized in carbodiimide (HNCNH), another interstellar relevant molecule, by a reaction involving the amorphous water-ice surface as catalyst. This isomerization occurs at low temperature (T < 100 K) which agrees quite well with that expected in the interstellar clouds composed of dust grains in which water is the most predominant constituent.

  10. Large-amplitude dynamics in vinyl radical: the role of quantum tunneling as an isomerization mechanism.

    PubMed

    Sharma, Amit R; Bowman, Joel M; Nesbitt, David J

    2012-01-21

    We report tunneling splittings associated with the large amplitude 1,2 H-atom migration to the global minima in the vinyl radical. These are obtained using a recent full-dimensional ab initio potential energy surface (PES) [A. R. Sharma, B. J. Braams, S. Carter, B. C. Shepler, and J. M. Bowman, J. Chem. Phys. 130(17), 174301 (2009)] and independently, directly calculated "reaction paths." The PES is a multidimensional fit to coupled cluster single and double and perturbative treatment of triple excitations coupled-cluster single double triple (CCSD(T)) with the augmented correlation consistent triple zeta basis set (aug-cc-pVTZ). The reaction path potentials are obtained from a series of CCSD(T)/aug-cc-pVnTZ calculations extrapolated to the complete basis set limit. Approximate 1D calculations of the tunneling splitting for these 1,2-H atom migrations are obtained using each of these potentials as well as quite different 1D Hamiltonians. The splittings are calculated over a large energy ranges, with results from the two sets of calculations in excellent agreement. Though negligibly slow (>1 s) for the vibrational ground state, this work predicts tunneling-promoted 1,2 hydride shift dynamics in vinyl to exhibit exponential growth with internal vibrational excitation, specifically achieving rates on the sub-μs time scale at energies above E ≈ 7500 cm(-1). Most importantly, these results begin to elucidate the possible role of quantum isomerization through barriers without dissociation, in competition with the more conventional picture of classical roaming permitted over a much narrower window of energies immediately below the bond dissociation limit. Furthermore, when integrated over a Boltzmann distribution of thermal energies, these microcanonical tunneling rates are consistent with sub-μs time scales for 1,2 hydride shift dynamics at T > 1400 K. These results have potential relevance for combustion modeling of low-pressure flames, as well as recent

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

    PubMed

    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.

  12. Proline Isomerization of the Immune Receptor-Interacting Protein RIN4 by a Cyclophilin Inhibits Effector-Triggered Immunity in Arabidopsis

    PubMed Central

    Li, Meng; Ma, Xiqing; Chiang, Yi-Hsuan; Yadeta, Koste A.; Ding, Pengfei; Dong, Liansai; Zhao, Yan; Li, Xiuming; Yu, Yufei; Zhang, Ling; Shen, Qian-Hua; Xia, Bin; Coaker, Gitta; Liu, Dong; Zhou, Jian-Min

    2016-01-01

    SUMMARY In the absence of pathogen infection, plant effector-triggered immune (ETI) receptors are maintained in a preactivation state by intermolecular interactions with other host proteins. Pathogen effector-induced alterations activate the receptor. In Arabidopsis, the ETI receptor RPM1 is activated via bacterial effector AvrB-induced phosphorylation of the RPM1-interacting protein RIN4 at Threonine 166. We find that RIN4 also interacts with the prolyl-peptidyl isomerase (PPIase) ROC1, which is reduced upon RIN4 Thr166 phosphorylation. ROC1 suppresses RPM1 immunity in a PPIase-dependent manner. Consistent with this, RIN4 Pro149 undergoes cis/trans isomerization in the presence of ROC1. While the RIN4P149V mutation abolishes RPM1 resistance, the deletion of Pro149 leads to RPM1 activation in the absence of RIN4 phosphorylation. These results support a model in which RPM1 directly senses conformational changes in RIN4 surrounding Pro149 that is controlled by ROC1. RIN4 Thr166 phosphorylation indirectly regulates RPM1 resistance by modulating the ROC1-mediated RIN4 isomerization. PMID:25299333

  13. Theoretical study on the isomeric structures and the stability of silylenoid (Tsi)Cl2SiLi (Tsi = C(SiMe3)3).

    PubMed

    Xie, Ju; Feng, Dacheng; Feng, Shengyu

    2006-06-01

    The structures and isomerization of silylenoid (Tsi)Cl(2)SiLi (Tsi = C(SiMe(3))(3)) were studied by density functional theory (DFT) at the B3LYP/6-31G(d) level. Four equilibrium structures and three isomeric transition states were located. The three-membered ring and p-complex structures, 1 and 2, are the two most stable forms. Two other local minima, the sigma-complex 3 and tetrahedron structure 4, should rearrange to 1 with very low barriers, and then to the most stable isomer 2. To exploit further the stability of silylenoid (Tsi)Cl(2)SiLi, the insertion reactions of 2 and silylene (Tsi)ClSi into the HF molecule have been investigated at the B3LYP/6-31G(d) level, respectively. The results show that the insertion of 2 into HF is very similar to that of (Tsi)ClSi into HF, but the latter is more favorable. To probe the influence of the substituent Tsi on the stability of silylenoid (Tsi)Cl(2)SiLi, the isomers and insertion reaction of silylenoid CH(3)Cl(2)SiLi were investigated in a similar way of those with (Tsi)Cl(2)SiLi. The results indicate that silylenoid containing very bulky group Tsi exhibits unusual stability because of the severe steric hindrance produced by Tsi at the center to which it is attached.

  14. A Cascade Isomerization/Prins Strategy through Iridium(III)/Brønsted Acid Cooperative Catalysis**

    PubMed Central

    Lombardo, Vince M.; Thomas, Christopher D.; Scheidt, Karl A.

    2014-01-01

    A mild and efficient isomerization/protonation sequence involving an appropriately functionalized indole precursor to generate a wide variety of pyran-fused indoles utilizing cooperative catalysis between cationic iridium (III) and bismuth triflate has been developed. Three distinct cyclization manifolds lead to bioactive scaffolds that can be obtained in good yields. In addition, N-substituted indoles can be synthesized enantioselectively via an oxocarbenium• chiral phosphate counterion strategy. PMID:24218144

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Catalytic cascade hydroalkoxylation/isomerization/ [4 + 2] cycloaddition using enyne alcohols as latent dienes or dienophiles.

    PubMed

    Guo, Rui; Li, Kang-Nan; Gong, Liu-Zhu

    2013-10-21

    Enyne alcohols can react as precursors of either dienes or dienophiles with different substrates after hydroxylation and isomerization by gold catalysis. As such, oxa-bridged tricyclo[5.2.2.02,6]-undec-8-ene-3,5-dione derivatives have been obtained by the Diels–Alder reaction and tetrahydro-1H-furo[3,4-c]pyran derivatives could be accessed by the hetero-Diels–Alder cycloaddition.

  17. Simulation of chemical isomerization reaction dynamics on a NMR quantum simulator.

    PubMed

    Lu, Dawei; Xu, Nanyang; Xu, Ruixue; Chen, Hongwei; Gong, Jiangbin; Peng, Xinhua; Du, Jiangfeng

    2011-07-08

    Quantum simulation can beat current classical computers with minimally a few tens of qubits. Here we report an experimental demonstration that a small nuclear-magnetic-resonance quantum simulator is already able to simulate the dynamics of a prototype laser-driven isomerization reaction using engineered quantum control pulses. The experimental results agree well with classical simulations. We conclude that the quantum simulation of chemical reaction dynamics not computable on current classical computers is feasible in the near future.

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

    PubMed

    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.

  19. Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water

    SciTech Connect

    Roman-Leshkov, Yuriy; Moliner, Manuel; Labinger, J. A.; Davis, Mark E.

    2010-10-20

    1H and 13C NMR spectroscopy on isotopically labeled glucose reveals that in the presence of tin-containing zeolite Sn-Beta, the isomerization reaction of glucose in water proceeds by way of an intramolecular hydride shift rather than proton transfer. This is the first mechanistic demonstration of Sn-Beta acting as a Lewis acid in a purely aqueous environment.

  20. A classical trajectory study of the dissociation and isomerization of C2H5.

    PubMed

    Wagner, Albert F; Rivera-Rivera, Luis A; Bachellerie, Damien; Perry, Jamin W; Thompson, Donald L

    2013-11-21

    Motivated by photodissociation experiments in which non-RRKM nanosecond lifetimes of the ethyl radical were reported, we have performed a classical trajectory study of the dissociation and isomerization of C2H5 over the energy range 100-150 kcal/mol. We used a customized version of the AIREBO semiempirical potential (Stuart, S. J.; et al. J. Chem. Phys. 2000, 112, 6472-6486) to more accurately describe the gas-phase decomposition of C2H5. This study constitutes one of the first gas-phase applications of this potential form. At each energy, 10,000 trajectories were run and all underwent dissociation in less than 100 ps. The calculated dissociation rate constants are consistent with RRKM models; no evidence was found for nanosecond lifetimes. An analytic kinetics model of isomerization/dissociation competition was developed that incorporated incomplete mode mixing through a postulated divided phase space. The fits of the model to the trajectory data are good and represent the trajectory results in detail through repeated isomerizations at all energies. The model correctly displays single exponential decay at lower energies, but at higher energies, multiexponential decay due to incomplete mode mixing becomes more apparent. At both ends of the energy range, we carried out similar trajectory studies on CD2CH3 to examine isotopic scrambling. The results largely support the assumption that a H or a D atom is equally likely to dissociate from the mixed-isotope methyl end of the molecule. The calculated fraction of products that have the D atom dissociation is ∼20%, twice the experimental value available at one energy within our range. The calculated degree of isotopic scrambling is non-monotonic with respect to energy due to a non-monotonic ratio of the isomerization to dissociation rate constants.

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

    NASA Astrophysics Data System (ADS)

    Denis-Petit, D.; Roig, O.; Méot, V.; Jandel, M.; Vieira, D. J.; Bond, E. M.; Bredeweg, T. A.; Couture, A. J.; Haight, R. C.; Keksis, A. L.; Rundberg, R. S.; Ullmann, J. L.

    2016-03-01

    The isomeric ratio for the neutron capture reaction 176Lu(n,γ) on the Jπ= 5/2-, 761.7 keV, T1/2=32.8 ns level of 177mLu, has been determined in the neutron energy range 8.5 eV-100 keV for the first time using the DANCE array at the Los Alamos National Laboratory.

  2. Qualification of a Quantitative Method for Monitoring Aspartate Isomerization of a Monoclonal Antibody by Focused Peptide Mapping.

    PubMed

    Cao, Mingyan; Mo, Wenjun David; Shannon, Anthony; Wei, Ziping; Washabaugh, Michael; Cash, Patricia

    Aspartate (Asp) isomerization is a common post-translational modification of recombinant therapeutic proteins that can occur during manufacturing, storage, or administration. Asp isomerization in the complementarity-determining regions of a monoclonal antibody may affect the target binding and thus a sufficiently robust quality control method for routine monitoring is desirable. In this work, we utilized a liquid chromatography-mass spectrometry (LC/MS)-based approach to identify the Asp isomerization in the complementarity-determining regions of a therapeutic monoclonal antibody. To quantitate the site-specific Asp isomerization of the monoclonal antibody, a UV detection-based quantitation assay utilizing the same LC platform was developed. The assay was qualified and implemented for routine monitoring of this product-specific modification. Compared with existing methods, this analytical paradigm is applicable to identify Asp isomerization (or other modifications) and subsequently develop a rapid, sufficiently robust quality control method for routine site-specific monitoring and quantitation to ensure product quality. This approach first identifies and locates a product-related impurity (a critical quality attribute) caused by isomerization, deamidation, oxidation, or other post-translational modifications, and then utilizes synthetic peptides and MS to assist the development of a LC-UV-based chromatographic method that separates and quantifies the product-related impurities by UV peaks. The established LC-UV method has acceptable peak specificity, precision, linearity, and accuracy; it can be validated and used in a good manufacturing practice environment for lot release and stability testing.

  3. Differences in sequence selectivity of DNA alkylation by isomeric intercalating aniline mustards.

    PubMed

    Prakash, A S; Denny, W A; Wakelin, L P

    1990-01-01

    Two DNA-targeted mustard derivatives, N,N-bis(2-chloroethyl)-4-(5-[9-acridinylamino]-pentamido)aniline and 4-(9-[acridinylamino]butyl 4-(N,N-bis[2-chloroethyl]-aminobenzamide, which are isomeric compounds where the mustard is linked to the DNA-binding 9-aminoacridine moiety by either a -CONH- or a -NHCO- group, show significant differences in the sequence selectivity of their alkylation of DNA. The CONH isomer is a more efficient alxylating agent than the NHCO compound by an order of magnitude, consistent with the larger electron release of the CONH group to the aniline ring. However, the pattern of alkylation by the two compounds is also very different, with the CONH isomer preferring alkylation of guanines adjacent to 3'- or 5'-adenines and cytosines (for example those in sequences 5'-CGC, 5'-AGC, 5'-CGG and 5'-AGA) while the isomeric NHCO compound shows preference for guanines in runs of Gs. In addition, both isomers alkylate 3'-adenines in runs of adenines. Both compounds also show completely different patterns of alkylation to their untargeted mustard counterparts, since 4-MeCONH-aniline mustard alkylates all guanines and adenines in runs of adenines, while 4-Me2NCO-aniline mustard fails to alkylate DNA at all. These differences in alkylation patterns between the CONH- and its isomeric NHCO- compounds and their relationships between the alkylation patterns of the isomers and their biological activities are discussed.

  4. An in vivo pathway for disulfide bond isomerization in Escherichia coli.

    PubMed

    Rietsch, A; Belin, D; Martin, N; Beckwith, J

    1996-11-12

    Biochemical studies have shown that the periplasmic protein disulfide oxidoreductase DsbC can isomerize aberrant disulfide bonds. Here we present the first evidence for an in vivo role of DsbC in disulfide bond isomerization. Furthermore, our data suggest that the enzymes DsbA and DsbC play distinct roles in the cell in disulfide bond formation and isomerization, respectively. We have shown that mutants in dsbC display a defect in disulfide bond formation specific for proteins with multiple disulfide bonds. The defect can be complemented by the addition of reduced dithiothreitol to the medium, suggesting that absence of DsbC results in accumulation of misoxidized proteins. Mutations in the dipZ and trxA genes have similar phenotypes. We propose that DipZ, a cytoplasmic membrane protein with a thioredoxin-like domain, and thioredoxin, the product of the trxA gene, are components of a pathway for maintaining DsbC active as a protein disulfide bond isomerase.

  5. Geometrical isomerization of carotenoids mediated by cation radical/dication formation

    SciTech Connect

    Gao, G.; Wei, C.C.; Jeevarajan, A.S.; Kispert, L.D.

    1996-03-28

    Electrochemical oxidation of all-trans-canthaxanthin and {beta}-carotene in dichloromethane leads to significant trans-to-cis isomerization, with cis isomers accounting for about 40% of the products formed. The electrochemically generated isomers were separated by reverse-phase high-performance liquid chromatography and identified as 9-cis, 13-cis, 15-cis, and 9,13-di-cis isomers of the carotenoids by {sup 1}H-NMR spectroscopy and optical spectroscopy (Q ratio). The results of simultaneous bulk electrolysis and optical absorption spectroscopy indicate the following isomerization mechanism: the all-trans cation radicals and/or dications formed by electrochemical oxidation of all-trans-carotenoids can easily undergo geometrical isomerization to form cis cation radicals and/or dications. The latter are converted by the comproportionation equilibrium to cation radicals which are then transformed to neutral cis-carotenoids by exchanging one electron with neutral carotenoids. AM1 molecular orbital calculations, which show that the energy barriers of configurational transformation from trans to cis are much lower in the cation radical and dication species than in the neutral molecule, strongly support the first step of this mechanism. 36 refs., 5 figs., 2 tabs.

  6. A dynamics prediction of nitromethane → methyl nitrite isomerization in external electric field.

    PubMed

    Ren, Fu-de; Cao, Duan-lin; Shi, Wen-jing

    2016-04-01

    As a follow-up to our investigation into the effect of external electric field on the chemical bond strength, the effects of external electric field on the CH3NO2 → CH3ONO isomerization dynamics were investigated using the MP2/6-311++G(2d,p) and CCSD/6-311++G(2d,p) methods. The rate constants in the absence and presence of various field strengths were calculated. The results show that, when the field strength is larger than +0.0060 a.u. along the C-NO2 bond axis, the barriers of the isomerization are lower than the C-NO2 bond dissociation energies, leading to the preferences of the isomerization over the C-NO2 bond dissociation. In this case, the sensitivities are higher than that in no field. However, in the other fields, the C-NO2 bond scission is favored and the sensitivities are almost equal to that in no field. Several good linear correlations are found between the field strengths and the changes of the bond lengths or corresponding electron densities.

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

    PubMed

    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).

  8. Human infrared vision is triggered by two-photon chromophore isomerization.

    PubMed

    Palczewska, Grazyna; Vinberg, Frans; Stremplewski, Patrycjusz; Bircher, Martin P; Salom, David; Komar, Katarzyna; Zhang, Jianye; Cascella, Michele; Wojtkowski, Maciej; Kefalov, Vladimir J; Palczewski, Krzysztof

    2014-12-16

    Vision relies on photoactivation of visual pigments in rod and cone photoreceptor cells of the retina. The human eye structure and the absorption spectra of pigments limit our visual perception of light. Our visual perception is most responsive to stimulating light in the 400- to 720-nm (visible) range. First, we demonstrate by psychophysical experiments that humans can perceive infrared laser emission as visible light. Moreover, we show that mammalian photoreceptors can be directly activated by near infrared light with a sensitivity that paradoxically increases at wavelengths above 900 nm, and display quadratic dependence on laser power, indicating a nonlinear optical process. Biochemical experiments with rhodopsin, cone visual pigments, and a chromophore model compound 11-cis-retinyl-propylamine Schiff base demonstrate the direct isomerization of visual chromophore by a two-photon chromophore isomerization. Indeed, quantum mechanics modeling indicates the feasibility of this mechanism. Together, these findings clearly show that human visual perception of near infrared light occurs by two-photon isomerization of visual pigments.

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

    PubMed

    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.

  10. Kinetic analysis for the isomerization of cellobiose to cellobiulose in subcritical aqueous ethanol.

    PubMed

    Soisangwan, Nontanut; Gao, Da-Ming; Kobayashi, Takashi; Khuwijitjaru, Pramote; Adachi, Shuji

    2016-10-04

    The isomerization of cellobiose to cellobiulose, and other degradation reactions of cellobiose were investigated in subcritical aqueous ethanol with concentrations of ethanol ranging from 0 to 60% (w/w) and at temperatures ranging from 170 to 200 °C. The maximum yield of cellobiulose (ca. 40%) was obtained from the treatment of cellobiose in 60% (w/w) aqueous ethanol at 190 °C. Glucose and fructose were also detected as byproducts. The concentration-time integral method was employed to analyze the rate constants for the isomerization and degradation processes. The rate constant of cellobiose isomerization to cellobiulose was greater than those of the degradation reactions under all experimental conditions, and it increased significantly with treatment temperature and ethanol concentration. However, the use of higher temperatures and ethanol concentrations was restricted due to decomposition of the saccharides and the low solubility of cellobiose, respectively. The effect of initial feed concentration (0.5-5.5% w/w) was also studied. The maximum productivity of cellobiulose, 54.1 kg/(h m(3)-reactor), was accomplished at a feed concentration of 5.5% (w/w) in 20% (w/w) subcritical aqueous ethanol.

  11. Human infrared vision is triggered by two-photon chromophore isomerization

    PubMed Central

    Palczewska, Grazyna; Vinberg, Frans; Stremplewski, Patrycjusz; Bircher, Martin P.; Salom, David; Komar, Katarzyna; Zhang, Jianye; Cascella, Michele; Wojtkowski, Maciej; Kefalov, Vladimir J.; Palczewski, Krzysztof

    2014-01-01

    Vision relies on photoactivation of visual pigments in rod and cone photoreceptor cells of the retina. The human eye structure and the absorption spectra of pigments limit our visual perception of light. Our visual perception is most responsive to stimulating light in the 400- to 720-nm (visible) range. First, we demonstrate by psychophysical experiments that humans can perceive infrared laser emission as visible light. Moreover, we show that mammalian photoreceptors can be directly activated by near infrared light with a sensitivity that paradoxically increases at wavelengths above 900 nm, and display quadratic dependence on laser power, indicating a nonlinear optical process. Biochemical experiments with rhodopsin, cone visual pigments, and a chromophore model compound 11-cis-retinyl-propylamine Schiff base demonstrate the direct isomerization of visual chromophore by a two-photon chromophore isomerization. Indeed, quantum mechanics modeling indicates the feasibility of this mechanism. Together, these findings clearly show that human visual perception of near infrared light occurs by two-photon isomerization of visual pigments. PMID:25453064

  12. Characteristic structural features of indolicidin: effects of the cis-trans isomerism on its conformation.

    PubMed

    Leitgeb, Balázs

    2014-01-01

    Indolicidin is an antimicrobial peptide showing a broad spectrum of antibacterial and antifungal activities, and according to the cis-trans isomerism of three Xaa-Pro peptide bonds, eight different stereoisomers could be distinguished for this peptide. As the cis-trans isomerism about the Xaa-Pro peptide bonds was not considered in previous studies, the structural features of distinct stereoisomeric forms were not characterized in detail, so far. In this theoretical study, the influences of cis-trans isomerism on the conformation of indolicidin were investigated, as well as the typical structural properties of each stereoisomer were determined, focusing on the secondary structures and intramolecular interactions. Based on the results derived from the molecular dynamics simulations, it could be concluded that the eight different stereoisomeric forms of indolicidin adopted characteristic conformational features. Nevertheless, the appearance of various turn structures and intramolecular interactions proved to be dependent on the cis or trans nature of Xaa-Pro peptide bonds, indicating the relevant role of Pro amino acids in determining the three-dimensional structure of this peptide.

  13. New insights on molybdenum suboxide: nature of carbons in isomerization reactions.

    PubMed

    Torres-García, Enelio; Rodríguez-Gattorno, Geonel; Ascencio, Jorge A; Aleman-Vazquez, Laura O; Cano-Domínguez, José L; Martínez-Hernandez, Angel; Santiago-Jacinto, Patricia

    2005-09-22

    MoO3 transformations under isomerization process conditions were studied. The products obtained after different times under stream (H2/n-heptane mixture, 18.5 bar, at 370 degrees C) were characterized by X-ray diffraction, Raman spectroscopy, thermal analysis, and high-resolution transmission electron microscopy (HRTEM). Theoretical quantum calculations were carried out with the aim of understanding the paradox of the real active phase in isomerization reactions. Theoretical calculations predict the existence of a metallic-like MoO phase with a structure that matches the X-ray diffraction experimental results. From experimental and simulated HRTEM images it was possible to identify the presence of small MoO cubic crystallites inside MoOx matrix phases. These results also support the previously proposed idea that isomerization reactions take place as a result of the existence of a bifunctional catalyst. The Raman and thermo-programmed oxidation (TPO) analyses show the existence of at least two types of carbonaceous deposits which tend to increase its ordering with the increase of time under stream. The carbon K edge in electron energy loss spectroscopy (EELS) of a sample after 24 h under stream shows that these carbonaceous deposits consist of a mixture of sp2- and sp3-hybridized carbons.

  14. DFT investigation of the mechanism of E/Z isomerization of nitrones.

    PubMed

    Roca-López, David; Tejero, Tomás; Merino, Pedro

    2014-09-05

    The hitherto unknown mechanism of E/Z isomerization of nitrones, with important implications in 1,3-dipolar cycloaddition chemistry, has been investigated using density functional theory calculations. Unimolecular and bimolecular processes have also been considered. Both concerted and stepwise mechanisms involving either zwitterionic or diradical species have been studied. The unimolecular torsional mechanism and isomerization through intermediate oxaziridines present energy barriers too high to justify the observed experimental results. Several bimolecular processes involving an initial dimerization are possible. Among them, the concerted process can be discarded in terms of energy barrier. Zwitterionic intermediates are too high in energy to be considered. From the two possible diradical approaches consisting of either C-O or C-C coupling, the latter is the most favored. Thus, the mechanism of E/Z isomerization of nitrones proceeds via a diradical bimolecular process involving an initial dimerization through a C-C coupling followed by a dedimerization, with energy barriers for the rate-limiting step of 29.9 kcal/mol for C-methyl nitrones and 25.8 kcal/mol for C-(methoxycarbonyl) nitrones. These values are in very good agreement with the experimental data previously measured through kinetic experiments.

  15. Isomerization and Aggregation of the Solar Cell Dye D149

    PubMed Central

    2012-01-01

    D149, a metal-free indoline dye, is one of the most promising sensitizers for dye-sensitized solar cells (DSSCs) and has shown very high solar energy conversion efficiencies of 9%. Effective electron injection from the excited state is a prerequisite for high efficiencies and is lowered by competing deactivation pathways. Previous investigations have shown surprisingly short-lived excited states for this dye, with maximum lifetime components of 100–720 ps in different solvents and less than 120 ps for surface-adsorbed D149. Using steady-state and time-resolved fluorescence, we have investigated the photochemical properties of D149 in nonpolar and polar solvents, polymer matrices, and adsorbed on ZrO2, partially including a coadsorbent. In solution, excitation to the S2 state yields a product that is identified as a photoisomer. The reaction is reversible, and the involved double-bond is identified by NMR spectroscopy. Our results further show that lifetimes of 100–330 ps in the solvents used are increased to more than 2 ns for D149 in polymer matrices and on ZrO2. This is in part attributed to blocked internal motion due to steric constraint. Conversely, concentration-dependent aggregation leads to a dramatic reduction in lifetimes that can affect solar cell performance. Our results explain the unexpectedly short lifetimes observed previously. We also show that photochemical properties such as lifetimes determined in solution are different from the ones determined on semiconductor surfaces used in solar cells. The obtained mechanistic understanding should help develop design strategies for further improvement of solar cell dyes. PMID:23378868

  16. A Crystallographic Study of Bright Far-Red Fluorescent Protein mKate Reveals pH-induced cis-trans Isomerization of the Chromophore

    SciTech Connect

    Pletnev, Sergei; Shcherbo, Dmitry; Chudakov, Dmitry M.; Pletneva, Nadezhda; Merzlyak, Ekaterina M.; Wlodawer, Alexander; Dauter, Zbigniew; Pletnev, Vladimir

    2008-11-03

    The far-red fluorescent protein mKate {lambda}{sup ex}, 588 nm; {lambda}{sub em}, 635 nm; chromophore-forming triad Met{sup 63}-Tyr{sup 64}-Gly{sup 65}, originating from wild-type red fluorescent progenitor eqFP578 (sea anemone Entacmaea quadricolor), is monomeric and characterized by the pronounced pH dependence of fluorescence, relatively high brightness, and high photostability. The protein has been crystallized at a pH ranging from 2 to 9 in three space groups, and four structures have been determined by x-ray crystallography at the resolution of 1.75--2.6 {angstrom}. The pH-dependent fluorescence of mKate has been shown to be due to reversible cis-trans isomerization of the chromophore phenolic ring. In the non-fluorescent state at pH 2.0, the chromophore of mKate is in the trans-isomeric form. The weakly fluorescent state of the protein at pH 4.2 is characterized by a mixture of trans and cis isomers. The chromophore in a highly fluorescent state at pH 7.0/9.0 adopts the cis form. Three key residues, Ser{sup 143}, Leu{sup 174}, and Arg{sup 197} residing in the vicinity of the chromophore, have been identified as being primarily responsible for the far-red shift in the spectra. A group of residues consisting of Val{sup 93}, Arg{sup 122}, Glu{sup 155}, Arg{sup 157}, Asp{sup 159}, His{sup 169}, Ile{sup 171}, Asn{sup 173}, Val{sup 192}, Tyr{sup 194}, and Val{sup 216}, are most likely responsible for the observed monomeric state of the protein in solution.

  17. Isomerization and fragmentation of acetonitrile upon interaction with N(4S) atoms: the chemistry of nitrogen in dense molecular clouds

    NASA Astrophysics Data System (ADS)

    Mencos, Alejandro; Krim, Lahouari

    2016-08-01

    We experimentally show that the reaction between ground state nitrogen atoms N(4S) and acetonitrile CH3CN can lead to two distinct chemical pathways that are both thermally activated at very low temperatures. First is CH3CN isomerization which produces CH3NC and H2CCNH. Second is CH3CN decomposition which produces HNC and CH3CNH+CN- fragments, with the possible release of H2. Our results reveal that the mobility of N(4S)-atoms is stimulated in the 3-11 K temperature range, and that its subsequent encounter with one acetonitrile molecule is sufficient for the aforementioned reactions to occur without the need for additional energy to be supplied to the CH3CN + N(4S) system. These findings shed more light on the nitrogen chemistry that can possibly take place in dense molecular clouds, which until now was thought to only involve high-energy processes and therefore be unlikely to occur in such cold and dark interstellar regions. The reaction pathways we propose in this study have very important astrochemical implications, as it was shown recently that the atomic nitrogen might be more abundant, in many interstellar icy grain mantles, than previously thought. Also, these reaction pathways can now be considered within dense molecular clouds, and possibly affect the branching ratios for N-bearing molecules computed in astrochemical modelling.

  18. Advances in Tagging Methods for Lifetimes of Isomeric- and Proton-Unbound States

    SciTech Connect

    Cullen, D. M.

    2008-11-11

    This paper summarises the programme of Recoil-isomer tagging that has been performed over the last ten years at the University of Jyvaeskylae, Finland. The nuclei studied lie in the mass 130-140 region of the Segre chart very close to the proton drip line. The evolution of the isomer character is seen to change from K-isomers, at N = 74, to shape-isomers in the gamma soft N = 77 nuclei to seniority-isomers around N = 82. The influence of the proton drip line on the N = 74 isomers and possible critical-point symmetries in the N = 77 nuclei are discussed and the latest results presented. Developments of the isomer-tagging technique, using large beam currents with a dual Multi-Wire Proportional Counter setup, and an Isomer-tagged Differential-Plunger setup are discussed along with a future programme of work at Jyvaeskylae.

  19. N+1 Engineering of an Aspartate Isomerization Hotspot in the Complementarity-Determining Region of a Monoclonal Antibody.

    PubMed

    Patel, Chetan N; Bauer, Scott P; Davies, Julian; Durbin, Jim D; Shiyanova, Tatiyana L; Zhang, Kai; Tang, Jason X

    2016-02-01

    Aspartate (Asp) isomerization is a common degradation pathway and a potential critical quality attribute that needs to be well characterized during the optimization and development of therapeutic antibodies. A putative Asp-serine (Ser) isomerization motif was identified in the complementarity-determining region of a humanized monoclonal antibody and shown to be a developability risk using accelerated stability analyses. To address this issue, we explored different antibody engineering strategies. Direct engineering of the Asp residue resulted in a greater than 5× loss of antigen-binding affinity and bioactivity, indicating a critical role for this residue. In contrast, rational engineering of the Ser residue at the n+1 position had a negligible impact on antigen binding affinity and bioactivity compared with the parent molecule. Furthermore, the n+1 engineering strategy effectively eliminated Asp isomerization as determined by accelerated stability analysis. This outcome affirms that the rate of Asp isomerization is strongly dependent on the identity of the n+1 residue. This report highlights a systematic antibody engineering strategy for mitigating an Asp isomerization developability risk during lead optimization.

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

    PubMed

    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.

  1. Molecular Structures of Isomeric Ortho, Meta, and Para Bromo-Substituted α-Methylsulfonyl-α-diethoxyphosphoryl Acetophenones by X-ray and DFT Molecular Orbital Calculations.

    PubMed

    Rodrigues, Alessandro; Olivato, Paulo R; Zukerman-Schpector, Julio; Maganhi, Stella H; Reis, Adriana K C A; Tiekink, Edward R T

    2015-08-13

    The X-ray single crystal analysis of isomeric ortho, meta, and para bromo-substituted α-methylsulfonyl-α-diethoxyphosphoryl acetophenones showed that this class of compound adopts synclinal (gauche) conformations for both [-P(O)(OEt)2] and [-S(O)2Me] groups, with respect to the carbonyl functional group. The phosphonate, sulfonyl, and carbonyl functional groups are joined through an intramolecular network of attractive interactions, as detected by molecular orbital calculations at the M06-2X/6-31G(d,p) level. These interactions are responsible for the more stable conformations in the gas phase, which also persist in the solid-state structures. The main structural distinction in the title compounds relates to the torsion angle of the aryl group (with respect to the carbonyl group), which gives rise to different interactions in the crystal packing, due to the different positions of the Br atom.

  2. Spectroscopic identification of isomeric jet-cooled benzyl-type radicals formed from 3-fluoro-o-xylene by corona discharge

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Chae, Sang Youl; Lee, Sang Kuk

    2013-10-01

    By means of a pinhole-type glass nozzle designed for supersonic jet expansion along with corona discharge, vibronically excited but jet-cooled isomeric benzyl-type radicals were generated from the precursor 3-fluoro-o-xylene. The visible vibronic emission spectrum was recorded from the discharge system with a long-path monochromator. From an analysis of the spectrum observed, we identified the formation of two isomers, 2-methyl-3-fluorobenzyl and 2-methyl-6-fluorobenzyl radicals in the corona discharge of precursor, and determined for the first time the electronic energy in the D1 → D0 transition and vibrational mode frequencies in the D0 state for both isomers.

  3. Minute Time Scale Prolyl Isomerization Governs Antibody Recognition of an Intrinsically Disordered Immunodominant Epitope*

    PubMed Central

    Fassolari, Marisol; Chemes, Lucia B.; Gallo, Mariana; Smal, Clara; Sánchez, Ignacio E.; de Prat-Gay, Gonzalo

    2013-01-01

    Conformational rearrangements in antibody·antigen recognition are essential events where kinetic discrimination of isomers expands the universe of combinations. We investigated the interaction mechanism of a monoclonal antibody, M1, raised against E7 from human papillomavirus, a prototypic viral oncoprotein and a model intrinsically disordered protein. The mapped 12-amino acid immunodominant epitope lies within a “hinge” region between the N-terminal intrinsically disordered and the C-terminal globular domains. Kinetic experiments show that despite being within an intrinsically disordered region, the hinge E7 epitope has at least two populations separated by a high energy barrier. Nuclear magnetic resonance traced the origin of this barrier to a very slow (t½ ∼4 min) trans-cis prolyl isomerization event involving changes in secondary structure. The less populated (10%) cis isomer is the binding-competent species, thus requiring the 90% of molecules in the trans configuration to isomerize before binding. The association rate for the cis isomer approaches 6 × 107 m−1 s−1, a ceiling for antigen-antibody interactions. Mutagenesis experiments showed that Pro-41 in E7Ep was required for both binding and isomerization. After a slow postbinding unimolecular rearrangement, a consolidated complex with KD = 1.2 × 10−7 m is reached. Our results suggest that presentation of this viral epitope by the antigen-presenting cells would have to be “locked” in the cis conformation, in opposition to the most populated trans isomer, in order to select the specific antibody clone that goes through affinity and kinetic maturation. PMID:23504368

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

    SciTech Connect

    Golczak, Marcin; Kiser, Philip D.; Lodowski, David T.; Maeda, Akiko; Palczewski, Krzysztof

    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

  5. Photo- and thermochromic spirans. XVII. Tautomerism and photoinduced isomerizations of aldonitrone vinylogs

    SciTech Connect

    Metelitsa, A.V.; Lyashik, O.T.; Volbushko, N.V.; Andreeva, I.M.; Knyazhanskii, M.I.; Medyantseva, E.A.; Minkin, V.I.

    1986-12-10

    Nitrones of o-hydroxycinnamaldehyde and its benzoannelated derivatives were prepared. A benzoid-quinoid tautomeric equilibrium was observed for 3-(1-hydroxy-4-methyl-2-naphthyl)propenal and 3-(1-hydroxy-4-naphthyl)-propenal nitrones in a polar solvent. On irradiation of o-cetyl derivatives (77-293/sup 0/K), oxaziranes are formed and reversible cis-trans-isomerization reactions with respect to the CH=CH bond are recorded. In the case of hydroxynitrones, the phototransformations are due to a proton transfer from the hydroxylic group to the nitrogen oxide group, followed by cyclization, leading to isomers with a cyclic 2H-chromene structure.

  6. On the dynamics of fragment isomerization in collision-induced dissociation of peptides.

    PubMed

    Polfer, Nick C; Bohrer, Brian C; Plasencia, Manolo D; Paizs, Béla; Clemmer, David E

    2008-02-14

    The structures of peptide collision-induced dissociation (CID) product ions are investigated using ion mobility/mass spectrometry techniques combined with theoretical methods. The cross-section results are consistent with a mixture of linear and cyclic structures for both b4 and a4 fragment ions. Direct evidence for cyclic structures is essential in rationalizing the appearance of fragments with scrambled (i.e., permutated) primary structures, as the cycle may not open up where it was initially formed. It is demonstrated here that cyclic and linear a4 structures can interconvert freely as a result of collisional activation, implying that isomerization takes place prior to dissociation.

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

    SciTech Connect

    Murgida, G. E.; Arranz, F. J.; Borondo, F.

    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.

  8. Isomeric differentiation of polycyclic aromatic hydrocarbons using silver nitrate reactive desorption electrospray ionization mass spectrometry

    PubMed Central

    Eftekhari, Mohammad; Ismail, Ali I.; Zare, Richard N.

    2014-01-01

    RATIONALE Polycyclic aromatic hydrocarbons (PAHs) are nonpolar and difficult to detect by desorption electrospray ionization. We present a new detection method based on cationization with silver ions, which has the added advantage of being able to differentiate PAHs with the same mass but different structure. METHODS 9,10-Diphenylanthracene and triptycene, in addition to four different groups of PAH isomers: (1) anthracene and phenanthrene, (2) pyrene and fluoranthene, (3) benz[a]anthracene, benz[b]anthracene (tetracene), and chrysene (4) benzo[a]pyrene and benzo[k]fluoranthene, were deposited on a paper surface and bombarded with methanol droplets containing silver nitrate. The resulting microdroplets entered a quadruple mass spectrometer for mass analysis. RESULTS The mass spectrum shows [PAH]+, [Ag + OH + PAH]+, and [Ag(PAH)n]+ n (n = 1, 2) (and [PAH + O2]+ in the case of benz[b]anthracene) ions. PAHs having a bay structure, such as phenanthrene, showed a different tendency to interact with silver ions from those PAHs having a linear arrangement of the fused benzene rings, such as anthracene. The ratios of the [PAH]+ peak intensity to that of [Ag–PAH]+, [Ag + OH + PAH]+, [Ag(PAH)2]+, and [PAH + O2]+ were used to differentiate the PAH isomers sharing the same molecular formula with different structures. For isomeric mixtures the [PAH]+ to [Ag + OH + PAH]+ ratio was found to be the most useful parameter. The uncertainty in the mole fraction of an isomeric mixture was ±0.09, 0.13, ±0.25, and ±0.1 for phenanthrene-anthracene, fl benz[a] anthracene-chrysene, and benzo[a]pyrene-benzo[k]fluoranthene, respectively. CONCLUSIONS A simple method has been developed for the detection of PAHs in desorption electrospray ionization mass spectrometry based on Ag(I) cationization. The method showed a capability to differentiate PAHs isomers (having the same molecular mass) in isomeric mixture with an uncertainty in the mole fraction of about 0.1. At high inlet temperature

  9. Effect of the Metal Ion on the Enantioselectivity and Linkage Isomerization of Thiosemicarbazone Helicates.

    PubMed

    Romero, María J; Suárez, Vanesa; Fernández-Fariña, Sandra; Maneiro, Marcelino; Martínez-Núñez, Emilio; Zaragoza, Guillermo; González-Noya, Ana M; Pedrido, Rosa

    2017-04-06

    The effect of the metal ion and ligand design on the enantioselectivity and linkage isomerization of neutral cobalt and zinc bisthiosemicarbazone metallohelicates has been investigated in this work. The electrochemical synthesis has afforded the enantioselective formation of chirally pure cobalt helicates, and the ΛΛ isomer of a single enantiomer has been crystallized as only product for the cobalt methyl-substituted thiosemicarbazone helicate. Interestingly linkage isomers have been formed from zinc ethyl-substituted thiosemicarbazone helicate enantiomers for the first time. The co-existence of these isomers has been evaluated from the point of view of both experimental results and computational calculations.

  10. Effects of Infrared Laser Radiation on the In Vitro Isomerization of All-Trans Retinal to 11-Cis Retinal

    PubMed Central

    Liegner, J.; Taboada, J.; Tsin, A. T. C.

    2015-01-01

    The in vitro effect of infrared laser light on the isomerization of all-trans retinal dissolved in an ether/hexane and also an ethanol solvent was studied. Pulsed laser energy at 1064 nm was used to drive the molecular reconfiguration of all-trans retinal to 11-cis retinal. High pressure liquid chromatography (HPLC) was used to quantify the conversion. Overall isomerization was minimal (0.2 percent to 1.0 percent), yet, a significant difference in isomerization due to pulsed infrared laser energy over non-modulated monochromatic laser light was detected (up to 168 percent difference). Potentially, pulsed laser radiation tuned to the ethylenic stretch frequency of the C11=C12 bond of retinal may induce rotational changes to the chromophore. PMID:26321787

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Unimolecular reactions in the CF3CH2Cl ↔ CF2ClCH2F system: isomerization by interchange of Cl and F atoms.

    PubMed

    Enstice, Erin C; Duncan, Juliana R; Setser, D W; Holmes, Bert E

    2011-02-17

    The recombination of CF(2)Cl and CH(2)F radicals was used to prepare CF(2)ClCH(2)F* molecules with 93 ± 2 kcal mol(-1) of vibrational energy in a room temperature bath gas. The observed unimolecular reactions in order of relative importance were: (1) 1,2-ClH elimination to give CF(2)═CHF, (2) isomerization to CF(3)CH(2)Cl by the interchange of F and Cl atoms and (3) 1,2-FH elimination to give E- and Z-CFCl═CHF. Since the isomerization reaction is 12 kcal mol(-1) exothermic, the CF(3)CH(2)Cl* molecules have 105 kcal mol(-1) of internal energy and they can eliminate HF to give CF(2)═CHCl, decompose by rupture of the C-Cl bond, or isomerize back to CF(2)ClCH(2)F. These data, which provide experimental rate constants, are combined with previously published results for chemically activated CF(3)CH(2)Cl* formed by the recombination of CF(3) and CH(2)Cl radicals to provide a comprehensive view of the CF(3)CH(2)Cl* ↔ CF(2)ClCH(2)F* unimolecular reaction system. The experimental rate constants are matched to calculated statistical rate constants to assign threshold energies for the observed reactions. The models for the molecules and transition states needed for the rate constant calculations were obtained from electronic structures calculated from density functional theory. The previously proposed explanation for the formation of CF(2)═CHF in thermal and infrared multiphoton excitation studies of CF(3)CH(2)Cl, which was 2,2-HCl elimination from CF(3)CH(2)Cl followed by migration of the F atom in CF(3)CH, should be replaced by the Cl/F interchange reaction followed by a conventional 1,2-ClH elimination from CF(2)ClCH(2)F. The unimolecular reactions are augmented by free-radical chemistry initiated by reactions of Cl and F atoms in the thermal decomposition of CF(3)CH(2)Cl and CF(2)ClCH(2)F.

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

    PubMed

    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.

  14. Sulfated nanozirconia: an investigation on acid-base properties and n-butane isomerization activity.

    PubMed

    Mishra, H K; Dalai, A K; Das, D D; Parida, K M; Pradhan, N C

    2004-04-15

    Hydrated zirconia was synthesized by an organo-inorganic route employing surfactant and was sulfated using aqueous ammonium persulfate, followed by drying at 110 degrees C. The sample thus obtained was calcined at 600 degrees C to obtain sulfated zirconia and was characterized by several physicochemical methods. Crystallite sizes of sulfated zirconia were calculated from X-ray line broadening using the Debye-Scherer equation and were found to be in the range of 25 nm. When pretreated in air, the catalyst was found to exhibit butane isomerization activity at a temperature as low as 35 degrees C under atmospheric pressure. It showed conversion as high as 37% at 100 degrees C under normal pressure when pretreated in air, whereas nitrogen-pretreated catalyst showed zero activity under similar conditions. NH(3) and CO(2) temperature-programmed desorption studies on air- and helium-pretreated samples indicated that the catalyst surface changes appreciably during air pretreatment. Results on butane isomerization in conjunction with TPD studies suggest that zirconium-oxy sites play an important role in butane activation during the reaction.

  15. On the mechanism of isomerization of ocular retinoids by the crayfish Procambarus clarkii.

    PubMed

    Srivastava, R; Goldsmith, T H

    1997-02-01

    The eyes of some crustaceans store substantial amounts of retinyl esters, with most of the retinol in the 11-cis configuration. Earlier work in this laboratory suggested that in lobster and crayfish the mechanism of isomerization of retinol to the 11-cis form involves the hydrolysis of all-trans retinyl esters. Although this is the same process as that occurring in the vertebrate eye, it is different from the retinal photoisomerase reaction known in other arthropods, specifically diurnal insects (Hymenoptera and probably Diptera). Using homogenates of crayfish, we have tested this proposed mechanism by inhibiting retinyl ester synthetase activity in the presence of exogenous all-trans retinol. Inhibition of lecithin:retinol acyl transferase with 5 mumol l-1 retinyl bromoacetate or 2 mmol l-1 phenylmethylsulfonyl fluoride blocks the formation of both all-trans and 11-cis retinyl esters as well as 11-cis retinol, as shown by direct assay and by the decrease in counts derived from tritiated all-trans retinol. The similarity of this isomerization to the mechanism in vertebrate pigment epithelium is thus an interesting example of convergent evolution in the biochemistry of visual pigments, in which the pigments themselves (the opsins) are largely conserved across phyla.

  16. Computational Studies Of Chemical Reactions: The Hnc-Hcn And Ch[subscript3]Nc-Ch[subscript3]Cn Isomerizations

    ERIC Educational Resources Information Center

    Halpern, Arthur M.

    2006-01-01

    The application of computational methods to the isomerization of hydrogen isocyanide to hydrogen cyanide, HNC-HCN is described. The logical extension to the exercise is presented to the isomerization of the methyl-substituted compounds, methylisocyanide and methylcyanide, Ch[subscript 3]NC-CH[subscript3]CN.

  17. Cyclohexane revisited: High pressure nuclear magnetic resonance rotating frame relaxation study of the dynamical solvent effects on the conformational isomerization of cyclohexane

    NASA Astrophysics Data System (ADS)

    Campbell, D. M.; Mackowiak, M.; Jonas, J.

    1992-02-01

    The main goal of this study is to extend the dynamic range of isomerization rates for cyclohexane in order to determine with high accuracy whether the barrier height to isomerization is pressure dependent. Therefore, the effect of pressure and temperature on the conformational isomerization of cyclohexane in carbon disulfide solvent has been investigated using the NMR (nuclear magnetic resonance) rotating frame relaxation technique. This technique, used for the first time in pressure studies of chemical exchange, allows the measurement of isomerization dynamics over a wide range of pressures and temperatures. By combining the rotating frame and NMR line shape techniques and generating the isoviscosity plots, it is shown that the barrier height to isomerization is independent of pressure. Since the experimental isomerization rate is accelerated by pressure, the viscosity dependence of the reduced transmission coefficient shows that the isomerization falls into the energy controlled (inertial) regime of the Kramers model in agreement with our earlier experimental findings. These experimental results, as interpreted in terms of stochastic models of isomerization reactions, indicate a strong collisional coupling and the presence of dynamical solvent effects.

  18. Folding of barstar C40A/C82A/P27A and catalysis of the peptidyl-prolyl cis/trans isomerization by human cytosolic cyclophilin (Cyp18).

    PubMed Central

    Golbik, R.; Fischer, G.; Fersht, A. R.

    1999-01-01

    Refolding of b*C40A/C82A/P27A is comprised of several kinetically detectable folding phases. The slowest phase in refolding originates from trans-->cis isomerization of the Tyr47-Pro48 peptide bond being in cis conformation in the native state. This refolding phase can be accelerated by the peptidyl-prolyl cis/trans isomerase human cytosolic cyclophilin (Cyp18) with a kcat/K(M) of 254,000 M(-1) s(-1). The fast refolding phase is not influenced by the enzyme. PMID:10422840

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

    PubMed

    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.

  20. Molecular tectonics of mixed-ligand metal-organic frameworks: positional isomeric effect, metal-directed assembly, and structural diversification.

    PubMed

    Du, Miao; Jiang, Xiu-Juan; Zhao, Xiao-Jun

    2007-05-14

    A series of nine mixed-ligand metal-organic frameworks (MOFs) have been prepared by the combination of a bent dipyridyl linker 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (bpt) and three benzenedicarboxylate isomers (pa = phthalate, ip = isophthalate, and tp = terephthalate), respectively, with different metal ions such as CoII, NiII, CuII, ZnII, and CdII. The framework structures of these neutral polymeric complexes have been determined by the X-ray single-crystal diffraction technique. Structural analysis reveals that the benzenedicarboxylate isomers display versatile coordination modes to manage the metal ions to form 1-D chain or ribbon arrays, which are further extended via the exo-bidentate bpt connectors to give rise to a variety of coordination networks, such as a simple (4,4) layer, 2-D double layer with decorated (4,4) topology, 2-D layer with decorated (3,6) topology, 2-D bilayer with 82.10 topology (2-fold interpenetration), 3-D polythreaded architecture (1-D + 2-D), and 2-fold interpenetrating porous lattice of (4,4) layers. The accessorial secondary interactions such as hydrogen bonding and/or aromatic stacking are also helpful for the extension and stabilization of the final supramolecular aggregates. This work evidently indicates that the isomeric effect of the anionic benzenedicarboxylate is significant in the construction of these network structures, which are also well regulated by the metal centers. The ZnII and CdII MOFs exhibit strong solid-state luminescence emissions at room temperature, which originate differently from intraligand transition or ligand-to-metal charge transfer. Thermal stability of these crystalline materials has been explored by thermogravimetric analysis of mass loss. The 3-D host frameworks of MOFs 8 and 9 show similar porous cavities, and their desorption/adsorption behaviors of guest solvents have also been investigated.

  1. Investigation of glassy state molecular motions in thermoset polymers

    NASA Astrophysics Data System (ADS)

    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

  2. Spectra of carbanions formed from allyl cyanide during isomerization in zeolite NaY-FAU with strong basic sites

    NASA Astrophysics Data System (ADS)

    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.

  3. Enantioselective Nickel-Catalyzed anti-Carbometallative Cyclizations of Alkynyl Electrophiles Enabled by Reversible Alkenylnickel E/Z Isomerization

    PubMed Central

    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

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

    PubMed

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

    2005-03-28

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

  5. Mechanistic interpretation of selective catalytic hydrogenation and isomerization of alkenes and dienes by ligand deactivated Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhu, Jie S.; Shon, Young-Seok

    2015-10-01

    Unsupported thiolate-capped palladium nanoparticle catalysts are found to be highly substrate-selective for alkene hydrogenation and isomerization. Steric and poisoning effects from thiolate ligands on the nanoparticle surface control reactivity and selectivity by influencing alkene adsorption and directing either di-σ or mono-σ bond formation. The presence of overlapping p orbitals and α protons in alkenes greatly influences the catalytic properties of deactivated palladium nanoparticles leading to easily predictable hydrogenation or isomerization products.Unsupported thiolate-capped palladium nanoparticle catalysts are found to be highly substrate-selective for alkene hydrogenation and isomerization. Steric and poisoning effects from thiolate ligands on the nanoparticle surface control reactivity and selectivity by influencing alkene adsorption and directing either di-σ or mono-σ bond formation. The presence of overlapping p orbitals and α protons in alkenes greatly influences the catalytic properties of deactivated palladium nanoparticles leading to easily predictable hydrogenation or isomerization products. Electronic supplementary information (ESI) available: Supplementary figures, methods, materials, and characterization data. See DOI: 10.1039/c5nr05090a

  6. Flavylium based dual photochromism: addressing cis-trans isomerization and ring opening-closure by different light inputs.

    PubMed

    Gago, Sandra; Basílio, Nuno; Moro, Artur J; Pina, Fernando

    2015-04-30

    The multistate system of 4',7-dihydroxy-3-methoxyflavylium is constituted by a multiequilibrium involving trans-chalcone, cis-chalcone, hemiketal, flavylium cation and quinoidal base. This system possesses two independently addressable inter-connected photochromic systems based on the cis-trans isomerization and ring opening-closure of the hemiketal.

  7. Asymmetric Synthesis of Ramariolides A and C through Bimetallic Cascade Cyclization and Z-E Isomerization Reaction.

    PubMed

    Pal, Pratik; Nanda, Samik

    2017-03-03

    A short and flexible asymmetric synthesis of ramariolides A and C was accomplished. A bimetallic catalytic system consisting of Pd-Cu-mediated cascade cyclization, unprecedented Z-E isomerization by a Ru-based metathesis catalyst, and late-stage stereoselective epoxidation are the key steps involved in the synthesis.

  8. Tandem isomerization-decarboxylation of unsaturated fatty acids to olefins via ruthenium metal-as-ligand catalysts

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new facile Ru-catalyzed route to bio-olefins3 from unsaturated fatty acids via readily accessible metal-as-ligand type catalyst precursors, [Ru(CO)2RCO2]n and Ru3(CO)12, will be described. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds i...

  9. How does the isomerization rate affect the photoisomerization-induced transport properties of a doped molecular glass-former?

    NASA Astrophysics Data System (ADS)

    Accary, J.-B.; Teboul, V.

    2013-07-01

    We investigate the effect of the isomerization rate f on the microscopic mechanisms at the origin of the massive mass transport found in glass-formers doped with isomerizing azobenzene molecules that result in surface relief gratings formation. To this end we simulate the isomerization of dispersed probe molecules embedded into a molecular host glass-former. The host diffusion coefficient first increases linearly with f and then saturates. The saturated value of the diffusion coefficient and of the viscosity does not depend on f but increases with temperature while the linear response for these transport coefficients depends only slightly on the temperature. We interpret this saturation as arising from the appearance of increasingly soft regions around the probes for high isomerization rates, a result in qualitative agreement with experiments. These two different physical behaviors, linear response and saturation, are reminiscent of the two different unexplained mass transport mechanisms observed for small or large light intensities (for small intensities the molecules move towards the dark regions while for large intensities they move towards the illuminated regions).

  10. Mechanism Elucidation of the cis–trans Isomerization of an Azole Ruthenium–Nitrosyl Complex and Its Osmium Counterpart

    PubMed Central

    2013-01-01

    Synthesis and X-ray diffraction structures of cis and trans isomers of ruthenium and osmium metal complexes of general formulas (nBu4N)[cis-MCl4(NO)(Hind)], where M = Ru (1) and Os (3), and (nBu4N)[trans-MCl4(NO)(Hind)], where M = Ru (2) and Os (4) and Hind = 1H-indazole are reported. Interconversion between cis and trans isomers at high temperatures (80–130 °C) has been observed and studied by NMR spectroscopy. Kinetic data indicate that isomerizations correspond to reversible first order reactions. The rates of isomerization reactions even at 110 °C are very low with rate constants of 10–5 s–1 and 10–6 s–1 for ruthenium and osmium complexes, respectively, and the estimated rate constants of isomerization at room temperature are of ca. 10–10 s–1. The activation parameters, which have been obtained from fitting the reaction rates at different temperatures to the Eyring equation for ruthenium [ΔHcis-trans‡= 122.8 ± 1.3; ΔHtrans-cis‡= 138.8 ± 1.0 kJ/mol; ΔScis-trans‡= −18.7 ± 3.6; ΔStrans-cis‡= 31.8 ± 2.7 J/(mol·K)] and osmium [ΔHcis-trans‡= 200.7 ± 0.7; ΔHtrans-cis‡= 168.2 ± 0.6 kJ/mol; ΔScis-trans‡= 142.7 ± 8.9; ΔStrans-cis‡= 85.9 ± 3.9 J/(mol·K)] reflect the inertness of these systems. The entropy of activation for the osmium complexes is highly positive and suggests the dissociative mechanism of isomerization. In the case of ruthenium, the activation entropy for the cis to trans isomerization is negative [−18.6 J/(mol·K)], while being positive [31.0 J/(mol·K)] for the trans to cis conversion. The thermodynamic parameters for cis to trans isomerization of [RuCl4(NO)(Hind)]−, viz. ΔH° = 13.5 ± 1.5 kJ/mol and ΔS° = −5.2 ± 3.4 J/(mol·K) indicate the low difference between the energies of cis and trans isomers. The theoretical calculation has been carried out on isomerization of ruthenium complexes with DFT methods. The dissociative, associative, and intramolecular twist isomerization mechanisms have

  11. Mechanism elucidation of the cis-trans isomerization of an azole ruthenium-nitrosyl complex and its osmium counterpart.

    PubMed

    Gavriluta, Anatolie; Büchel, Gabriel E; Freitag, Leon; Novitchi, Ghenadie; Tommasino, Jean Bernard; Jeanneau, Erwann; Kuhn, Paul-Steffen; González, Leticia; Arion, Vladimir B; Luneau, Dominique

    2013-06-03

    Synthesis and X-ray diffraction structures of cis and trans isomers of ruthenium and osmium metal complexes of general formulas (nBu4N)[cis-MCl4(NO)(Hind)], where M = Ru (1) and Os (3), and (nBu4N)[trans-MCl4(NO)(Hind)], where M = Ru (2) and Os (4) and Hind = 1H-indazole are reported. Interconversion between cis and trans isomers at high temperatures (80-130 °C) has been observed and studied by NMR spectroscopy. Kinetic data indicate that isomerizations correspond to reversible first order reactions. The rates of isomerization reactions even at 110 °C are very low with rate constants of 10(-5) s(-1) and 10(-6) s(-1) for ruthenium and osmium complexes, respectively, and the estimated rate constants of isomerization at room temperature are of ca. 10(-10) s(-1). The activation parameters, which have been obtained from fitting the reaction rates at different temperatures to the Eyring equation for ruthenium [ΔH(cis-trans)‡ = 122.8 ± 1.3; ΔH(trans-cis)‡ = 138.8 ± 1.0 kJ/mol; ΔS(cis-trans)‡ = -18.7 ± 3.6; ΔS(trans-cis)‡ = 31.8 ± 2.7 J/(mol·K)] and osmium [ΔH(cis-trans)‡ = 200.7 ± 0.7; ΔH(trans-cis)‡ = 168.2 ± 0.6 kJ/mol; ΔS(cis-trans)‡ = 142.7 ± 8.9; ΔS(trans-cis)‡ = 85.9 ± 3.9 J/(mol·K)] reflect the inertness of these systems. The entropy of activation for the osmium complexes is highly positive and suggests the dissociative mechanism of isomerization. In the case of ruthenium, the activation entropy for the cis to trans isomerization is negative [-18.6 J/(mol·K)], while being positive [31.0 J/(mol·K)] for the trans to cis conversion. The thermodynamic parameters for cis to trans isomerization of [RuCl4(NO)(Hind)]-, viz. ΔH° = 13.5 ± 1.5 kJ/mol and ΔS° = -5.2 ± 3.4 J/(mol·K) indicate the low difference between the energies of cis and trans isomers. The theoretical calculation has been carried out on isomerization of ruthenium complexes with DFT methods. The dissociative, associative, and intramolecular twist isomerization

  12. Acetylene/Vinylidene Isomerization after Carbon K-shell Photo-Ionization

    NASA Astrophysics Data System (ADS)

    Osipov, Timut; Weber, T.; Jahnke, T.; Alnaser, A.; Landers, A.; Hertlein, M.; Jagutzki, O.; Schmidt, L.; Schöffler, M.; Prior, M.; Feinberg, B.; Cocke, C. L.; Dörner, R.; Belkacem, A.

    2006-05-01

    Comprehensive study of the acetylene/vinylidene isomerization dynamics after the carbon k-shell photoionization followed by the Auger decay was performed by means of the COLTRIMS (COLd Target Recoil Ion Momentum Spectroscopy) technique. The Auger electrons, produced in this reaction, were detected in coincidence with the products of the Coulomb explosion of the dication C2H2^2+. Measurement of the 3d vector momenta for all detected particles inferred the Auger electron energies and directions in the body fixed molecular frame along with the KER (Kinetic Energy Release) for different break up channels. This highly differential reaction cross-section study provided very unique information about the fragmentation pathways of the doubly charged acetylene molecule.

  13. Holographic recording materials development. [development of cis-trans isomerization for holographic memory

    NASA Technical Reports Server (NTRS)

    1974-01-01

    Developments in the area of organic cis-trans isomerization systems for holographic memory applications are reported. The chemical research effort consisted of photochemical studies leading to the selection of a stilbene derivative and a polymer matrix system which have greatly improved refractive index differences between the cis and trans isomers as well as demonstrated efficiency of the photoisomerization process. In work on lithium niobate effects of sample stoichiometry and of read and write beam polarizations on recording efficiency were investigated. LiNbO3 was used for a study of angular sensitivity and of capability for simultaneous recording of extended objects without interference. The current status of LiNbO3 as a holographic recording material is summarized.

  14. Coherent chemistry with THz pulses: Ultrafast field-driven isomerization of LiNC

    NASA Astrophysics Data System (ADS)

    Pellouchoud, L. A.; Reed, E. J.

    2015-05-01

    The ability to coherently rearrange structures at the atomic scale is among the grand challenges of physical science. Some of the primary obstacles are nonadiabatic increases in energy, such as intramolecular vibrational relaxation (IVR) and electronic excitations. Motivated by recent advances in strong terahertz (THz) pulse generation, we investigate the potential of THz to circumvent these obstacles. Employing TDDFT-Ehrenfest simulations, we discover that strong THz pulses can drive isomerization of the LiNC molecule over barriers greater than 0.2 eV with very low ionization rates and, in the best case, less than 3 meV of residual excess energy. This work points to new possibilities in predictively manipulating chemical bonds in molecules and materials.

  15. Structural Isomerization of the Gas Phase 2-NORBORNYL Cation Revealed with Infrared Spectroscopy and Computational Chemistry

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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 (<0.1%) isolate unimolecular decomposition. Products were identified by tunable VUV photoionization mass spectroscopy, photoionization appearance thresholds, and complementary matrix infrared absorption spectroscopy. Thermal cracking of 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.

  17. Mechanism for generation of left isomerism in Ccdc40 mutant embryos

    PubMed Central

    Sugrue, Kelsey F.

    2017-01-01

    Leftward fluid flow in the mouse node is generated by cilia and is critical for initiating asymmetry of the left-right axis. Coiled-coil domain containing-40 (Ccdc40) plays an evolutionarily conserved role in the assembly of motile cilia and establishment of the left-right axis. Approximately one-third of Ccdc40lnks mutant embryos display situs defects and here we investigate the underlying mechanism. Ccdc40lnks mutants show delayed induction of markers of the left-lateral plate mesoderm (L-LPM) including Lefty1, Lefty2 and Nodal. Consistent with defective cilia motility compromising fluid flow across the node, initiation of asymmetric perinodal Cerberus like-2 (Cerl2) expression is delayed and then randomized. This is followed by delayed and then randomized asymmetric Nodal expression around the node. We propose a model to explain how left isomerism arises in a proportion of Ccdc40lnks mutants. We postulate that with defective motile cilia, Cerl2 expression remains symmetric and Nodal is antagonized equally on both sides of the node. This effectively reduces Nodal activation bilaterally, leading to reduced and delayed activation of Nodal and its antagonists in the LPM. This model is further supported by the failure to establish Nodal expression in the left-LPM with reduced Nodal gene dosage in Ccdc40lnks/lnks;NodalLacZ/+ mutants causing a predominance of right not left isomerism. Together these results suggest a model where cilia generated fluid flow in the node functions to ensure robust Nodal activation and a timely left-sided developmental program in the LPM. PMID:28182636

  18. Cardiovascular MR imaging findings of total anomalous pulmonary venous connection to the portal vein in a patient with right atrial isomerism.

    PubMed

    Koplay, Mustafa; Paksoy, Yahya; Erol, Cengiz; Arslan, Derya; Kivrak, Ali Sami; Karaaslan, Sevim

    2012-12-01

    Total anomalous pulmonary venous connection (TAPVC) is a rare congenital cardiovascular anomaly in which the pulmonary veins fail to join to the left atrium and drain directly to the right atrium or to one of the systemic veins. This anomaly is frequently seen together with complex cardiac anomalies especially as a part of right atrial isomerism syndrome. Atrial isomerism is called that the same morphological structure of both atria. We reported a very rare case demonstrating TAPVC between the portal vein and the pulmonary veins in a patient with right atrial isomerism by magnetic resonance imaging.

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

    PubMed Central

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

    2015-01-01

    Background: Lycopene, which is a red carotenoid in tomatoes, has been hypothesized to mediate disease-preventive effects associated with tomato consumption. Lycopene is consumed primarily as the all-trans geometric isomer in foods, whereas human plasma and tissues show greater proportions of cis isomers. Objective: With the use of compartmental modeling and stable isotope technology, we determined whether endogenous all-trans-to-cis-lycopene isomerization or isomeric-bioavailability differences underlie the greater proportion of lycopene cis isomers in human tissues than in tomato foods. Design: Healthy men (n = 4) and women (n = 4) consumed 13C-lycopene (10.2 mg; 82% all-trans and 18% cis), and plasma was collected over 28 d. Unlabeled and 13C-labeled total lycopene and lycopene-isomer plasma concentrations, which were measured with the use of high-performance liquid chromatography–mass spectrometry, were fit to a 7-compartment model. Results: Subjects absorbed a mean ± SEM of 23% ± 6% of the lycopene. The proportion of plasma cis-13C-lycopene isomers increased over time, and all-trans had a shorter half-life than that of cis isomers (5.3 ± 0.3 and 8.8 ± 0.6 d, respectively; P < 0.001) and an earlier time to reach maximal plasma concentration than that of cis isomers (28 ± 7 and 48 ± 9 h, respectively). A compartmental model that allowed for interindividual differences in cis- and all-trans-lycopene bioavailability and endogenous trans-to-cis-lycopene isomerization was predictive of plasma 13C and unlabeled cis- and all-trans-lycopene concentrations. Although the bioavailability of cis (24.5% ± 6%) and all-trans (23.2% ± 8%) isomers did not differ, endogenous isomerization (0.97 ± 0.25 μmol/d in the fast-turnover tissue lycopene pool) drove tissue and plasma isomeric profiles. Conclusion: 13C-Lycopene combined with physiologic compartmental modeling provides a strategy for following complex in vivo metabolic processes in humans and reveals that

  20. Accurate prediction of diradical chemistry from a single-reference density-matrix method: Model application to the bicyclobutane to gauche-1,3-butadiene isomerization

    SciTech Connect

    Bertels, Luke W.; Mazziotti, David A.

    2014-07-28

    Multireference correlation in diradical molecules can be captured by a single-reference 2-electron reduced-density-matrix (2-RDM) calculation with only single and double excitations in the 2-RDM parametrization. The 2-RDM parametrization is determined by N-representability conditions that are non-perturbative in their treatment of the electron correlation. Conventional single-reference wave function methods cannot describe the entanglement within diradical molecules without employing triple- and potentially even higher-order excitations of the mean-field determinant. In the isomerization of bicyclobutane to gauche-1,3-butadiene the parametric 2-RDM (p2-RDM) method predicts that the diradical disrotatory transition state is 58.9 kcal/mol above bicyclobutane. This barrier is in agreement with previous multireference calculations as well as recent Monte Carlo and higher-order coupled cluster calculations. The p2-RDM method predicts the Nth natural-orbital occupation number of the transition state to be 0.635, revealing its diradical character. The optimized geometry from the p2-RDM method differs in important details from the complete-active-space self-consistent-field geometry used in many previous studies including the Monte Carlo calculation.

  1. Crystallographic study of red fluorescent protein eqFP578 and its far-red variant Katushka reveals opposite pH-induced isomerization of chromophore

    SciTech Connect

    Pletneva, Nadya V.; Pletnev, Vladimir Z.; Shemiakina, Irina I.; Chudakov, Dmitriy M.; Artemyev, Igor; Wlodawer, Alexander; Dauter, Zbigniew; Pletnev, Sergei

    2012-08-10

    The wild type red fluorescent protein eqFP578 (from sea anemone Entacmaea quadricolor, {lambda}{sub ex} = 552 nm, {lambda}{sub em} = 578 nm) and its bright far-red fluorescent variant Katushka ({lambda}{sub ex} = 588 nm, {lambda}{sub em} = 635 nm) are characterized by the pronounced pH dependence of their fluorescence. The crystal structures of eqFP578f (eqFP578 with two point mutations improving the protein folding) and Katushka have been determined at the resolution ranging from 1.15 to 1.85 {angstrom} at two pH values, corresponding to low and high level of fluorescence. The observed extinguishing of fluorescence upon reducing pH in eqFP578f and Katushka has been shown to be accompanied by the opposite trans-cis and cis-trans chromophore isomerization, respectively. Asn143, Ser158, His197 and Ser143, Leu174, and Arg197 have been shown to stabilize the respective trans and cis fluorescent states of the chromophores in eqFP578f and Katushka at higher pH. The cis state has been suggested as being primarily responsible for the observed far-red shift of the emission maximum of Katushka relative to that of eqFP578f.

  2. 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.

    PubMed

    Loomba, Rohit S; Danduran, Michael; Nielsen, Kim G; Ring, Astrid M; Kovach, Joshua; Anderson, Robert H

    2017-02-01

    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 postoperative ventilatory support. Additionally, these patients often have congenital heart disease requiring Fontan palliation. What has not been previously described, and is the focus of this study, is the results of cardiopulmonary exercise testing in those who have undergone Fontan palliation with and without isomerism. We have now compared these finding with those from patients with primary ciliary dyskinesia, as many patients with isomerism have ciliary dyskinesia. We identified patients having the Fontan circulation with and without isomerism who had undergone cardiopulmonary exercise testing, comparing the findings from healthy individuals undergoing exercise, and a comparable number of individuals with primary ciliary dyskinesia but no congenital heart disease. We were able to include a total of 68 patients in our study, with 17 in each of the four groups. Cardiopulmonary exercise testing yielded the best results in healthy patients. All patients with the Fontan circulation demonstrated mixed pulmonary disease, although those with isomerism had greater FVC and FEV1. Exercise times did not differ, although peak consumption of oxygen was greater in those with isomerism. Those with ciliary dyskinesia had only obstructive pulmonary disease and had the lowest FEF25-75 between all groups. Those with isomerism had a lesser degree of obstructive pulmonary disease when compared to those with primary ciliary dyskinesia. Patients with the Fontan circulation with and without isomerism have relatively subtle differences in their cardiopulmonary exercise testing, with both groups demonstrating restrictive lung disease. In regard to obstructive lung disease, those with isomerism tend

  3. Ru-Catalyzed Estragole Isomerization under Homogeneous and Ionic Liquid Biphasic Conditions

    PubMed Central

    2017-01-01

    The isomerization of estragole to trans-anethole is an important reaction and is industrially performed using an excess of NaOH or KOH in ethanol at high temperatures with very low selectivity. Simple Ru-based transition-metal complexes, under homogeneous, ionic liquid (IL)-supported (biphasic) and “solventless” conditions, can be used for this reaction. The selectivity of this reaction is more sensitive to the solvent/support used than the ligands associated with the metal catalyst. Thus, under the optimized reaction conditions, 100% conversion can be achieved in the estragole isomerization, using as little as 4 × 10–3 mol % (40 ppm) of [RuHCl(CO)(PPh3)3] in toluene, reflecting a total turnover number (TON) of 25 000 and turnover frequencies (TOFs) of up to 500 min–1 at 80 °C. Using a dimeric Ru precursor, [RuCl(μ-Cl)(η3:η3-C10H16)]2, in ethanol associated with P(OEt)3, a TON of 10 000 and a TOF of 125 min–1 are obtained with 100% conversion and 99% selectivity. These two Ru catalytic systems can be transposed to biphasic IL systems by using ionic-tagged P-ligands such as 1-(3-(diphenylphosphanyl)propyl)-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide immobilized in 1-(3-hydroxypropyl)-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl) imide with up to 99% selectivity and almost complete estragole conversion. However, the reaction is much slower than that performed under solventless or homogeneous conditions. The use of ionic-tagged ligands significantly reduces the Ru leaching to the organic phase, compared to that in reactions performed under homogeneous conditions, where the catalytic system loses catalytic performance after the second recycling. Detailed kinetic investigations of the reaction catalyzed by [RuHCl(CO)(PPh3)3] indicate that a simplified kinetic model (a monomolecular reversible first-order reaction) is adequate for fitting the homogeneous reaction at 80 °C and under biphasic conditions. However, the kinetics of

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

    PubMed

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

    2015-12-24

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

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

    PubMed

    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.

  6. Results of a Direct Search Using Synchrotron Radiation for the Low-Energy Th229 Nuclear Isomeric Transition

    DOE PAGES

    Jeet, Justin; Schneider, Christian; Sullivan, Scott T.; ...

    2015-06-23

    We report the results of a direct search for the 229Tn (Iπ = 3/2+ ← 5/2+) nuclear isomeric transition, performed by exposing 229Tn-doped LiSrAlF6 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. Lastly, this measurement excludes roughly half of the favored transition search area and can be used to direct future searches.

  7. Acidic and basic properties of zeolite-containing cracking catalyst in the process of butene-1 isomerization

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

    We report the results of a direct search for the 229Th (Iπ=3 /2+←5 /2+ ) nuclear isomeric transition, performed by exposing 229Th -doped LiSrAlF6 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.

  9. Complementary in situ reactivity of isomeric dipyridylamide precursors and its effect on dimensionality of cadmium 5-nitroisophthalate coordination polymers

    NASA Astrophysics Data System (ADS)

    O'Donovan, Megan E.; LaDuca, Robert L.

    2014-07-01

    Hydrothermal treatment of cadmium nitrate, 5-nitroisophthalic acid (H2nip) and one of two isomeric dipyridylamides resulted in coordination polymer crystalline solids that manifested different in situ reactivity and dimensionality, as ascertained by single crystal X-ray diffraction. Hydrolysis of 3-pyridylisonicotinamide (3-pina) afforded the 3-aminopyridine (3-ampyr) ligands observed in the 1-D ladder polymer {[Cd(nip)(3-ampyr)(H2O)]ṡ2H2O}n (1). Conversely, hydrolysis of the isomeric precursor 3-pyridylnicotinamide (3-pna) generated the monoanionic nicotinate ligands in the 2-D coordination polymer [Cd2(nip)(nic)2(H2O)2]n (2). Compound 2 displays {Cd2(OCO)2} eight-membered ring dimeric units linked into (6,3) graphite-type slab motifs. Luminescent properties of these two new materials are also presented.

  10. Kinetics of n-butoxy and 2-pentoxy isomerization and detection of primary products by infrared cavity ringdown spectroscopy.

    PubMed

    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

  11. Isomeric ratio measurements for the radiative neutron capture 176Lu(n ,γ ) at the LANL DANCE facility

    NASA Astrophysics Data System (ADS)

    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. Light induced E-Z isomerization in a multi-responsive organogel: elucidation from (1)H NMR spectroscopy.

    PubMed

    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.

  13. Skeletal isomerization accompanying the reactions of the thiabirdcage hydroxy derivative. Synthesis of sulfur-containing oxabirdcage derivatives

    SciTech Connect

    Tolstikov, G.A.; Lerman, B.M.; Belogaeva, T.A.; Sultanova, V.S.; Khalilov, L.M.; Panasenko, A.A.

    1986-09-20

    The thermolysis and oxidation of the hydroxy derivative of the diabirdcage compound in acetic acid is accompanied by skeletal isomerization and leads to mono- and biframework sulfur-containing derivatives of oxabirdcage. It was established by the /sup 13/C NMR method that the biframework compounds with S, SS, and SO/sub 2/ bridges are formed as mixtures of the erythro and threo isomers.

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

    SciTech Connect

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

    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.

  15. An Exceptionally Facile Two-Step Structural Isomerization and Detoxication via a Water-Assisted Double Lossen Rearrangement

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Distribution, isomerization and enantiomer selectivity of hexabromocyclododecane (HBCD) diastereoisomers in different tissue and subcellular fractions of earthworms.

    PubMed

    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.

  18. An Exceptionally Facile Two-Step Structural Isomerization and Detoxication via a Water-Assisted Double Lossen Rearrangement.

    PubMed

    Li, Feng; Huang, Chun-Hua; Xie, Lin-Na; Qu, Na; Shao, Jie; Shao, Bo; Zhu, Ben-Zhan

    2016-12-23

    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.

  19. An Exceptionally Facile Two-Step Structural Isomerization and Detoxication via a Water-Assisted Double Lossen Rearrangement

    PubMed Central

    Li, Feng; Huang, Chun-Hua; Xie, Lin-Na; Qu, Na; Shao, Jie; Shao, Bo; Zhu, Ben-Zhan

    2016-01-01

    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. PMID:28008985

  20. Solution NMR structure and inhibitory effect against amyloid-β fibrillation of Humanin containing a d-isomerized serine residue.

    PubMed

    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. Effect of Asp 96 isomerization on the properties of a lens αB-crystallin-derived short peptide.

    PubMed

    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.

  2. Comparisons of Caenorhabditis Fucosyltransferase Mutants Reveal a Multiplicity of Isomeric N-Glycan Structures.

    PubMed

    Yan, Shi; Jin, Chunsheng; Wilson, Iain B H; Paschinger, Katharina

    2015-12-04

    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.

  3. Characteristics of the isomeric flavonoids apigenin and genistein binding to hemoglobin by spectroscopic methods

    NASA Astrophysics Data System (ADS)

    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.

  4. Lycopene: Heterogeneous Catalytic E/Z Isomerization and In Vitro Bioaccessibility Assessment Using a Diffusion Model.

    PubMed

    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.

  5. Failure in closure of the anterior neural tube causes left isomerization of the zebrafish epithalamus.

    PubMed

    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.

  6. Statistical thermodynamics of the isomerization reaction between n-heptane and isoheptane.

    PubMed

    Yu, Tao; Zheng, Jingjing; Truhlar, Donald G

    2012-01-14

    We have employed electronic structure calculations and the recently proposed multi-structural (MS) anharmonicity method to calculate partition functions and thermodynamic quantities, in particular entropy and heat capacity, for n-heptane and isoheptane. We included all structures, of which there are 59 for n-heptane and 37 for isoheptane, and we carried out the calculations both in the local harmonic approximation and by including torsional (T) anharmonicity. In addition, ΔS°, ΔH, and ΔG° for the isomerization reaction between these two species were also calculated. It is found that all calculated thermodynamic quantities based on the MS-T approximation in the temperature range from 298 K to 1500 K agree well with experimental data from the American Petroleum Institute (API) tables or Thermodynamics Research Center (TRC) data series and with values obtained from Benson's empirical parameters fit to experiment. This demonstrates not only the high accuracy of the electronic structure calculations but also that the MS-T method can be used to include both multiple-structure anharmonicity and torsional anharmonicity in the calculation of thermodynamic properties for complex molecules that contain many torsions. It also gives us confidence that we can apply the MS-T statistical thermodynamic method to obtain thermodynamic properties (i) over a broader temperature range than that for which data are available in the API tables, TRC data series, or from empirical estimation and (ii) to the many molecules for which experimental data are not available at any temperature.

  7. Stereochemical aspects of the metabolism of the isomeric methylcyclohexanols and methylcyclohexanones

    PubMed Central

    Elliott, T. H.; Tao, Rosaline C. C.; Williams, R. T.

    1965-01-01

    1. The seven isomeric optically inactive forms of methylcyclohexanol (i.e. 1-, and cis- and trans-2-, -3- and -4-) are excreted by rabbits mainly as glucuronides of the thermodynamically more stable forms of the alcohols. The eighth isomer, cyclohexylmethanol, however, undergoes aromatization in vivo, giving rise to benzoic acid and hippuric acid. The (±)-2-, (±-3- and 4-methylcyclohexanones are reduced in the rabbit and excreted mainly as the glucuronides of the thermodynamically more stable forms of the corresponding methylcyclohexanols. 2. Racemic cis- and trans-2-methylcyclohexanol and 2-methylcyclohexanone are all excreted as conjugated trans-2-methylcyclohexanol. However, when the (±)-cis-alcohol or the (±)-ketone is fed, (+)-trans-2-methylcyclohexanol is excreted, whereas when the (±)-trans-alcohol is fed it is excreted as the (±)-trans-alcohol. 3. Racemic cis- and trans-3-methylcyclohexanol and 3-methylcyclohexanone are all excreted as conjugated racemic cis-3-methylcyclohexanol. cis- and trans-4-Methylcyclohexanol and 4-methylcyclohexanone are all excreted as conjugated trans-4-methylcyclohexanol. 4. The metabolic differences between the various methylcyclohexanols are explicable in terms of their conformations and of Vennesland's (1958) hypothesis of the role of NADH in dehydrogenation reactions. PMID:14333568

  8. A rapid ambient ionization-mass spectrometry approach to monitoring the relative abundance of isomeric glycerophospholipids.

    PubMed

    Kozlowski, Rachel L; Mitchell, Todd W; Blanksby, Stephen J

    2015-04-02

    Glycerophospholipids with two, non-equivalent fatty acyl chains can adopt one of two isomeric forms depending on the relative position of substitutions on the glycerol backbone. These so-called sn-positional isomers can have distinct biophysical and biochemical behaviors making it desirable to uniquely assign their regiochemistries. Unambiguous assignment of such similar molecular structures in complex biological extracts is a significant challenge to current analytical technologies. We have recently reported a novel mass spectrometric method that combines collision- and ozone-induced dissociation in series (CID/OzID) to yield product ions characteristic of acyl chain substitution patterns in glycerophospholipids. Here phosphatidylcholines are examined using the CID/OzID protocol combined with desorption electrospray ionization (DESI) to facilitate the rapid exploration of sample arrays comprised of a wide variety of synthetic and biological sources. Comparison of the spectra acquired from different extracts reveals that the sn-positional isomers PC 16:0/18:1 and PC 18:1/16:0 (where the 18:1 chain is present at the sn-2 and sn-1 position of the glycerol backbone, respectively) are most often found together in lipids of either natural or synthetic origin. Moreover, the proportions of the two isomers vary significantly between extracts from different organisms or even between adjacent tissues from the same organism.

  9. Benzimidazole-Branched Isomeric Dyes: Effect of Molecular Constitution on Photophysical, Electrochemical, and Photovoltaic Properties.

    PubMed

    Bodedla, Govardhana Babu; Justin Thomas, K R; Fan, Miao-Syuan; Ho, Kuo-Chuan

    2016-01-15

    Three benzimidazole-based isomeric organic dyes possessing two triphenylamine donors and a cyanoacrylic acid acceptor are prepared by stoichiometrically controlled Stille or Suzuki-Miyaura coupling reaction which predominantly occurs on the N-butyl side of benzimidazole due to electronic preferences. Combined with the steric effect of the N-butyl substituent, placement of the acceptor segment at various nuclear positions of benzimidazole such as C2, C4, and C7 led to remarkable variations in intramolecular charge transfer absorption, electron injection efficiency, and charge recombination kinetics. The substitution of acceptor on the C4 led to red-shifted absorption, while that on C7 retarded the charge transfer due to twisting in the structure caused by the butyl group. Because of the cross-conjugation nature and poor electronic interaction between the donor and acceptor, the dye containing triphenylamine units on C4 and C7 and the acceptor unit on C2 showed the low oxidation potential. Thus, this dye possesses favorable HOMO and LUMO energy levels to render efficient sensitizing action in solar cells. Consequently, it results in high power conversion efficiency (5.01%) in the series with high photocurrent density and open circuit voltage. The high photocurrent generation by this dye is reasoned to it exceptional charge collection efficiency as determined from the electron impedance spectroscopy.

  10. Strong-field isomerization dynamics of fast beams of hydrocarbon ions

    NASA Astrophysics Data System (ADS)

    Jochim, Bethany; Rajput, Jyoti; Berry, Ben; Severt, T.; Zohrabi, M.; Feizollah, Peyman; Carnes, K. D.; Esry, B. D.; Ben-Itzhak, I.

    2016-05-01

    Bond rearrangement and fragmentation of hydrocarbons in intense laser fields has been a topic of considerable interest in the strong-field community in recent years. We study the interactions of keV hydrocarbon ion beams with ultrafast, intense laser pulses, employing coincidence 3D momentum imaging to elucidate the fragmentation dynamics and identify laser parameters that might be used for controlling outcomes such as the branching ratios. We focus on dissociation to ensure that isomerization occurs on the particular electronic channels of the molecular ion investigated. In C2 H2+, for example, we measure the intensity-dependent branching ratios of the acetylene (CH++CH) and vinylidene (e . g . , C++ CH2) channels. The relative fragmentation rates between the acetylene and vinylidene channels change by a factor of ~ 2 over the range of experimental intensities (1013- 1015 W/ cm2). Other hydrocarbons of interest include not only cations but also anions, such as C2 H 2 -. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U. S. Department of Energy. BJ was also supported in part by DOE-SCGF (DE-AC05-06OR23100).

  11. Laser probes of the potential energy landscapes and conformational isomerization dynamics of flexible biomolecules

    NASA Astrophysics Data System (ADS)

    Dian, Brian; Clarkson, Jasper; Zwier, Timothy

    2003-03-01

    Using a combination of 2-color resonant two-photon ionization (R2PI), laser-induced fluorescence excitation (LIF), resonant ion-dip infrared spectroscopy (RIDIRS), fluorescence-dip infrared spectroscopy (FDIRS), and UV-UV hole-burning spectroscopy, the conformational preferences of a series of flexible biomolecules, including melatonin, N-acetyl-tryptophan methyl amide (NATMA), and their close analogs, have been determined in a molecular beam. These molecules are sufficiently complex to have hundreds of conformational minima, yet small enough that their potential energy landscapes can be explored in some detail. Once the conformational preferences of the molecules are established, these molecules are then studied using infrared-ultraviolet hole-filling and IR-induced population transfer spectroscopy. These methods utilize selective infrared excitation of single conformations of the molecule in the early portions of a gas-phase expansion, followed by collisional re-cooling of the excited population into its conformational minima for subsequent conformation-specific detection. Efficient isomerization is induced by the infrared excitation that redistributes population between the same conformations that have population in the absence of infrared excitation. Examples will be given in which the quantum yields for transfer of the population into the various conformational minima depend both on which conformation is excited and on which hydride stretch vibration is excited within a given conformation; that is, they are both conformation-selective and mode-selective.

  12. Isomerization of 1-butene on silica-alumina: Kinetic modeling and catalyst deactivation

    SciTech Connect

    Garcia-Ochoa, F.; Santos, A. . Dept. de Ingenieria Quimica)

    1995-02-01

    In the study of 1-butene isomerization on a silica-alumina catalyst 448--523 K, cis-2-butene and trans-2-butene are detected. Based on BSTR experimental data and zero-time prediction kinetic models using the Langmuir-Hinshelwood mechanism are assumed to develop kinetic equations for which a triangular reaction scheme is used. In four different mechanisms, one and two active sites take part in the surface reaction as the controlling step and then the deactivation rate determined considering two types of experimental data from BSTR and by measuring weight changes of a catalyst particle from coke deposition in an electrobalance. A coke precursor is assumed formed by reaction of adsorbed molecules (of any butene isomer) and gas-phase molecules. Activity and coke-content-time data allow one to choose a model whose activation energies of the deactivation kinetic parameter are closer in value. Coke is assumed deposited in a monolayer. The model chosen shows a triangular scheme, kinetic equations of the reaction for fresh catalyst with two active sites in the surface reaction, and the deactivation rate according to a coke formation mechanism in which a precursor is formed by reaction of 3 adsorbed molecules and 1 molecule in the gas phase. It accurately fits both BSTR conversion-time data and electrobalance coke-content data. The coke formation mechanism establishes relationships of activity vs. coke content and catalyst acidity which are supported by experimental results.

  13. Cyanides and isocyanides of first-row transition metals: molecular structure, bonding, and isomerization barriers.

    PubMed

    Rayón, Víctor M; Redondo, Pilar; Valdés, Haydee; Barrientos, Carmen; Largo, Antonio

    2007-07-19

    Cyanides and isocyanides of first-row transition metal M(CN) (M=Sc-Zn) are investigated with quantum chemistry techniques, providing predictions for their molecular properties. A careful analysis of the competition between cyanide and isocyanide isomers along the transition series has been carried out. In agreement with the experimental observations, late transition metals (Co-Zn) clearly prefer a cyanide arrangement. On the other hand, early transition metals (Sc-Fe), with the only exception of the Cr(CN) system, favor the isocyanide isomer. The theoretical calculations predict the following unknown isocyanides, ScNC(3Delta), TiNC(4Phi), VNC(5Delta), and MnNC(7Sigma+), and agree with the experimental observation of FeNC(6Delta) and the CrCN(6Sigma+) cyanide. First-row transition metal cyanides and isocyanides are predicted to have relatively large dissociation energies with values within the range 80-101 kcal mol(-1), except Zn(CN), which has a dissociation energy around 50-55 kcal mol(-1), and low isomerization barriers. A detailed analysis of the bonding has been carried out employing the topological analysis of the charge density and an energy decomposition analysis. The role of the covalent and electrostatic contributions to the metal-ligand bonding, as well as the importance of pi bonding, are discussed.

  14. Extrapolating Potential Energy Surfaces by Scaling Electron Correlation: Isomerization of Bicyclobutane to Butadiene

    NASA Astrophysics Data System (ADS)

    Lutz, Jesse J.; Piecuch, Piotr

    2008-04-01

    The recently proposed potential energy surface (PES) extrapolation scheme, which predicts smooth molecular PESs corresponding to larger basis sets from the relatively inexpensive calculations using smaller basis sets by scaling electron correlation energies [A.J.C. Varandas and P. Piecuch, Chem. Phys. Lett. 430,448 (2006)], is applied to the PESs associated with the conrotatory and disrotatory isomerization pathways of bicyclo[l.l.0]butane to buta-l,3-diene. The relevant electronic structure calculations are performed using the completely renormalized coupled-cluster method with singly and doubly excited clusters, and a non-iterative treatment of connected triply excited clusters, termed CR-CC(2,3). A comparison with the explicit CR-CC(2,3) calculations using the large correlation-consistent basis set of the cc-pVQZ quality shows that the cc-pVQZ PESs obtained by the extrapolation from the smaller basis set calculations employing the cc-pVDZ and cc-pVTZ basis sets are practically identical, to within fractions of a millihartree, to the true cc-pVQZ PESs. It is also demonstrated that one can use a similar extrapolation procedure to accurately predict the complete basis set (CBS) limits of the calculated PESs from the results of smaller basis set calculations at a fraction of the effort required by the conventional point-wise CBS extrapolations.

  15. Proline cis-trans isomerization is influenced by local lysine acetylation-deacetylation

    PubMed Central

    Howe, Françoise S.; Mellor, Jane

    2014-01-01

    Acetylation of lysine residues has several characterised functions in chromatin. These include neutralization of the lysine’s positive charge to directly influence histone tail-DNA/internucleosomal interactions or indirect effects via bromodomain-containing effector proteins. Recently, we described a novel function of lysine acetylation to influence proline isomerization and thus local protein conformation. We found that acetylation of lysine 14 in the histone H3 N-terminal tail (H3K14ac), an intrinsically disordered domain, increased the proportion of neighbouring proline 16 (H3P16) in the trans conformation. This conformation of the tail was associated with reduced tri-methylation on histone H3 lysine 4 (H3K4me3) due to both decreased methylation by the Set1 methyltransferase (with the me3-specific subunit Spp1) and increased demethylation by the demethylase Jhd2. Interestingly, H3K4me3 on individual genes was differentially affected by substitution of H3K14 or H3P16, with ribosomal protein genes losing the least H3K4me3 and environmental stress-induced genes losing the most. PMID:28357218

  16. DETECTION OF TWO ISOMERIC BINDING CONFIGURATIONS IN A PROTEIN-APTAMER COMPLEX WITH A BIOLOGICAL NANOPORE

    PubMed Central

    Van Meervelt, Veerle; Soskine, Misha; Maglia, Giovanni

    2015-01-01

    Protein-DNA interactions play critical roles in biological systems, and they often involve complex mechanisms and dynamics that are not easily measured by ensemble experiments. Recently, we have shown that folded proteins can be internalised inside ClyA nanopores and studied by ionic current recordings at the single-molecule level. Here, we use ClyA nanopores to sample the interaction between the G-quadruplex fold of the thrombin binding aptamer (TBA) and human thrombin (HT). Surprisingly, the internalisation of the HT:TBA complex inside the nanopore induced two types of current blockades with distinguished residual current and lifetime. Using single nucleobase substitutions to TBA we showed that these two types of blockades originate from TBA binding to thrombin with two isomeric orientations. Voltage dependencies and the use of ClyA nanopores with two different diameters allowed assessing the effect of the applied potential and confinement, and revealed that the two binding configurations of TBA to HT display different lifetimes. These results show that the ClyA nanopores might provide a new approach to probe conformational heterogeneity in protein:DNA interactions. PMID:25493908

  17. a Joint Theoretical and Experimental Study of the SiH_2OO Isomeric System

    NASA Astrophysics Data System (ADS)

    McCarthy, Michael C.; Gauss, Jürgen

    2015-06-01

    In contrast to the CH_2OO isomers, those of SiH_2OO have received relatively little attention, either theoretically or experimentally. High-level coupled cluster calculations predict a much different energy ordering in comparison to that found for CH_2OO, with the three conformers of Si-dihydroxycarbene, HOSiOH, most stable, followed by the Si-analogues of cis and trans formic acid, and then a cyclic isomer with C2v symmetry, c-SiH_2OO. Guided by these theoretical predictions, rotational lines of the cis, trans isomer of HOSiOH, as well as c-SiH_2OO, have been detected by Fourier transform microwave spectroscopy. The lines of the cyclic form are sufficiently strong that several rare isotopic species have also been found, enabling, in combination with calculated vibrational corrections, a precise semi-experimental structure to be derived. This talk will provide a status report on our joint study of this unusual isomeric system, and an update on searches for still other isomers.

  18. LC-MSn Analysis of Isomeric Chondroitin Sulfate Oligosaccharides Using a Chemical Derivatization Strategy

    PubMed Central

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

    2011-01-01

    Improved methods for structural analyses of glycosaminoglycans (GAGs) are required to understand their functional roles in various biological processes. Major challenges in structural characterization of complex GAG oligosaccharides using liquid chromatography-mass spectrometry (LC-MS) include the accurate determination of the patterns of sulfation due to gas-phase losses of the sulfate groups upon collisional activation and inefficient on-line separation of positional sulfation isomers prior to MS/MS analyses. Here, a sequential chemical derivatization procedure including permethylation, desulfation, and acetylation was demonstrated to enable both on-line LC separation of isomeric mixtures of chondroitin sulfate (CS) oligosaccharides and accurate determination of sites of sulfation by MSn. The derivatized oligosaccharides have sulfate groups replaced with acetyl groups, which are sufficiently stable to survive MSn fragmentation and reflect the original sulfation patterns. A standard reversed-phase LC-MS system with a capillary C18 column was used for separation, and MSn experiments using collision-induced dissociation (CID) were performed. Our results indicate that the combination of this derivatization strategy and MSn methodology enables accurate identification of the sulfation isomers of CS hexasaccharides with either saturated or unsaturated nonreducing ends. Moreover, derivatized CS hexasaccharide isomer mixtures become separable by LC-MS method due to different positions of acetyl modifications. PMID:21953261

  19. Pharmacokinetics and tissue distribution of two novel isomerism anticancer platinum compounds.

    PubMed

    He, Donglin; Yin, Shuhui; Han, Fuguo; Zhu, Jingjie; Shi, Yun; Tong, Zhiyuan; Liu, Qingfei

    2016-11-01

    LLC-0601(S,S) and LLC-0601(R,R) are two novel synthesized isomerism platinum compounds both with encouraging anticancer activity. However, the previous study showed that toxicity of LLC-0601(R,R) was much higher than that of LLC-0601(S,S) with higher body weight loss and mortality rate of tested rats. This paper is focused on the comparison of the two compounds with their pharmacokinetic (PK) profiles in rats and tissue distribution in mice after intravenous administration. The atomic absorption spectrometry (AAS) method was successfully developed and applied for the determination of platinum in plasma and tissues. The results showed that main PK parameters such as half-life, AUC and MRT of the two compounds had no significant difference after intravenous administration to rats (p  > 0.05). The tissue distribution after intravenous administration to mice showed that the concentration of LLC-0601(R,R) in heart at 0.083 h was higher than that of LLC-0601(S,S) (p  < 0.05) and it was the same case for AUC5min-4 h (p  < 0.05). Different distribution of the two compounds in heart was possibly the main reason of different toxicity and more in-depth research on the metabolites and other mechanism are needed to investigate the toxicity.

  20. Simulated (n,f) cross section of isomeric 235m-U

    SciTech Connect

    Becker, J; Britt, H; Younes, W

    2003-12-18

    The neutron-induced fission cross section on the {sup 235}U, T{sub 1/2} {approx} 26 min isomer has been deduced for incident neutron energies in the range E{sub n}=0.1-2.5 MeV, using the surrogate-reaction technique. In this technique, {sup 236}U fission probabilities measured in the {sup 234}U(t, pf) reaction have been converted into {sup 235}U(n,f) and {sup 235m}U(n,f) cross sections, using reaction theory to compensate for the differences in angular-momentum and parity distributions in the fissioning systems, transferred by the (t,p) and neutron-induced reactions. Based on the comparison between the {sup 235}U(n,f) cross section extracted in this work and independent experimental data, the deduced {sup 235m}U(n,f) cross section is believed to be reliable to 20% below E{sub n} {approx} 0.5 MeV and 10% at higher energies. The surrogate-reaction technique, its validation in the case of the {sup 235}U(n,f) cross section, and the deduced {sup 235m}U(n,f) cross section are discussed. Validation of this method allows (n,f) cross sections for many short-lived nuclei, as well as isomeric nuclei, to be extracted from measured fission probabilities.

  1. Interfaces Select Specific Stereochemical Conformations: The Isomerization of Glyoxal at the Liquid Water Interface.

    PubMed

    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.

  2. Understanding M-ligand bonding and mer-/fac-isomerism in tris(8-hydroxyquinolinate) metallic complexes.

    PubMed

    Lima, Carlos F R A C; Taveira, Ricardo J S; Costa, José C S; Fernandes, Ana M; Melo, André; Silva, Artur M S; Santos, Luís M N B F

    2016-06-28

    Tris(8-hydroxyquinolinate) metallic complexes, Mq3, are one of the most important classes of organic semiconductor materials. Herein, the nature of the chemical bond in Mq3 complexes and its implications on their molecular properties were investigated by a combined experimental and computational approach. Various Mq3 complexes, resulting from the alteration of the metal and substitution of the 8-hydroxyquinoline ligand in different positions, were prepared. The mer-/fac-isomerism in Mq3 was explored by FTIR and NMR spectroscopy, evidencing that, irrespective of the substituent, mer- and fac-are the most stable molecular configurations of Al(iii) and In(iii) complexes, respectively. The relative M-ligand bond dissociation energies were evaluated experimentally by electrospray ionization tandem mass spectrometry (ESI-MS-MS), showing a non-monotonous variation along the group (Al > In > Ga). The results reveal a strong covalent character in M-ligand bonding, which allows for through-ligand electron delocalization, and explain the preferred molecular structures of Mq3 complexes as resulting from the interplay between bonding and steric factors. The mer-isomer reduces intraligand repulsions, being preferred for smaller metals, while the fac-isomer is favoured for larger metals where stronger covalent M-ligand bonds can be formed due to more extensive through-ligand conjugation mediated by metal "d" orbitals.

  3. Characterization of Secondary Amide Peptide Bonds Isomerization: Thermodynamics and Kinetics from 2D NMR Spectroscopy

    PubMed Central

    Zhang, Jin; Germann, Markus W.

    2011-01-01

    Secondary amide cis peptide bonds are of even lower abundance than the cis tertiary amide bonds of prolines, yet they are of biochemical importance. Using 2D NMR exchange spectroscopy we investigated the formation of cis peptide bonds in several oligopeptides: Ac-G-G-G-NH2, Ac-I-G-G-NH2, Ac-I-G-G-N-NH2 and its cyclic form: I-G-G-N in DMSO. From the NMR studies, using the amide protons as monitors, an occurrenc.e of 0.13% – 0.23% of cis bonds was obtained at 296 K. The rate constants for the trans to cis conversion determined from 2D EXSY spectroscopy were 4–9·10−3 s−1. Multiple minor conformations were detected for most peptide bonds. From their thermodynamic and kinetic properties the cis isomers are distinguished from minor trans isomers that appear because of an adjacent cis peptide bond. Solvent and sequence effects were investigated utilizing N-methylacetamide and various peptides, which revealed an unique enthalpy profile in DMSO. The cyclization of a tetrapeptide resulted in greatly lowered cis populations and slower isomerization rate compared to its linear counterpart, further highlighting the impact of structural constraints. PMID:21538331

  4. KSHV Reactivation and Novel Implications of Protein Isomerization on Lytic Switch Control

    PubMed Central

    Guito, Jonathan; Lukac, David M.

    2015-01-01

    In Kaposi’s sarcoma-associated herpesvirus (KSHV) oncogenesis, both latency and reactivation are hypothesized to potentiate tumor growth. The KSHV Rta protein is the lytic switch for reactivation. Rta transactivates essential genes via interactions with cofactors such as the cellular RBP-Jk and Oct-1 proteins, and the viral Mta protein. Given that robust viral reactivation would facilitate antiviral responses and culminate in host cell lysis, regulation of Rta’s expression and function is a major determinant of the latent-lytic balance and the fate of infected cells. Our lab recently showed that Rta transactivation requires the cellular peptidyl-prolyl cis/trans isomerase Pin1. Our data suggest that proline‑directed phosphorylation regulates Rta by licensing binding to Pin1. Despite Pin1’s ability to stimulate Rta transactivation, unchecked Pin1 activity inhibited virus production. Dysregulation of Pin1 is implicated in human cancers, and KSHV is the latest virus known to co-opt Pin1 function. We propose that Pin1 is a molecular timer that can regulate the balance between viral lytic gene expression and host cell lysis. Intriguing scenarios for Pin1’s underlying activities, and the potential broader significance for isomerization of Rta and reactivation, are highlighted. PMID:25588053

  5. GC-IRD methods for the identification of isomeric ethoxyphenethylamines and methoxymethcathinones.

    PubMed

    Belal, Tarek; Awad, Tamer; DeRuiter, Jack; Clark, C Randall

    2009-01-30

    A series of 12 isomeric phenethylamines were evaluated by gas chromatography using vapor phase infrared spectrophotometric detection. The major mass spectral fragments for each of these unique isomers occur at equivalent mass and all have equal molecular weight. The infrared spectra for these compounds allow for identification of any one of these amines to the exclusion of all other isomers. This differentiation is accomplished without the need for chemical derivatization. The methoxymethcathinones show unique infrared absorption bands in the 1690-1700 cm(-1) range for the carbonyl group and the ring substitution pattern in the ethoxymethamphetamines can be differentiated by several bands in the 700-1610 cm(-1) region. Side chain and degree of nitrogen substitution can be evaluated in the 2770-3000 cm(-1) region of the infrared range. All the studied regioisomers could be differentiated from 3,4-MDMA via their vapor phase IR spectra. Capillary gas chromatography on an Rxi-50 stationary phase successfully resolved the side chain regioisomers, the substituted methamphetamines and the methoxymethcathinones.

  6. Electron Anisotropy as a Signature of Mode Specific Isomerization in Vinylidene

    NASA Astrophysics Data System (ADS)

    Gibson, Stephen T.; Laws, Benjamin A.; Mabbs, Richard; Neumark, Daniel; Lineberger, Carl; Field, Robert W.

    2016-06-01

    he nature of the isomerization process that turns vinylidene into acetylene has been awaiting advances in experimental methods, to better define fractionation widths beyond those available in the seminal 1989 photoelectron spectrum measurement. This has proven a challenge. The technique of velocity-map imaging (VMI) is one avenue of approach. Images of electrons photodetached from vinylidene negative-ions, at various wavelengths, 1064 nm shown, provide more detail, including unassigned structure, but only an incremental improvement in the instrument line width. Intriguingly, the VMIs demonstrate a mode dependent variation in the electron anisotropy. Most notable in the figure, the inner-ring transition clusters are discontinuously, more isotropic. Electron anisotropy may provide an alternative key to examine the character of vinylidene transitions, mediating the necessity for an extreme resolution measurement. Vibrational dependent anisotropy has previously been observed in diatomic photoelectron spectra, associated with the coupling of electronic and nuclear motions. Research supported by the Australian Research Council Discovery Project Grant DP160102585. K. M. Ervin, J. Ho, and W. C. Lineberger, J. Chem. Phys. 91, 5974 (1989). doi:10.1063/1.457415 M. van Duzor et al. J. Chem. Phys. 133, 174311 (2010). doi:10.1063/1.3493349

  7. {gamma}-vibrational states in superheavy nuclei

    SciTech Connect

    Sun Yang; Long Guilu; Al-Khudair, Falih; Sheikh, Javid A.

    2008-04-15

    Recent experimental advances have made it possible to study excited structure in superheavy nuclei. The observed states have often been interpreted as quasiparticle excitations. We show that in superheavy nuclei collective vibrations systematically appear as low-energy excitation modes. By using the microscopic Triaxial Projected Shell Model, we make a detailed prediction on {gamma}-vibrational states and their E2 transition probabilities to the ground state band in fermium and nobelium isotopes where active structure research is going on, and in {sup 270}Ds, the heaviest isotope where decay data have been obtained for the ground-state and for an isomeric state.

  8. Differential Gelation and Self-Sorting Properties of Two Isomeric Polyamides Due to the Parallel vs Anti-Parallel Alignment of Backbone Dipoles.

    PubMed

    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.

  9. Activation and isomerization of n-butane on sulfated zirconia model systems--an integrated study across the materials and pressure gaps.

    PubMed

    Breitkopf, C; Papp, H; Li, X; Olindo, R; Lercher, J A; Lloyd, R; Wrabetz, S; Jentoft, F C; Meinel, K; Förster, S; Schindler, K-M; Neddermeyer, H; Widdra, W; Hofmann, A; Sauer, J

    2007-07-21

    Butane activation has been studied using three types of sulfated zirconia materials, single crystalline epitaxial films, nanocrystalline films, and powders. A surface phase diagram of zirconia in interaction with SO(3) and water was established by DFT calculations, which was verified by LEED investigations on single-crystalline films and by IR spectroscopy on powders. At high sulfate surface densities a pyrosulfate species is the prevailing structure in the dehydrated state; if such species are absent, the materials are inactive. Theory and experiment show that the pyrosulfate can react with butane to give butene, H(2)O and SO(2), hence butane can be activated via oxidative dehydrogenation. This reaction occurred on all investigated materials; however, isomerization could only be proven for powders. Transient and equilibrium adsorption measurements in a wide pressure and temperature range (isobars measured via UPS on nanocrystalline films, microcalorimetry and temporal analysis of products measurements on powders) show weak and reversible interaction of butane with a majority of sites but reactive interaction with <5 micromol g(-1) sites. Consistently, the catalysts could be poisoned by adding sodium to the surface in a ratio S/Na = 35. Future research will have to clarify what distinguishes these few sites.

  10. Lysergamides of isomeric 2,4-dimethylazetidines map the binding orientation of the diethylamide moiety in the potent hallucinogenic agent N,N-diethyllysergamide (LSD).

    PubMed

    Nichols, David E; Frescas, Stewart; Marona-Lewicka, Danuta; Kurrasch-Orbaugh, Deborah M

    2002-09-12

    Lysergic acid amides were prepared from (R,R)-(-)-, (S,S)-(+)-, and cis-2,4-dimethyl azetidine. The dimethylazetidine moiety is considered here to be a rigid analogue of diethylamine, and thus, the target compounds are all conformationally constrained analogues of the potent hallucinogenic agent, N,N-diethyllysergamide, LSD-25. Pharmacological evaluation showed that (S,S)-(+)-2,4-dimethylazetidine gave a lysergamide with the highest LSD-like behavioral activity in the rat two lever drug discrimination model that was slightly more potent than LSD itself. This same diastereomer also had the highest affinity and functional potency at the rat serotonin 5-HT(2A) receptor, the presumed target for hallucinogenic agents, and a receptor affinity profile in a panel of screens that was most similar to that of LSD itself. Both cis- and the (R,R)-trans-dimethylazetidines gave lysergamides that were less potent in all relevant assays. The finding that the S,S-dimethylazetidine gave a lysergamide with pharmacology most similar to LSD indicates that the N,N-diethyl groups of LSD optimally bind when they are oriented in a conformation distinct from that observed in the solid state by X-ray crystallography. The incorporation of isomeric dialkylazetidines into other biologically active molecules may be a useful strategy to model the active conformations of dialkylamines and dialkylamides.

  11. Non-adiabatic dynamics investigation of the radiationless decay mechanism of trans-urocanic acid in the S2 state

    NASA Astrophysics Data System (ADS)

    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.

  12. Counteranion and solvent assistance in ruthenium-mediated alkyne to vinylidene isomerizations.

    PubMed

    Jiménez-Tenorio, Manuel; Puerta, M Carmen; Valerga, Pedro; Ortuño, Manuel A; Ujaque, Gregori; Lledós, Agustí

    2013-08-05

    The complex [Cp*RuCl((i)Pr2PNHPy)] (1) reacts with 1-alkynes HC≡CR (R = COOMe, C6H4CF3) in dichloromethane furnishing the corresponding vinylidene complexes [Cp*Ru═C═CHR((i)Pr2PNHPy)]Cl (R = COOMe (2a-Cl), C6H4CF3 (2b-Cl)), whereas reaction of 1 with NaBPh4 in MeOH followed by addition of HC≡CR (R = COOMe, C6H4CF3) yields the metastable π-alkyne complexes [Cp*Ru(η(2)-HC≡CR)((i)Pr2PNHPy)][BPh4] (R = COOMe (3a-BPh4), C6H4CF3 (3b-BPh4)). The transformation of 3a-BPh4/3b-BPh4 into their respective vinylidene isomers in dichloromethane is very slow and requires hours to its completion. However, this process is accelerated by addition of LiCl in methanol solution. Reaction of 1 with HC≡CR (R = COOMe, C6H4CF3) in MeOH goes through the intermediacy of the π-alkyne complexes [Cp*Ru(η(2)-HC≡CR)((i)Pr2PNHPy)]Cl (R = COOMe (3a-Cl), C6H4CF3 (3b-Cl)), which rearrange to vinylidenes in minutes, i.e., much faster than their counterparts containing the [BPh4](-) anion. The kinetics of these isomerizations has been studied in solution by NMR. With the help of DFT studies, these observations have been interpreted in terms of chloride- and methanol-assisted hydrogen migrations. Calculations suggest participation of a hydrido-alkynyl intermediate in the process, in which the hydrogen atom can be transferred from the metal to the β-carbon by means of species with weak basic character acting as proton shuttles.

  13. pH-Stimulated Reconfiguration and Structural Isomerization of Origami Dimer and Trimer Systems.

    PubMed

    Wu, Na; Willner, Itamar

    2016-10-12

    Reversible pH-responsive dimer or trimer origami structures are assembled by bridging origami frames with pH-responsive units. The cyclic pH-stimulated separation and reassembly of dimer origami structures is demonstrated using i-motif or Hoogsteen-type (C-G·C(+) or T-A·T) interactions. The duplex-bridged dimer T1-T2 is separated by the pH-induced formation of an i-motif structure (pH = 4.5), and the dimer is reassembled at pH = 7.0. The duplex-bridged dimer, T3-T4, is separated at pH = 4.5 through the formation of C-G·C(+) triplex structures and is reassembled to the dimer at pH = 7.0. Similarly, the T-A·T triplex-bridged dimer, T5-T6, is separated at pH = 9.5 and is reassembled at neutral pH. Finally, a trimer, T3-T7-T6, that includes C-G·C(+) and T-A·T pH-responsive bridges reveals pH-programmed cleavage to selectively yield the dimers T3-T7 or T7-T6, which reassemble to the trimer at pH = 7.0. A linear three-frame origami structure bridged by duplexes including caged i-motif units undergoes pH-stimulated isomerization to a bent structure (pH = 4.5) through the formation of i-motif complex and bridging T-A·T triplex units.

  14. A computational investigation of HCN2+ isomeric structures: implications for the chemistry of Titan's atmosphere.

    PubMed

    Antoniotti, Paola; Borocci, Stefano; Bronzolino, Nicoletta; Grandinetti, Felice

    2004-09-20

    The structure and stability of various HCN2+ isomeric structures have been investigated at the complete active space SCF (CASSCF) and multireference-configuration interaction [MR-Cl-SD(Q)] levels of theory with the 6-31G(d) and 6-311G(d,p) basis sets. The investigated species include the singlet (S) and triplet (T) open-chain H-N-C-N+ ions 1S, 1S', and 1T, the open-chain H-C-N-N+ ions 2S, 2S', and 2T, the HC-N2+ cyclic structures 3S and 3T, and the HN-CN+ cyclic structures 4S and 4T. All these species have been identified as true energy minima on the CASSCF(8,7)/6-31G(d) potential energy surface, and their optimised geometries, refined at the CASSCF(8,8)/6-31G(d) level of theory, have been used to perform single point calculations at the [MR-Cl-SD(Q]/6-311G(d,p) computational level. The most stable structure was the H-N-C-N+ ion 1T, whose absolute enthalpy of formation at 298.15 K has been estimated as 333.9 +/- 2 kcalmol(-1) using the Gaussian-3 (G3) procedure. The two species closest in energy to 1T are the triplet H-C-N-N+ ion 2T and the singlet diazirinyl cation 3S, whose G3 enthalpies of formation at 298.15 K are 343.5 +/- 2 and 340.6 +/- 2 kcalmol(-1), respectively. Finally, we have discussed the implications of our calculations for the detailed structure of the HCN2+ ions formed in the reaction between N3+ and HCN, experimentally observed by flowing after-glow-selected ion flow/drift tube mass spectrometry and possibly occurring in Titan's atmosphere.

  15. Two isomeric lead(II) carboxylate-phosphonates: syntheses, crystal structures and characterizations

    NASA Astrophysics Data System (ADS)

    Lei, Chong; Mao, Jiang-Gao; Sun, Yan-Qiong

    2004-07-01

    Two isomeric layered lead(II) carboxylate-phosphonates of N-(phosphonomethyl)- N-methyl glycine ([MeN(CH 2CO 2H)(CH 2PO 3H 2)]=H 3L), namely, monoclinic Pb 3L 2·H 2O 1 and triclinic Pb 3L 2·H 2O 2, have been synthesized and structurally determined. Compound 1 synthesized by hydrothermal reaction at 150°C is monoclinic, space group C2/ c with a=19.9872(6), b=11.9333(1) and c=15.8399(4) Å, β=110.432(3)°, V=3540.3(1) Å 3, and Z=8. The structure of compound 1 features a <400> layer in which the lead(II) ions are bridged by both phosphonate and carboxylate groups. The lattice water molecules are located between the layers, forming hydrogen bonds with the non-coordinated carboxylate oxygen atoms. Compound 2 with a same empirical formula as compound 1 was synthesized by hydrothermal reaction at 170°C. It has a different layer structure from that of compound 1 due to the adoption of a different coordination mode for the ligand. It crystallizes in the triclinic system, space group P 1¯ with cell parameters of a=7.1370(6), b=11.522(1), c=11.950(1) Å, α=110.280(2), β=91.625(2), γ=95.614(2)°, V=915.3(1) Å 3 and Z=2. The structure of compound 2 features a <020> metal carboxylate-phosphonate double layer built from 1D lead(II) carboxylate chains interconnected with 1D lead(II) phosphonate double chains. XRD powder patterns of compounds 1 and 2 indicate that each compound exists as a single phase.

  16. Cis→Trans Isomerization of Pro7 in Oxytocin Regulates Zn2+ Binding

    NASA Astrophysics Data System (ADS)

    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.

  17. Synthesis and Photoirradiation of Isomeric Ethylchrysenes by UVA Light Leading to Lipid Peroxidation

    PubMed Central

    Chen, Hui-Chan; Xia, Qingsu; Cherng, Shu-Hui; Chen, Shoujun; Lai, Ching-Cheng; Yu, Hongtao; Fu, Peter P.

    2007-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are widespread genotoxic environmental pollutants. We have recently demonstrated that photoirradiation of PAHs leads to cytotoxicity, DNA damage, and induction of lipid peroxidation. In this paper we report the synthesis of all the six isomeric ethylchrysenes and the study of light-induced lipid peroxidation by these ethylchrysenes. 5-Ethylchrysene was synthesized by reaction of 5-keto-5,6,6a,7,8,9,10,10a-octahydrochrysene with CH3CH2MgBr followed by dehydration catalyzed by p-toluenesulfonic acid and dehydrogenation with DDQ in benzene. 1- and 4-Ethylchrysenes were similarly prepared by reaction of 1-keto-1,2,3,4,5,6-hexahydrochrysene and 4-keto-1,2,3,4-tetrahydrochrysenes, respectively with CH3CH2MgBr followed by dehydration and dehydrogenation. Direct acetylation of chrysene followed by Wolff-Kishner or Clemmensen reduction resulted in the formation of 2-, 3-, and 6-ethylchrysenes in 4%, 16%, and 43% yields, respectively. Photoirradiation of these compounds with 7 and 21 J/cm2 UVA light in the presence of methyl linoleate all resulted in lipid peroxidation. For comparison, photoirradiation of 4-methylchrysene and 5-methylchrysene was similarly conducted. For irradiation at a UVA light dose of 21 J/cm2, the level of induced lipid peroxidation is in the order 4-methylchrysene = 5-methylchrysene = 5-ethylchrysene = 4-ethylchrysene = chrysene > 1-ethylchrysene = 2-ethylchrysene > 3-ethylchrysene > 6-ethylchrysene. Compared with chrysene, these results indicate that the ethyl group at C4 or C5 position either slightly enhances or has no effect on the light-induced lipid peroxidation, while at C1-, C2-, C3-, or C6 position reduces light-induced lipid peroxidation. PMID:17617678

  18. Cis→Trans Isomerization of Pro(7) in Oxytocin Regulates Zn(2+) Binding.

    PubMed

    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 Zn(2+) to the nine-residue peptide hormone oxytocin (OT, Cys(1)-Tyr(2)-Ile(3)-Gln(4)-Asn(5)-Cys(6)-Pro(7)-Leu(8)-Gly(9)-NH2, having a disulfide bond between Cys(1) and Cys(6) residues). Zn(2+) 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 Zn(2+), we find evidence for two primary OT conformations, which arise because the Cys(6)-Pro(7) peptide bond exists in both the trans- and cis-configurations. Upon addition of Zn(2+), 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 Zn(2+) bound form of OT, having a cross section of Ω = 235 Å(2), has Pro(7) 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 Zn(2+) binds to the peptide ring and is further coordinated by interaction of the C-terminal, Pro(7)-Leu(8)-Gly(9)-NH2, tail. The present work shows that the cis-configuration of OT isomerizes to the trans-configuration upon binding Zn(2+). In this way, the proline residue regulates Zn(2+) binding to OT and, hence, is important in receptor binding. Graphical Abstract ᅟ.

  19. Isomeric Distinction of Small Oligosaccharides: A Bottom-Up Approach Using the Kinetic Method

    NASA Astrophysics Data System (ADS)

    Major, Mohamed; Fouquet, Thierry; Charles, Laurence

    2011-07-01

    Isomeric distinction of di- and tri-saccharides could be efficiently achieved by using data previously obtained while performing experiments aimed at discriminating monosaccharides using trimeric ion dissociation with data analysis by the kinetic method. This study shows that effects observed for lower homologues when one of the partners is changed in the metal/reference system (typically a transition metal divalent cation associated to amino acids) can be extrapolated to upper homologues, at least for the tested analyte series. Systems allowing galactose, glucose, and fructose distinction were used as starting conditions to resolve cellobiose, lactose, maltose, and saccharose disaccharides. When a unique dissociation reaction was observed from the trimeric clusters, a new reference was selected based on its propensity to favor the analyte or the reference release, as revealed from monosaccharide experiments, depending on the desired effect. The same approach could be implemented from data obtained for disaccharides to select efficient metal/reference systems to distinguish cellotriose, isomaltotriose, maltotriose, and panose trisaccharides. As a result, method optimization is greatly improved due to an enhanced rationalization of the search for discriminant systems. While 40 systems had to be tested for monosaccharides, by screening five transition metals and eight amino acids, the proposed approach allowed efficient metal/reference systems to be found for disaccharides after testing 18 combinations; then, only four systems had to be scrutinized to achieve trisaccharide distinction. Accurate quantitative analyses could be performed in binary mixtures using three-point calibration curves to correct for competition effects between analytes for the formation of the trimeric clusters.

  20. Light-induced isomerization causes an increase in the chromophore tilt in the M intermediate of bacteriorhodopsin: a neutron diffraction study.

    PubMed Central

    Hauss, T; Büldt, G; Heyn, M P; Dencher, N A

    1994-01-01

    Bacteriorhodopsin (BR) was regenerated with two selectively deuterated retinals, one with 11 deuterons in the beta-ionone ring (D11) and the other with 5 deuterons (D5) at the end of the polyene chain closest to the Schiff base at carbon atoms C-14, C-15, and C-20. Both label positions (centers of deuteration) were obtained from difference Fourier maps of projections onto the plane of the membrane by neutron diffraction at 90 K, both in the light-adapted ground-state BR568 and in the photocycle intermediate M412. To retard the decay of M412, purple membrane films were soaked in 0.1 M or 1 M guanidine hydrochloride at pH 9.6. M412 was produced by illuminating oriented membrane films at physiological temperature (278 K), followed by rapid cooling to 90 K in the absence of light. The results show that in the projected structure the ring position is unaltered during the transition from BR568 to M412, whereas the position of the D5 label shifts by 1.4 +/- 0.9 A toward the ring. The shortened interlabel distance in the projected structure for the M412 state implies that as a result of the all-trans/13-cis isomerization, the C-5 to C-13 part of the polyene chain tilts out of the plane of the membrane toward the cytoplasm by about 11 degrees +/- 6 degrees. Pairwise comparison of data sets with the same retinal for the two photocycle states M412 and BR568 leads to four difference-density maps for the protein, which are in agreement with previous work. They show changes in the protein density near helices G and F. PMID:7991546

  1. Isomerization of 5-Hydroxy-5-methylhydantoin 2'-Deoxynucleoside into α-Furanose, β-Furanose, α-Pyranose, and β-Pyranose Anomers.

    PubMed

    Ali, Anum; Wagner, J Richard

    2016-01-19

    Oxidative damage is one of the most frequent types of DNA damage resulting from biologically generated oxygen or nitrogen reactive species. Hydroxyl radicals, one electron oxidants, and various chemical oxidants, such as permanganate and ozone, react with pyrimidine bases in DNA, cytosine and thymine, to produce 5-hydroxyhydantoin derivatives. 5-Hydroxyhydantoin modifications are interesting because they undergo ring-chain tautomerism into a pair of diastereomers via an open chain carbonyl intermediate. Here, we show that purified diastereomers of N1-(2-deoxy-β-D-erythro-pentofuranosyl)-5-hydroxy-5-methylhydantoin not only undergo isomerization into a mixture of 5R and 5S diastereomers of the hydantoin ring but also into three additional pairs of diastereomers, in which the sugar moiety transforms into α-furanose, β-pyranose, and α-pyranose anomers. The novel 5-hydroxy-5-methylhydantoin derivatives were characterized by extensive NMR analyses. Further studies indicate that isomerization is greatly suppressed at pH 6 compared to that at higher pH. A novel mechanism of isomerization is proposed to account for the formation of nucleoside anomers at neutral pH, which involves ring-chain tautomerism of both the hydantoin and sugar moieties. Last, the isomerization of β-furanose into the corresponding α-furanose is shown to take place in purified DNA, albeit to a slower extent than that in solution. The ability of 5-hydroxyhydantoin nucleosides to undergo isomerization may complicate the biological processing of this damage in cellular DNA.

  2. Anharmonic Rice-Ramsperger-Kassel-Marcus (RRKM) and product branching ratio calculations for the partially deuterated protonated water dimers: Dissociation and isomerization

    NASA Astrophysics Data System (ADS)

    Song, Di; Su, Hongmei; Kong, Fan-ao; Lin, Sheng-Hsien

    2013-03-01

    Partially deuterated protonated water dimers, H2O.H+.D2O, H2O.D+.HDO, and HDO.H+.HDO, as important intermediates of isotopic labeled reaction of H3O+ + D2O, undergo direct dissociation and indirect dissociation, i.e., isomerization before the dissociation. With Rice-Ramsperger-Kassel-Marcus theory and ab initio calculations, we have computed their dissociation and isomerization rate constants separately under the harmonic and anharmonic oscillator models. On the basis of the dissociation and isomerization rate constants, branching ratios of two primary products, [HD2O+]/[H2DO+], are predicted under various kinetics models with the harmonic or anharmonic approximation included. The feasible kinetics model accounting for experimental results is shown to include anharmonic effect in describing dissociation, while adopting harmonic approximation for isomerization. Thus, the anharmonic effect is found to play important roles affecting the dissociation reaction, while isomerization rates are shown to be insensitive to whether the anharmonic or harmonic oscillator model is being applied.

  3. A Novel Chromone Schiff-Base Fluorescent Chemosensor for Cd(II) Based on C=N Isomerization.

    PubMed

    Yan, Jun; Fan, Long; Qin, Jing-Can; Li, Chao-Rui; Yang, Zheng-Yin

    2016-05-01

    A new chromone Schiff-base fluorescent probe 7'-methoxychromone-3'-methylidene-1,2,4-triazole-3-imine (L) was designed and synthesized for selective recognition Cd(2+). With the fluorescence titration and the ESI-MS data, we reach the conclusion that the binding mode of the ligand-metal (L-Cd (2+) ) complex is 1:1. The sensor showed a strong fluorescence enhancement in ethanol system of Cd(2+) (excitation 409 nm and emission 462 nm) and the sensing mechanism based on the fact that C=N isomerization can be used to explain this phenomenon.

  4. Stabilization and isomerization of radical cations generated by fast electron irradiation of unsaturated organic molecules in a solid argon matrix

    NASA Astrophysics Data System (ADS)

    Feldman, V. I.; Sukhov, F. F.; Orlov, A. Yu.; Tyulpina, I. V.; Ivanchenko, V. K.

    2006-01-01

    Matrix isolation EPR spectroscopy was used to study the fate of "hot" unsaturated radical cations produced by fast electron irradiation in solid argon. It was found that the radical cations of cis-2-butene, trans-2-butene and ethyl vinyl ether resulting from highly exothermic hole transfer (excess energy>6 eV) underwent effective relaxation in an argon matrix. 1-Butene radical cation exhibits isomerization to cis-2-butene radical cation. The role of molecular structure of organic radical cations in excess energy relaxation is discussed.

  5. A Photoresponsive Surface Covalent Organic Framework: Surface-Confined Synthesis, Isomerization, and Controlled Guest Capture and Release.

    PubMed

    Liu, Chunhua; Zhang, Wei; Zeng, Qingdao; Lei, Shengbin

    2016-05-10

    By introducing an azobenzene group to the backbone of diboronic acid, we have obtained a surface-confined, photoresponsive single-layer covalent organic framework with long-range order and almost entire surface coverage. Scanning tunneling microscopic characterization indicates that though the covalent linkage provides a significant locking effect, isomerization can still happen under UV irradiation, which causes destruction of the surface COF. Furthermore, the decomposed surface COF can recover upon annealing. This photoinduced decomposition provides a facile approach for the controlled capture and release of targeted objects using these nanoporous surface COFs as a host, which has been demonstrated in this work using copper phthalocyanine as a model guest.

  6. Unprecedented Dawson isomerism induced by a central [WO5] and four 45°-rotated belt square pyramids.

    PubMed

    Xu, Xin; Dong, Huan-Li; Sang, Rui-Li; Xu, Li

    2012-12-28

    The seventh type of Wells-Dawson isomer, δ-[(WO(5))W(17)Cu(H(2)O)O(55)](10-) (1a) was obtained as a consequence of the formation of the first central square-pyramidal [WO(5)] moiety that results in a 45° rotation of the four belt [CuO(5)]/[WO(5)] square pyramids, establishing a new type of WD isomerism involving the rotation of the belt polyhedra, that were previously believed to stay unchanged.

  7. Sensitivity enhancement of electro-optic polymer probing system using photo-isomerization and Fabry-Pérot effects

    NASA Astrophysics Data System (ADS)

    Kuo, Wen-Kai; Su, Tzu-Mao; Ke, Zong-You; Lin, Hui-Chi; Wu, Chien-Jang

    2013-07-01

    A sensitivity enhancement method for an external electro-optic (EO) probing system using a poled polymer as an EO sensor is proposed. A pumping laser, which induces the photo-isomerization effect in a prepoled EO polymer, and a tunable probing laser, which induces Fabry-Pérot effect, are combined to enhance the polymer EO sensor sensitivity. Results of an experiment with an EO sensor made of Disperse Red 1 poly(methy1 methacrylate) that demonstrates this combined effect are reported.

  8. The oxidation of n-butane and n-heptane in a CFR engine; Isomerization reactions and delay of autoignition

    SciTech Connect

    Sahetchian, K.A.; Blin, N.; Rigny, R.; Seydi, A. ); Murat, M. )

    1990-03-01

    During the oxidation of {ital n}-butane in a flow system and also in a motored CFR engine (600 rpm) hydrogen peroxide, primary and secondary butylhydroperoxides, and peracetic acid are formed. In the CFR engine these peroxides appear only when the compression ratio is larger than 10:1 ({ital T}{sub max} = 650 K). No autoignition has been observed. A comparison of {ital n}-butane and {ital n}-heptane oxidation is presented. Isomerization reactions,which are correlated with the alkane structure and the octane number, account for the differences in the experimental results.

  9. Improved bond-orbital calculations of rotation barriers and geometrical isomerism

    NASA Astrophysics Data System (ADS)

    Musso, Gian Franco; Magnasco, Valerio

    Rotational barriers in 19 molecules possessing a single internal rotation angle around a B-N, C-C, C-N, C-O, N-N, N-O, O-O central bond and geometrical isomerism in 3 molecules possessing a N=N double bond have been studied ab initio by the improved bond-orbital method. The first approximation, where the chemical groups occurring in these molecules are described in terms of non-orthogonal SCF bond-orbitals constructed from energy-optimized bond hybrids and polarities, is improved in second order of perturbation theory by admitting single excitations from bonding to antibonding orbitals and accounting for induction including exchange (polarization and delocalization). The molecules studied possess 16 to 34 electrons and a variety of functional groups differing in their chemical structure (CH3, NH2, OH, NO, CHO, CH=CH2, NH= and some of their F-derivatives). The overall results obtained using a STO-3G basis, rigid rotation and experimental geometries, are close to experiment and to the corresponding MO-SCF calculations in the same basis, but individual energy components allow us to establish a clear correlation between barriers and chemical structure, grouping the 22 molecules into 4 classes. In the first class (CH3-X molecules and 1,2-difluoroethane) barriers are dominated by steric interactions (Pauli repulsions) which are sufficiently well described in first order. In the second class (N2H4, NH2OH, NH=NH and its fluoroderivatives, molecules all possessing lone pairs adjacent to the central bond) barriers are due to competition between first-order Pauli repulsion and characteristic geminal σ-σ* delocalization occurring in second order. In the third class (1,3-butadiene, glyoxal, formamide and formic acid, molecules possessing double bonds and/or π-lone pairs at both ends of the rotation axis) barriers are dominated by large π-π* vicinal delocalization. In the fourth class (HNO2, H2O2 and its fluoroderivatives, molecules presenting both previous structural

  10. Synthesis and Isomeric Analysis of Ru(II) Complexes Bearing Pentadentate Scaffolds.

    PubMed

    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.

  11. Syn/anti isomerization of 2,4-dinitrophenylhydrazones in the determination of airborne unsymmetrical aldehydes and ketones using 2,4-dinitrophenylhydrazine derivation.

    PubMed

    Binding, N; Müller, W; Witting, U

    1996-10-01

    Aldehydes and ketones readily react with 2,4-dinitrophenylhydrazine (2,4-DNPH) to form the corresponding hydrazones. This reaction has been frequently used for the quantification of airborne carbonyl compounds. Since unsymmetrical aldehydes and ketones are known to form isomeric 2,4-dinitrophenylhydrazones (syn/ anti-isomers), the influence of isomerization on the practicability and accuracy of the 2,4-DNPH-method using 2,4-dinitrophenylhydrazine-coated solid sorbent samplers has been studied with three ketones (methyl ethyl ketone (MEK), methyl isopropyl ketone (MIPK), and methyl isobutyl ketone (MIBK)). With all three ketones the reaction with 2,4-DNPH resulted in mixtures of the isomeric hydrazones which were separated by HPLC and GC and identified by mass spectroscopy and (1)H nuclear magnetic resonance spectroscopy. The isomers show similar chromatographic behaviour in HPLC as well as in GC, thus leading to problems in quantification and interpretation of chromatographic results.

  12. ‘Horror vacui’ or topological in-out isomerism in perhydrogenated fullerenes: C60H60 and monoalkylated perhydrogenated fullerenes

    NASA Astrophysics Data System (ADS)

    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.

  13. Parity violation in the γ-decay of polarized 93Tc nuclei in the {17}/{2}- isomeric state

    NASA Astrophysics Data System (ADS)

    Hass, M.; Broude, C.; Weissman, L.; Müller, L.; Montagnoli, G.; Scarlassara, F.; Segato, G. F.; Signorini, C.; Goldring, G.; Ackermann, D.; Bednarczyk, P.; Corradi, L.; Spolaore, P.; Lindroos, M.; Hormann, S.; Ninov, V.; Hessberger, F. P.; Soramel, F.; Takahashi, N.; Brown, B. A.

    1996-02-01

    We report on a determination of the parity nonconserving (PNC) matrix element in the bound parity doublet {17 -}/{2} - {17 +}/{2} of 93Tc. The experiment was carried out at the GSI, Darmstadt and LNL, Legnaro laboratories. The recoil-mass-separated radioactive beam of 93Tc nuclei in the {17 -}/{2} isomer, following a fusion-evaporation reaction, was polarized by the tilted-foil method and the resulting 0°-180° γ asymmetry with respect to the induced polarization direction was measured by two large-volume Ge detectors. The measured γ asymmetry of 3-σ significance, Aγ = 8.4(2.7) · 10 -4, yields a matrix element of |< {17 -}/{2}|H pnc| {17 +}/{2}>| = 0.59(19)(25) meV. This experimental result is c microscopic calculations based on the DDH “best value” interaction for the nuclear weak Hamiltonian. We discuss our results and their significance with respect to the existing data regarding PNC effects in bound nuclear systems.

  14. Playing with isomerism and N substitution in pentalenedione derivatives for organic electrode batteries: how high are the stakes?

    PubMed

    Tomerini, Daniele; Gatti, Carlo; Frayret, Christine

    2016-01-28

    New concepts to design innovating and top-performing redox-active organic molecules based electrodes should push forward and promote an eco-friendly alternative to classical Li-ion batteries. In this promising research area, density functional theory calculations lend support to experiments through the prediction of redox voltage and give promise to rationalize the trends, thus providing a general approach for engineering advanced materials. In this study in which we analysed spin density/net atomic charges distribution along with global energy decomposition thanks to Bader's partitioning of the molecular space, a vision for designing pentalenedione derivatives by fine tuning of the redox potential properties is presented. The concept relies on combined effects of isomerism and N single/double substitution for CH on the parent backbone. Such dual nature modification is able to provide a series of compounds within the range of 2.2-3.6 V vs. Li(+)/Li (against a more restricted range of 2.2-2.8 V vs. Li(+)/Li for the sole effect of isomerism on the unsubstituted parent compounds). The incidence of double N substitution alone generally follows an almost additive rule based on the combined actions of the composing single N substitutions. Few exceptions to the rule were, however, also observed and rationalized. Beyond learning gained for this peculiar family, these results may have exciting implications for future design strategies.

  15. Analysis of ECs and related compounds in plasma: artifactual isomerization and ex vivo enzymatic generation of 2-MGs[S

    PubMed Central

    Pastor, Antoni; Farré, Magí; Fitó, Montserrat; Fernandez-Aranda, Fernando; de la Torre, Rafael

    2014-01-01

    The analysis of peripheral endocannabinoids (ECs) is a good biomarker of the EC system. Their concentrations, from clinical studies, strongly depend on sample collection and time processing conditions taking place in clinical and laboratory settings. The analysis of 2-monoacylglycerols (MGs) (i.e., 2-arachidonoylglycerol or 2-oleoylglycerol) is a particularly challenging issue because of their ex vivo formation and chemical isomerization that occur after blood sample collection. We provide evidence that their ex vivo formation can be minimized by adding Orlistat, an enzymatic lipase inhibitor, to plasma. Taking into consideration the low cost of Orlistat, we recommend its addition to plasma collecting tubes while maintaining sample cold chain until storage. We have validated a method for the determination of the EC profile of a range of MGs and N-acylethanolamides in plasma that preserves the original isomer ratio of MGs. Nevertheless, the chemical isomerization of 2-MGs can only be avoided by an immediate processing and analysis of samples due to their instability during conservation. We believe that this new methodology can aid in the harmonization of the measurement of ECs and related compounds in clinical samples. PMID:24610889

  16. Surface chemistry and catalytic performance of amorphous NiB/Hβ catalyst for n-hexane isomerization

    NASA Astrophysics Data System (ADS)

    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.

  17. Chemical kinetics of 5-o-caffeoylquinic acid in superheated steam: effect of isomerization on mate (Ilex paraguariensis) manufacturing.

    PubMed

    Zanoelo, Everton Fernando; Benincá, Cristina

    2009-12-23

    A set of experiments was carried out to investigate the chemical stability of 5-o-caffeoylquinic acid (5-CQA) in the presence of superheated steam. A batch cylindrical reactor made of glass and isothermally operated between 398 and 499 K was used in the experiments. A high-performance liquid chromatograph equipped with a diode array detector was applied to monitor the 5-CQA concentrations. The conversions of 5-CQA were correctly reproduced with a simplified kinetic model represented by a reversible pseudofirst-order reaction of isomerization. The effect of temperature on the forward rate constant was represented by the Arrhenius equation with parameters tuned on experimental data. The heat of isomerization of 5-CQA and the equilibrium constant at 298 K were calculated by involving the integrated form of the van't Hoff equation. The observed reaction was revealed to not be detrimental for the quality of manufactured leaves and branches of mate because the content of total chlorogenic acids was not changed.

  18. Titanium-Beta Zeolites Catalyze the Stereospecific Isomerization of D-Glucose to L-Sorbose via Intramolecular C5-C1 Hydride Shift

    SciTech Connect

    Gounder, Rajamani; Davis, Mark E.

    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

  19. Unimolecular isomerization of CH2FCD2Cl via the interchange of Cl and F atoms: assignment of the threshold energy to the 1,2-dyotropic rearrangement.

    PubMed

    Tucker, Mary K; Rossabi, Samuel M; McClintock, Corey E; Heard, George L; Setser, D W; Holmes, Bert E

    2013-08-08

    The room-temperature gas-phase recombination of CH2F and CD2Cl radicals was used to prepare CH2FCD2Cl molecules with 91 kcal mol(-1) of vibrational energy. Three unimolecular processes are in competition with collisional deactivation of CH2FCD2Cl; HCl and DF elimination to give CHF═CD2 and CH2═CDCl plus isomerization to give CH2ClCD2F by the interchange of F and Cl atoms. The Cl/F interchange reaction was observed, and the rate constant was assigned from measurement of CHCl═CD2 as a product, which is formed by HF elimination from CH2ClCD2F. These experiments plus previously published results from chemically activated CH2ClCH2F and electronic structure and RRKM calculations for the kinetic-isotope effects permit assignment of the three rate constants for CH2FCD2Cl (and for CH2ClCD2F). The product branching ratio for the interchange reaction versus elimination is 0.24 ± 0.04. Comparison of the experimental rate constant with the RRKM calculated rate constant permitted the assignment of a threshold energy of 62 ± 3 kcal mol(-1) for this type-1 dyotropic rearrangement. On the basis of electronic structure calculations, the nature of the transition state for the rearrangement reaction is discussed. The radical recombination reactions in the chemical system also generate vibrationally excited CD2ClCD2Cl and CH2FCH2F molecules, and the rate constants for DCl and HF elimination were measured in order to confirm that the photolysis of CD2ClI and (CH2F)2CO mixtures was giving reliable data for CH2FCD2Cl.

  20. Two highly connected POM-based hybrids varying from 2D to 3D: The use of the isomeric ligands

    SciTech Connect

    Zhang Chunjing; Pang Haijun; Hu Mixia; Li Jia; Chen Yaguang

    2009-07-15

    Through employing two isomeric ligands, isonicotinic acid (HINA) and nicotinic acid (HNA), with different electron delocalization nature, two high-dimensional hybrids based on highly connected alpha-metatungstate clusters, [Na{sub 2}(H{sub 2}O){sub 8}Ag{sub 2}(HINA){sub 3}(INA)][Na(H{sub 2}O){sub 2}Ag{sub 2}(HINA){sub 4}(H{sub 2}W{sub 12}O{sub 40})].2H{sub 2}O (1) and [Na{sub 2}(H{sub 2}O){sub 4}Ag{sub 6}(HNA){sub 2}(NA){sub 2}(H{sub 2}W{sub 12}O{sub 40})].8H{sub 2}O (2), have been conventionally synthesized and structurally characterized. 1 exhibits an unusual 1D-in-2D pseudo-polyrotaxane entangled structure, namely, the 2D sheets [Na(H{sub 2}O){sub 2}Ag{sub 2}(HINA){sub 4}(H{sub 2}W{sub 12}O{sub 40})]{sub n}{sup 3n-} are penetrated by enantiomorphous meso-helical chains [Na{sub 2}(H{sub 2}O){sub 8}Ag{sub 2}(HINA){sub 3}(INA)]{sub n}{sup 3n+}. In the 2D sheets, each [H{sub 2}W{sub 12}O{sub 40}]{sup 6-} cluster is surrounded by six Ag and two Na atoms. 2 exhibits a 3D (4, 6)-net structure with (3{sup 2}6{sup 2}7{sup 2})(3{sup 2}4{sup 4}5{sup 4}6{sup 4}7)(3{sup 2}4{sup 4}6{sup 8}7) topology, in which each [H{sub 2}W{sub 12}O{sub 40}]{sup 6-} cluster is connected with ten Ag atoms. These facts indicate that the isomeric ligands play a key role in the formation of final structures. From 1 to 2, the connection number of the [H{sub 2}W{sub 12}O{sub 40}]{sup 6-} cluster changes from 8 to 10 and the dimensionality increases from 2 to 3. Moreover, 1 and 2 display photoluminescent properties in the blue range at room temperature. - Graphical abstract: Two high-dimensional and highly connected alpha-metatungstate-compounds modified by Ag{sup I}-HINA/HNA TMCs were successful obtained and the effect of isomeric organic ligands on the structures was systematically elucidated.

  1. Transient-Absorption Spectroscopy of Cis-Trans Isomerization of N,N-dimethyl-4,4'-Azodianiline with 3D-Printed Temperature-Controlled Sample Holder

    ERIC Educational Resources Information Center

    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…

  2. The 181Ta(7Li,5n)183Os reaction: Measurement and analysis of the excitation function and isomeric cross-section ratios

    NASA Astrophysics Data System (ADS)

    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.

  3. Characterization of isomeric VX nerve agent adducts on albumin in human plasma using liquid chromatography-tandem mass spectrometry.

    PubMed

    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.

  4. Volumetric study of the mixtures n-hexane + isomeric chlorobutane: experimental characterization and volume translated Peng-Robinson predictions.

    PubMed

    Guerrero, Hernando; Cea, Pilar; Gascón, Ignacio; Royo, Félix M; Lafuente, Carlos

    2013-09-05

    The pρTx behavior of the binary mixtures n-hexane + isomeric chlorobutane has been studied over the whole composition range at temperatures between 283.15 and 323.15 K and pressures from 0.1 to 65.0 MPa. Experimental densities have been used to obtain different excess properties: excess molar volume, excess isobaric expansibility, excess isothermal compressibility, and excess internal pressure. These excess properties have been analyzed in terms of molecular interactions and structural effects. Finally, experimental densities of the binary mixtures have been compared with the predictions of the volume translated Peng-Robinson (VTPR) model. The overall average deviation between experimental and calculated densities is 0.00427 g·cm(-3), which can be considered reasonably good predictions.

  5. Phosphorylation and metabolism of sucrose and its five linkage-isomeric alpha-D-glucosyl-D-fructoses by Klebsiella pneumoniae.

    PubMed

    Thompson, J; Robrish, S A; Pikis, A; Brust, A; Lichtenthaler, F W

    2001-03-22

    Not only sucrose but the five isomeric alpha-D-glucosyl-D-fructoses trehalulose, turanose, maltulose, leucrose, and palatinose are utilized by Klebsiella pneumoniae as energy sources for growth, thereby undergoing phosphorylation by a phosphoenolpyruvate-dependent phosphotransferase system uniformly at 0-6 of the glucosyl moiety. Similarly, maltose, isomaltose, and maltitol, when exposed to these conditions, are phosphorylated regiospecifically at O-6 of their non-reducing glucose portion. The structures of these novel compounds have been established unequivocally by enzymatic analysis, acid hydrolysis, FAB negative-ion spectrometry, and 1H and 13C NMR spectroscopy. In cells of K. pneumoniae, hydrolysis of sucrose 6-phosphate is catalyzed by sucrose 6-phosphate hydrolase from Family 32 of the glycosylhydrolase superfamily. The five 6'-O-phosphorylated alpha-D-glucosyl-fructoses are hydrolyzed by an inducible (approximately 49-50 Kda) phospho-alpha-glucosidase from Family 4 of the glycosylhydrolase superfamily.

  6. Conversion of alkanes to linear alkylsilanes using an iridium-iron-catalysed tandem dehydrogenation-isomerization-hydrosilylation

    NASA Astrophysics Data System (ADS)

    Jia, Xiangqing; Huang, Zheng

    2016-02-01

    The conversion of inexpensive, saturated hydrocarbon feedstocks into value-added speciality chemicals using regiospecific, catalytic functionalization of alkanes is a major goal of organometallic chemistry. Linear alkylsilanes represent one such speciality chemical—they have a wide range of applications, including release coatings, silicone rubbers and moulding products. Direct, selective, functionalization of alkanes at primary C-H bonds is difficult and, to date, methods for catalytically converting alkanes into linear alkylsilanes are unknown. Here, we report a well-defined, dual-catalyst system for one-pot, two-step alkane silylations. The system comprises a pincer-ligated Ir catalyst for alkane dehydrogenation and an Fe catalyst that effects a subsequent tandem olefin isomerization-hydrosilylation. This method exhibits exclusive regioselectivity for the production of terminally functionalized alkylsilanes. This dual-catalyst strategy has also been applied to regioselective alkane borylations to form linear alkylboronate esters.

  7. The role of nonbonding interactions and the presence of fluoride on the conformational isomerism of 1,2-ethanediol

    NASA Astrophysics Data System (ADS)

    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.

  8. Elemental isomerization processes for a photochromic diarylethene film based on carrier injection toward all-electrically operable organic memory

    NASA Astrophysics Data System (ADS)

    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.

  9. Theoretical study on the formation of tetraoxygen conformational isomerism in the CO 2 with O 3 reaction

    NASA Astrophysics Data System (ADS)

    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.

  10. A semiclassical study of cis-trans isomerization in HONO using an interpolating moving least-squares potential

    NASA Astrophysics Data System (ADS)

    Pham, Phong; Guo, Yin

    2013-04-01

    The interpolating moving least-squares (IMLS) approach for constructing potential energy surfaces has been developed and employed in standard classical trajectory simulations in the past few years. We extend the approach to the tunneling regime by combining the IMLS fitting method and the semiclassical scheme that incorporates tunneling into classical trajectory calculations. Dynamics of cis-trans isomerization in nitrous acid (HONO) is studied as a test case to investigate various aspects of the approach such as the strategy for growing the surface, the basis set employed, the scaling of the IMLS fits, and the accuracy of the surface required for obtaining converged rate coefficients. The validity of the approach is demonstrated through comparison with other semiclassical and quantum mechanical studies on HONO.

  11. Identification of isomeric dicaffeoylquinic acids from Eleutherococcus senticosus using HPLC-ESI/TOF/MS and 1H-NMR methods.

    PubMed

    Tolonen, Ari; Joutsamo, Topi; Mattlla, Sampo; Kämäräinen, Terttu; Jalonen, Jorma

    2002-01-01

    Liquid chromatography-electrospray time-of-flight mass spectrometry (HPLC-ESI/TOF/MS) and a novel NMR technique, developed to maximise the sensitivity obtained from the standard NMR spectrometer, have been applied to the identification of the phenolic constituents of Eleutherococcus senticosus. In addition, molecular modelling and dihedral bond angle calculations based on the vicinal 3JHH-coupling constants have been used in the unambiguous assignment of signals in the 1H-NMR spectra. 5'-O-Caffeoylquinic acid and three isomeric compounds, 1',5'-O-dicaffeoylquinic acid, 3',5'-O-dicaffeoylquinic acid and 4',5'-O-dicaffeoylquinic acid, have been isolated and identified from a sample. The isolation and structure determination of the latter two compounds are reported for the first time from this plant.

  12. Resolution and quantification of isomeric fatty acids by silver ion HPLC: fatty acid composition of aniseed oil (Pimpinella anisum, Apiaceae).

    PubMed

    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.

  13. Solvated molecular dynamics of LiCN isomerization: All-atom argon solvent versus a generalized Langevin bath.

    PubMed

    Junginger, Andrej; Garcia-Muller, Pablo L; Borondo, F; Benito, R M; Hernandez, Rigoberto

    2016-01-14

    The reaction rate rises and falls with increasing density or friction when a molecule is activated by collisions with the solvent particles. This so-called Kramers turnover has recently been observed in the isomerization reaction of LiCN in an argon bath. In this paper, we demonstrate by direct comparison with those results that a reduced-dimensional (generalized) Langevin description gives rise to similar reaction dynamics as the corresponding (computationally expensive) full molecular dynamics calculations. We show that the density distributions within the Langevin description are in direct agreement with the full molecular dynamics results and that the turnover in the reaction rates is reproduced qualitatively and quantitatively at different temperatures.

  14. Adaptive single replica multiple state transition interface sampling

    NASA Astrophysics Data System (ADS)

    Du, Wei-Na; Bolhuis, Peter G.

    2013-07-01

    The multiple state transition path sampling method allows sampling of rare transitions between many metastable states, but has the drawback that switching between qualitatively different pathways is difficult. Combination with replica exchange transition interface sampling can in principle alleviate this problem, but requires a large number of simultaneous replicas. Here we remove these drawbacks by introducing a single replica sampling algorithm that samples only one interface at a time, while efficiently walking through the entire path space using a Wang-Landau approach or, alternatively, a fixed bias. We illustrate the method on several model systems: a particle diffusing in a simple 2D potential, isomerization in a small Lennard Jones cluster, and isomerization of the alanine dipeptide in explicit water.

  15. LC-ESI-QTOF-MS based screening and identification of isomeric jujubogenin and pseudojujubogenin aglycones in Bacopa monnieri extract.

    PubMed

    Nuengchamnong, Nitra; Sookying, Sontaya; Ingkaninan, Kornkanok

    2016-09-10

    Bacopa monnieri (L.) Wettst. (Scrophulariaceae) is an Ayurvedic medicinal plant used as a memory enhancer. Its major chemical constituents are Bacopa saponins consisting of jujubogenin and pseudojujubogenin glycosides. These two aglycones are isomers different at the positions of prenyl substitution i.e., at C-23 for jujubogenin and at C-22 for pseudojujubogenin. In this study, we demonstrate the rapid and comprehensive characterization of saponin glycosides in B. monnieri using liquid chromatography with electrospray ionization quadrupole time-of-flight mass spectrometer (LC-ESI-QTOF-MS). This shows that ESI-QTOF-MS in positive-ion mode, jujubogenin and pseudojujubogenin glycosides could be discriminated by the peak abundance ratio of m/z 455 [Aglycone+H-H2O](+) to m/z of 473 [Aglycone+H](+). Furthermore, the sequence of sugar moieties can be observed. In a similar manner, the isomeric saponins; deoxyjujubogenin and deoxypseudojujubogenin glycosides can be distinguished using the m/z 437[Aglycone+H-H2O](+) and m/z 455[Aglycone+H](+) peak ratio. Use of the negative-ion mode with MS/MS fragmentation can provide information about the type of sugar linked to the aglycone i.e., at m/z 633 (aglycone+glucose) or at m/z 603 (aglycone+arabinose). With our method, 62 chemical constituents in B. monnieri including saponin glycosides, flavonoids, and alkaloids were identified. This is the first systematic study in structural characterization on isomeric saponins and other metabolites in B. monnieri using ESI-QTOF-MS.

  16. Purification and Quantification of an Isomeric Compound in a Mixture by Collisional Excitation in Multistage Mass Spectrometry Experiments.

    PubMed

    Jeanne Dit Fouque, Dany; Maroto, Alicia; Memboeuf, Antony

    2016-11-15

    The differentiation, characterization, and quantification of isomers and/or isobars in mixtures is a recurrent problem in mass spectrometry and more generally in analytical chemistry. Here we present a new strategy to assess the purity of a compound that is susceptible to be contaminated with another isomeric side-product in trace levels. Providing one of the isomers is available as pure sample, this new strategy allows the detection of isomeric contamination. This is done thanks to a "gas-phase collisional purification" inside an ion trap mass spectrometer paving the way for an improved analysis of at least similar samples. This strategy consists in using collision induced dissociation (CID) multistage mass spectrometry (MS(2) and MS(3)) experiments and the survival yield (SY) technique. It has been successfully applied to mixtures of cyclic poly(L-lactide) (PLA) with increasing amounts of its linear topological isomer. Purification in gas phase of PLA mixtures was established based on SY curves obtained in MS(3) mode: all samples gave rise to the same SY curve corresponding then to the pure cyclic component. This new strategy was sensitive enough to detect traces of linear PLA (<3%) in a sample of cyclic PLA that was supposedly pure according to other characterization techniques ((1)H NMR, MALDI-HRMS, and size-exclusion chromatography). Moreover, in this case, the presence of linear isomer was undetectable according to MS/MS or MS/MS/MS analysis only as fragment ions are also of the same m/z values. This type of approach could easily be implemented in hyphenated mass spectrometric techniques to improve the structural and quantitative analysis of complex samples.

  17. A pseudospectral solution of a Fokker-Planck equation to model isomerization reactions

    NASA Astrophysics Data System (ADS)

    Shizgal, Bernie D.

    2016-11-01

    A Fokker-Planck equation is used to model a reactive system with two stable states. The barrier of the potential that separates the states is controlled with a parameter, ɛ, that alters the height of the barrier that separates the two states of the system. The rate of transitions between the two states, equivalently the rate of reaction, can be treated with a transition state theory as for a large class of chemical reactions. The Fokker-Planck equation is solved with a pseudospectral method based on nonclassical basis polynomials. The time dependent solution is expressed in terms of the eigenvalues and eigenfunctions of the linear Fokker-Planck operator. This eigenvalue problem can be written as the solution of a Schrödinger equation with a potential function defined by the drift and diffusion coefficients in the Fokker-Planck equation.

  18. Synthesis, crystal structure and antimicrobial activities of two isomeric gold(I) complexes with nitrogen-containing heterocycle and triphenylphosphine ligands, [Au(L)(PPh3)] (HL = pyrazole and imidazole).

    PubMed

    Nomiya, K; Noguchi, R; Ohsawa, K; Tsuda, K; Oda, M

    2000-03-01

    Two isomeric gold(I)-triphenylphosphine complexes with nitrogen-containing heterocycles, [Au(L)(PPh3) (HL = pyrazole (1), imidazole (2)) were isolated as colorless cubic crystals for 1 and colorless plate crystals for 2, respectively. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction. These complexes were also fully characterized by complete elemental analyses, thermogravimetric/differential thermal analyses (TG/DTA) and FT-IR in the solid state and by solution NMR (31P, 1H and 13C) spectroscopy and molecular weight measurements in acetone solution. These complexes consisted of a monomeric 2-coordinate AuNP core both in the solid state and in solution. The molecular structures of 1 and 2 were compared with those of related gold(I) complexes, [Au(1,2,3-triz)(PPh3)] (3, Htriz = triazole), [Au(1,2,4-triz)(PPh3)]2 (4) as a dimer through a gold(I)-gold(I) bond in the solid state, and [Au(tetz)(PPh3)] (5, Htetz = tetrazole). Selective and effective antimicrobial activities against two gram-positive bacteria (B. subtilis, S. aureus) and modest activities against one yeast (C. albicans) found in these gold(I) complexes 1-4 are noteworthy, in contrast to poor activities observed in the corresponding silver(I) complexes.

  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.

    PubMed

    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.

    PubMed

    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. Isomerization of neopentyl chloride and neopentyl bromide by a 1,2-interchange of a halogen atom and a methyl group.

    PubMed

    Lisowski, Carmen E; Duncan, Juliana R; Ranieri, Anthony J; Heard, George L; Setser, D W; Holmes, Bert E

    2010-09-30

    The recombination of chloromethyl and t-butyl radicals at room temperature was used to generate neopentyl chloride molecules with 89 kcal mol(-1) of internal energy. The observed unimolecular reactions, which give 2-methyl-2-butene and 2-methyl-1-butene plus HCl, as products, are explained by a mechanism that involves the interchange of a methyl group and the chlorine atom to yield 2-chloro-2-methylbutane, which subsequently eliminates hydrogen chloride by the usual four-centered mechanism to give the observed products. The interchange isomerization process is the rate-limiting step. Similar experiments were done with CD(2)Cl and C(CH(3))(3) radicals to measure the kinetic-isotope effect to help corroborate the proposed mechanism. Density functional theory was employed at the B3PW91/6-31G(d',p') level to verify the Cl/CH(3) interchange mechanism and to characterize the interchange transition state. These calculations, which provide vibrational frequencies and moments of inertia of the molecule and transition state, were used to evaluate the statistical unimolecular rate constants. Matching the calculated and experimental rate constants, gave 62 ± 2 kcal mol(-1) as the threshold energy for interchange of the Cl atom and a methyl group. The calculated models also were used to reinterpret the thermal unimolecular reactions of neopentyl chloride and neopentyl bromide. The previously assumed Wagner-Meerwein rearrangement mechanism for these reactions can be replaced by a mechanism that involves the interchange of the halogen atom and a methyl group followed by HCl or HBr elimination from 2-chloro-2-methylbutane and 2-bromo-2-methylbutane. Electronic structure calculations also were done to find threshold energies for several related molecules, including 2-chloro-3,3-dimethylbutane, 1-chloro-2-methyl-2-phenylpropane, and 1-chloro-2-methyl-2-vinylpropane, to demonstrate the generality of the interchange reaction involving a methyl, or other hydrocarbon groups, and a

  2. Configurations and decay hindrances of high-K states in 180Hf

    NASA Astrophysics Data System (ADS)

    Tandel, S. K.; Chowdhury, P.; Kondev, F. G.; Janssens, R. V. F.; Khoo, T. L.; Carpenter, M. P.; Lauritsen, T.; Lister, C. J.; Seweryniak, D.; Zhu, S.; Deacon, A.; Freeman, S. J.; Hammond, N. J.; Jones, G. D.; Moore, E. F.; Smith, J. F.

    2016-12-01

    Multi-quasiparticle high-K states, several of which are isomeric, were observed in 180Hf with the Gammasphere array. Lifetimes in the ns-μ s range were determined using centroid-shift and decay measurements within a μ s coincidence time window. The configurations of high-K states involve two and four quasiparticles, with states up to Kπ=(18-) established. High-K excitations are found to be progressively more favored with increasing excitation energy. The K quantum number is quite robust up to the highest spins observed, as evidenced by the large values of the reduced hindrance for isomeric decays. Rotational bands built on three high-K states are identified, and the measured branching ratios in these sequences enable the assignment of underlying configurations. Multi-quasiparticle calculations using the Lipkin-Nogami approach for pairing, with blocking included, reproduce the observed high-K energies quite well.

  3. A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

    PubMed

    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. Unusually large secondary deuterium isotope effect. Thermal trans-cis isomerization of trans-1-phenylcyclohexene

    SciTech Connect

    Caldwell, R.A.; Misawa, H.; Healy, E.F.; Dewar, M.J.S.

    1987-10-28

    The magnitudes of secondary deuterium isotope effects (SDIE) are generally in the range of 0.9 < k/sub H//k/sub D/ < 1.25, and are often satisfactorily rationalized by the zero-point energy (ZPE) change on going from reactant to transition state due to C-H rehybridization. They now report a far larger SDIE for the title reaction. Its rationalization on the basis of transition state theory suggests that it more closely resembles a primary isotope effect.

  5. The 559-to-600 nm shift observed in red fluorescent protein eqFP611 is attributed to cis-trans isomerization of the chromophore in an anionic protein pocket.

    PubMed

    Yan, Weizhong; Xie, Daiqian; Zeng, Jun

    2009-08-07

    Fluorescent proteins are commonly used as molecular labels, noninvasive markers of gene expression, and reporters of environmental conditions in live cells. We investigate the structural and spectroscopic properties of the chromophore of a far-red fluorescent protein eqFP611. Both the cis and trans isomers of the chromophore are examined within the protein for which both anionic and neutral states of protonation are considered. Spectroscopic properties are examined using time-dependent density functional theory (TDDFT), employing the B3LYP, PBE and B3PW91 density functionals. Intermolecular and long-range contributions to the structure and spectroscopy were treated using the own n-layered integrated molecular orbital and molecular mechanics (ONIOM) approach. The results indicated that the chromophore before excitation is in an anionic, protonated state, with the long-range contributions inducing a blue shift in the absorption and fluorescence maxima of the chromophore. Moreover, the calculated changes of the lowest pi-pi* excitation energy upon isomerization match the observed shift from 559 to 600 nm in the absorption maximum of the system following prolonged irradiation. Furthermore, decomposition analysis of the electrostatic contributions from individual residues indicated that the interactions from four residues Arg92, Lys67, Glu145, and His197 to the chromophore play a key role in the absorption and fluorescence spectra of eqFP611, suggesting that mutations at these sites should provide very useful mechanistic information.

  6. N-Succinimidyl guanidinomethyl iodobenzoate protein radiohalogenation agents: Influence of isomeric substitution on radiolabeling and target cell residualization

    PubMed Central

    Choi, Jaeyeon; Vaidyanathan, Ganesan; Koumarianou, Eftychia; McDougald, Darryl; Pruszynski, Marek; Osada, Takuya; Lahoutte, Tony; Lyerly, H. Kim; Zalutsky, Michael R.

    2014-01-01

    Introduction N-succinimidyl 4-guanidinomethyl-3-[*I]iodobenzoate ([*I]SGMIB) has shown promise for the radioiodination of monoclonal antibodies (mAbs) and other proteins that undergo extensive internalization after receptor binding, enhancing tumor targeting compared to direct electrophilic radioiodination. However, radiochemical yields for [131I]SGMIB synthesis are low, which we hypothesize is due to steric hindrance from the Boc-protected guanidinomethyl group ortho to the tin moiety. To overcome this, we developed the isomeric compound, N-succinimidyl 3-guanidinomethyl-5-[131I]iodobenzoate (iso-[131I]SGMIB) wherein this bulky group was moved from ortho to meta position. Methods Boc2-iso-SGMIB standard and its tin precursor, N-succinimidyl 3-((1,2-bis(tert-butoxycarbonyl)guanidino)methyl)-5-(trimethylstannyl)benzoate (Boc2-iso-SGMTB), were synthesized using two disparate routes, and iso-[*I]SGMIB synthesized from the tin precursor. Two HER2-targeted vectors — trastuzumab (Tras) and a nanobody 5F7 (Nb) — were labeled using iso-[*I]SGMIB and [*I]SGMIB. Paired-label internalization assays in vitro with both proteins, and biodistribution in vivo with trastuzumab, labeled using the two isomeric prosthetic agents were performed. Results When the reactions were performed under identical conditions, radioiodination yields for the synthesis of Boc2-iso-[131I]SGMIB were significantly higher than those for Boc2-[131I]SGMIB (70.7 ± 2.0% vs 56.5 ± 5.5%). With both Nb and trastuzumab, conjugation efficiency also was higher with iso-[131I]SGMIB than with [131I]SGMIB (Nb, 33.1 ± 7.1% vs 28.9 ± 13.0%; Tras, 45.1 ± 4.5% vs 34.8 ± 10.3%); however, the differences were not statistically significant. Internalization assays performed on BT474 cells with 5F7 Nb indicated similar residualizing capacity over 6 h; however, at 24 h, radioactivity retained intracellularly for iso-[131I]SGMIB-Nb was lower than for [125I]SGMIB-Nb (46.4 ± 1.3% vs 56.5 ± 2.5%); similar results were

  7. Evaluation of the α-phenylvinyl cation as a chemical ionization reagent for the differentiation of isomeric substituted phenols in an ITMS.

    PubMed

    Begala, Michela

    2015-04-01

    Ion-molecule reactions between the α-phenylvinyl cation and isomeric naturally occurring phenols were investigated using a quadruple ion trap mass spectrometer. The α-phenylvinyl cation m/z 103, generated by chemical ionization from phenylacetylene, reacts with neutral aromatic compounds to form the characteristic species: [M + 103](+) adduct ions and the trans-vinylating product ions [M + 25](+) , which correspond to [M + 103](+) adduct after the loss of benzene. Isomeric differentiation of several ring-substituted phenols was achieved by using collision-induced dissociation of the [M + 103](+) adduct ions. This method also showed to be effective in the differentiation of 4-ethylguaiacol from one of its structural isomers that displays identical EI and EI/MS/MS spectra. The effects of gas-phase alkylation with phenylvinyl cation on the dissociation behavior were examined using mass spectrometry(n) and labeled derivatives. Copyright © 2015 John Wiley & Sons, Ltd.

  8. Chain folding controlled by an isomeric repeat unit: helix formation versus random aggregation in acetylene-bridged carbazole-bipyridine co-oligomers.

    PubMed

    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.

  9. First isomeric quadrupole moment measured in fragmentation reactions: The case of {sup 61}Fe{sup m}(9/2{sup +})

    SciTech Connect

    Vermeulen, N.; Yordanov, D. T.; Neyens, G.; Chamoli, S. K.; Hass, M.; Goldring, G.; Singh, B. S. Nara; Daugas, J. M.; Delaroche, J. P.; Girod, M.; Goutte, H.; Morel, P.; Perru, O.; Peru, S.; Roig, O.; Oliveira-Santos, F. de; Grevy, S.; Perrot, L.; Stefan, I.

    2007-05-15

    This paper demonstrates the feasibility of quadrupole moment measurements on isomeric levels populated in projectile fragmentation reactions. The neutron-rich {sup 61}Fe(9/2{sup +}) [E*= 861 keV, T{sub 1/2}= 239(5) ns] isomer was produced and spin aligned by the intermediate energy fragmentation of a {sup 64}Ni beam and implanted in a Cd single crystal. Its spectroscopic quadrupole moment |Q{sub s}|=41(6) e fm{sup 2} agrees with mean-field based calculations using the finite-range Gogny force, suggesting a moderately deformed shape characterized by an intrinsic charge quadrupole moment Q{sub 0}=-85 e fm{sup 2} or Q{sub 0}=+115 e fm{sup 2}. The present measurement paves the way for future determinations of isomeric quadrupole moments in more exotic nuclei.

  10. Infrared multiphoton induced isomerization and dissociation of FCN, ClCN, and BrCN in liquid Ar: A classical simulation study

    SciTech Connect

    Zhang Ming; Gong Jiangbin; Ma Ao; Rice, Stuart A.

    2007-10-14

    We report the results of classical mechanics simulations of infrared multiphoton induced control of isomerization of FCN, ClCN, and BrCN in liquid Ar, using ab initio potential energy and dipole moment surfaces for the XCN molecules. The field induced isomerization and fragmentation dynamics of these molecules are found to be different from that of HCN in liquid Ar. In particular, the scheme that provides complete controlled conversion of HCN to CNH in liquid Ar fails to generate complete conversion of XCN to CNX in liquid Ar for X=F,Cl,Br. It is suggested that the sources of the differences in behavior arise from differences in the spectra of vibrational nonlinear resonances in HCN and XCN and to the occurrence of monodromy in the dynamics of the XCN molecules.

  11. Platinum and Other Transition Metal Nanoclusters (Pd, Rh) Stabilized by PAMAM Dendrimer as Excellent Heterogeneous Catalysts: Application to the Methylcyclopentane (MCP) Hydrogenative Isomerization.

    PubMed

    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.

  12. Four-Quasiparticle High-K States in Neutron-Deficient Lead and Polonium Nuclei

    NASA Astrophysics Data System (ADS)

    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.

  13. High-K multi-quasiparticle states and rotational bands in {sub 103}{sup 255}Lr

    SciTech Connect

    Jeppesen, H. B.; Clark, R. M.; Gregorich, K. E.; Cromaz, M.; Deleplanque, M. A.; Dvorak, J.; Fallon, P.; Gros, S.; Lee, I. Y.; Macchiavelli, A. O.; Stavsetra, L.; Stephens, F. S.; Wiedeking, M.; Afanasjev, A. V.; Ali, M. N.; Dragojevic, I.; Ellison, P. A.; Garcia, M. A.; Gates, J. M.; Nelson, S. L.

    2009-09-15

    Two isomeric states have been identified in {sup 255}Lr. The decay of the isomers populates rotational structures. Comparison with macroscopic-microscopic calculations suggests that the lowest observed sequence is built upon the [624]9/2{sup +} Nilsson state. However, microscopic cranked relativistic Hartree-Bogoliubov (CRHB) calculations do not reproduce the moment of inertia within typical accuracy. This is a clear challenge to theories describing the heaviest elements.

  14. Kinetics of the competitive reactions of isomerization and peptide bond cleavage at l-α- and d-β-aspartyl residues in an αA-crystallin fragment.

    PubMed

    Aki, Kenzo; Okamura, Emiko

    2017-01-01

    d-β-aspartyl (Asp) residue has been found in a living body such as aged lens crystallin, although l-α-amino acids are constituents in natural proteins. Isomerization from l-α- to d-β-Asp probably modulates structures to affect biochemical reactions. At Asp residue, isomerization and peptide bond cleavage compete with each other. To gain insight into how fast each reaction proceeds, the analysis requires the consideration of both pathways simultaneously and independently. No information has been provided, however, about these competitive processes because each reaction has been studied separately. The contribution of Asp isomers to the respective pathways has still been veiled. In this work, the two competitive reactions, isomerization and spontaneous peptide bond cleavage at Asp residue, were simultaneously observed and compared in an αA-crystallin fragment, S(51) LFRTVLD(58) SG(60) containing l-α- and d-β-Asp58 isomers. The kinetics showed that the formation of l- and d-succinimide (Suc) intermediate, as a first step of isomerization, was comparable at l-α- and d-β-Asp. Although l-Suc was converted to l-β-Asp, d-Suc was liable to return to the original d-β-Asp, the reverse reaction marked enough to consider d-β-Asp as apparently stable. d-β-Asp was also resistant to the peptide bond cleavage. Such apparent less reactivity is probably the reason for gradual and abnormal accumulation of d-β-Asp in a living body under physiological conditions. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd.

  15. Sex pheromone of the European grapevine moth,Lobesia botrana Schiff. (Lepidoptera: Tortricidae): Synthesis and effect of isomeric purity on biological activity.

    PubMed

    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.

  16. Are the Radical Centers in Peptide Radical Cations Mobile? The Generation, Tautomerism, and Dissociation of Isomeric α-Carbon-Centered Triglycine Radical Cations in the Gas Phase

    SciTech Connect

    Chu, Ivan K.; Zhao, Junfang; Xu, Minjie; Siu, Shiu On; Hopkinson, Alan C.; Siu , K W Michael

    2008-05-31

    The mobility of the radical center in three isomeric triglycine radical cationss[G•GG]+, [GG•G]+, and [GGG•]+shas been investigated theoretically via density functional theory (DFT) and experimentally via tandem mass spectrometry. These radical cations were generated by collision-induced dissociations (CIDs) of Cu(II)-containing ternary complexes that contain the tripeptides YGG, GYG, and GGY, respectively (G and Y are the glycine and tyrosine residues, respectively). Dissociative electron transfer within the complexes led to observation of [Y•GG]+, [GY•G]+, and [GGY•]+; CID resulted in cleavage of the tyrosine side chain as p-quinomethide, yielding [G•GG]+, [GG•G]+, and [GGG•]+, respectively. Interconversions between these isomeric triglycine radical cations have relatively high barriers (g44.7 kcal/mol), in support of the thesis that isomerically pure [G•GG]+, [GG•G]+, and [GGG•]+ can be experimentally produced. This is to be contrasted with barriers < 17 kcal/mol that were encountered in the tautomerism of protonated triglycine [Rodriquez C. F. et al. J. Am. Chem. Soc. 2001, 123, 3006-3012]. The CID spectra of [G•GG]+, [GG•G]+, and [GGG•]+ were substantially different, providing experimental proof that initially these ions have distinct structures. DFT calculations showed that direct dissociations are competitive with interconversions followed by dissociation.

  17. Ruthenium(IV)-catalyzed isomerization of the C=C bond of o-allylic substrates: a theoretical and experimental study.

    PubMed

    Varela-Álvarez, Adrián; Sordo, José A; Piedra, Estefanía; Nebra, Noel; Cadierno, Victorio; Gimeno, José

    2011-09-12

    A general mechanism to rationalize Ru(IV) -catalyzed isomerization of the C=C bond in O-allylic substrates is proposed. Calculations supporting the proposed mechanism were performed at the MPWB1K/6-311+G(d,p)+SDD level of theory. All experimental observations in different solvents (water and THF) and under different pH conditions (neutral and basic) can be interpreted in terms of the new mechanism. Theoretical analysis of the transformation from precatalyst to catalyst led to structural identification of the active species in different media. The experimentally observed induction period is related to the magnitudes of the energy barriers computed for that process. The theoretical energy profile for the catalytic cycle requires application of relatively high temperatures, as is experimentally observed. Participation of a water molecule in the reaction coordinate is mechanistically essential when the reaction is carried out in aqueous medium. The new mechanistic proposal helped to develop a new experimental procedure for isomerization of allyl ethers to 1-propenyl ethers under neutral aqueous conditions. This process is an unique example of efficient and selective catalytic isomerization of allyl ethers in aqueous medium.

  18. Kinetics of thermal gas-phase isomerizations and fragmentations of cis- and trans-1-(E)-propenyl-2-methylcyclobutanes at 275 degrees C.

    PubMed

    Baldwin, John E; Burrell, Richard C

    2002-05-17

    Kinetic studies of the thermal isomerization and fragmentation reactions exhibited by cis- and trans-1-(E)-propenyl-2-methylcyclobutanes at 275 degrees C in the gas phase have provided first-order rate constants for cis,trans interconversions of the cyclobutanes, 1,3-carbon migrations leading to 3,4- and 3,6-dimethylcyclohexenes, isomerizations providing directly and indirectly four acyclic dienes, and fragmentations to ethylene, propene, and mixtures of pentadienes and hexadienes. Both cis and trans isomers of 1-(E)-propenyl-2-methylcyclobutane form trans-3,4-dimethylcyclohexene faster than they are converted to cis-3,4-dimethylcyclohexene; the trans reactant gives rise to cis-3,6-dimethylcyclohexene in preference to its trans isomer, while the cis starting material gives neither at measurable rates; both form the relatively minor product 1,6-(Z)-octadiene. The rate constants derived from 35 kinetic runs starting with four distinct 1-(E)-propenyl-2-methylcyclobutane samples are consistent to within narrow error limits. The stereomutations, isomerizations, and fragmentations of the 1-(E)-propenyl-2-methylcyclobutanes are interpreted in terms of competitive processes involving conformationally flexible short-lived 2-(E)-octene-4,7-diyl and 3-methyl-5-(E)-heptene-1,4-diyl diradicals.

  19. L-Arabinose binding, isomerization, and epimerization by D-xylose isomerase: X-ray/neutron crystallographic and molecular simulation study.

    PubMed

    Langan, Paul; Sangha, Amandeep K; Wymore, Troy; Parks, Jerry M; Yang, Zamin Koo; Hanson, B Leif; Fisher, Zoe; Mason, Sax A; Blakeley, Matthew P; Forsyth, V Trevor; Glusker, Jenny P; Carrell, Horace L; Smith, Jeremy C; Keen, David A; Graham, David E; Kovalevsky, Andrey

    2014-09-02

    D-xylose isomerase (XI) is capable of sugar isomerization and slow conversion of some monosaccharides into their C2-epimers. We present X-ray and neutron crystallographic studies to locate H and D atoms during the respective isomerization and epimerization of L-arabinose to L-ribulose and L-ribose, respectively. Neutron structures in complex with cyclic and linear L-arabinose have demonstrated that the mechanism of ring-opening is the same as for the reaction with D-xylose. Structural evidence and QM/MM calculations show that in the reactive Michaelis complex L-arabinose is distorted to the high-energy (5)S1 conformation; this may explain the apparent high KM for this sugar. MD-FEP simulations indicate that amino acid substitutions in a hydrophobic pocket near C5 of L-arabinose can enhance sugar binding. L-ribulose and L-ribose were found in furanose forms when bound to XI. We propose that these complexes containing Ni(2+) cofactors are Michaelis-like and the isomerization between these two sugars proceeds via a cis-ene-diol mechanism.

  20. Isomerization and epimerization of the aspartyl tetrapeptide Ala-Phe-Asp-GlyOH at pH 10-A CE study.

    PubMed

    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.