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101.
102.
We report density functional and coupled cluster calculations on numerous monocyclic and bicyclic (CH)12(*-) isomers. At the RCCSD(T)/cc-pVDZ//UB3LYP/6-31+G* level, a nearly planar, bond-equalized radical anion of 1,7-di-trans-[12]annulene (4a(*-)) is lowest in energy; several other isomers and conformations lie within 3 kcal/mol of 4a(*-). RCCSD(T)/AUG-cc-pVDZ//UB3LYP/6-31+G* results place the all-cis isomer 3(*-) slightly below 4a(*-) in energy. Validation studies on the heptalene radical anion, [16]annulene radical anion, and tri-trans-[12]annulene radical anion indicate that electron spin resonance (ESR) hyperfine coupling constants (aH values) computed at the BLYP/EPR-III level on DFT geometries give much better agreement with experimental values than those computed using B3LYP/6-31G*. We were unable to locate any C12H12(*-) isomer that could account for the ESR spectrum previously attributed to a highly twisted structure for the 1,7-di-trans-[12]annulene radical anion. Our computed energetic and ESR data for [12]annulene radical anions and their valence isomers suggest that 4a(*-) may have been made, yet its ESR spectrum was incorrectly assigned to the bicyclic isomer 6b(*-). Finally, the computed (1)H NMR shift values of the dianion of 4 reveal a distinct diatropic ring current that should aid in its characterization. 相似文献
103.
Oganesyan A Cruz IA Amador RB Sorto NA Lozano J Godinez CE Anguiano J Pace H Sabih G Gutierrez CG 《Organic letters》2007,9(24):4967-4970
An advance in the selective acylation of polyamines having identical or similar amine functions is reported. While nucleophilicity differences between the various amine functions are slight, the corresponding conjugate acids exhibit pKa values over a significant range. We have used proton as polyamine protecting group: the monoamine resulting from single deprotonation of a polyammonium compound has allowed for high yields of selective acylation. 相似文献
104.
Sébastien Laulhé Bogdan Bogdanov Leah M. Johannes Osvaldo Gutierrez Jason G. Harrison Dean J. Tantillo Xiang Zhang Michael H. Nantz 《Journal of mass spectrometry : JMS》2012,47(6):676-686
The McLafferty rearrangement is an extensively studied fragmentation reaction for the odd‐electron positive ions from a diverse range of functional groups and molecules. Here, we present experimental and theoretical results of 12 model compounds that were synthesized and investigated by GC‐TOF MS and density functional theory calculations. These compounds consisted of three main groups: carbonyls, oximes and silyl oxime ethers. In all electron ionization mass spectra, the fragment ions that could be attributed to the occurrence of a McLafferty rearrangement were observed. For t‐butyldimethylsilyl oxime ethers with oxygen in a β‐position, the McLafferty rearrangement was accompanied by loss of the t‐butyl radical. The various mass spectra showed that the McLafferty rearrangement is relatively enhanced compared with other primary fragmentation reactions by the following factors: oxime versus carbonyl, oxygen versus methylene at the β‐position and ketone versus aldehyde. Calculations predict that the stepwise mechanism is favored over the concerted mechanism for all but one compound. For carbonyl compounds, C–C bond breaking was the rate‐determining step. However, for both the oximes and t‐butyldimethylsilyl oxime ethers with oxygen at the β‐position, the hydrogen transfer step was rate limiting, whereas with a CH2 group at the β‐position, the C–C bond breaking was again rate determining. n‐Propoxy‐acetaldehyde, bearing an oxygen atom at the β‐position, is the only case that was predicted to proceed through a concerted mechanism. The synthesized oximes exist as both the (E)‐ and (Z)‐isomers, and these were separable by GC. In the mass spectra of the two isomers, fragment ions that were generated by the McLafferty rearrangement were observed. Finally, fragment ions corresponding to the McLafferty reverse charge rearrangement were observed for all compounds at varying relative ion intensities compared with the conventional McLafferty rearrangement. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
105.
The mechanism of the acid-catalyzed intramolecular Schmidt reaction of 2-azidopropylcyclohexanones was studied using density functional theory (primarily M06-2X). The reaction was found to proceed through rapid formation of azidohydrin intermediates followed by rate-determining concerted N(2)-loss/shift of the alkyl group antiperiplanar to the N(2) leaving group. For cases where steric, lone pair-cation, and cation-π effects have been invoked previously as regiocontrol elements, the origins and magnitudes of these effects have been examined theoretically. 相似文献
106.
Roberto Cesareo Angel D. Bustamante Julio S. Fabian Sandra Del Pilar Zambrano Walter Alva Luis Z. Chero Maria C. Del Carmen Espinoza Rosendo R. Rodriguez Marco F. Seclen Fidel V. Gutierrez Edgard B. Levano Juan A. Gonzales Marcia A. Rizzutto Enrico Poli Cristiane Calza Marcelino Dos Anjos Renato Pereira De Freitas Ricardo T. Lopes Carlos Elera Izumi Shimada Victor Curay Maria G. Castillo Giovanni E. Gigante Gabriel M. Ingo Fabio Lopes Ulla Holmquist David Diestra 《Applied Physics A: Materials Science & Processing》2013,113(4):889-903
Three types of alloys were recognized when analyzing pre-Columbian artifacts from the North of Peru: gold, silver, and copper alloys; gilded copper and silver; silvered copper; tumbaga, i.e., copper or silver enriched on gold at the surface by depletion gilding. In this paper, a method is described to differentiate gold alloys from gilded copper and from copper–gold tumbaga, and silver alloys from silvered copper and copper–silver tumbaga. This method is based on the use of energy-dispersive X-ray fluorescence, i.e., on a sophisticated analysis of XRF-spectra carrying out an accurate determination of Cu(K α /K β ), Ag(K α /K β ), Au(L α /L β ), and Au-L α /Cu-K α or Ag-K α /Cu-K α ratios. That implies a dedicated software for the quantitative determination of the area of X-ray peaks. This method was first checked by a relevant number of standard samples and then it was applied to pre-Columbian alloys from the North of Peru. 相似文献
107.
Abstract We show global existence and uniqueness for a system of partial differential equations that is a model for chalcopyrite disease within sphalerite. Using direct methods in the calculus of variations, we proof existence of a solution to an implicit time discretisation, derive uniform bounds and pass to the limit. By considering a regularised problem, it is possible to extend the existence results to logarithmic free energies. Furthermore, by an integration in time method we can show uniqueness of the solution. Additionally a free energy inequality affirms thermodynamical correctness of the model. 相似文献
108.
E. Butler G. B. Andresen M. D. Ashkezari M. Baquero-Ruiz W. Bertsche P. D. Bowe C. L. Cesar S. Chapman M. Charlton A. Deller S. Eriksson J. Fajans T. Friesen M. C. Fujiwara D. R. Gill A. Gutierrez J. S. Hangst W. N. Hardy M. E. Hayden A. J. Humphries R. Hydomako M. J. Jenkins S. Jonsell L. V. J?rgensen S. L. Kemp L. Kurchaninov N. Madsen S. Menary P. Nolan K. Olchanski A. Olin A. Povilus P. Pusa C. ?. Rasmussen F. Robicheaux E. Sarid S. Seif el Nasr D. M. Silveira C. So J. W. Storey R. I. Thompson D. P. van der Werf J. S. Wurtele Y. Yamazaki 《Hyperfine Interactions》2012,212(1-3):15-29
109.
T. Friesen G. B. Andresen M. D. Ashkezari M. Baquero-Ruiz W. Bertsche P. D. Bowe E. Butler C. L. Cesar S. Chapman M. Charlton S. Eriksson J. Fajans M. C. Fujiwara D. R. Gill A. Gutierrez J. S. Hangst W. N. Hardy R. S. Hayano M. E. Hayden A. J. Humphries R. Hydomako S. Jonsell L. Kurchaninov N. Madsen S. Menary P. Nolan K. Olchanski A. Olin A. Povilus P. Pusa F. Robicheaux E. Sarid D. M. Silveira C. So J. W. Storey R. I. Thompson D. P. van der Werf J. S. Wurtele Y. Yamazaki 《Hyperfine Interactions》2012,212(1-3):117-123
The goal of the ALPHA experiment is the production, trapping and spectroscopy of antihydrogen. A direct comparison of the ground state hyperfine spectra in hydrogen and antihydrogen has the potential to be a high-precision test of CPT symmetry. We present a novel method for measuring the strength of a microwave field for hyperfine spectroscopy in a Penning trap. This method incorporates a non-destructive plasma diagnostic system based on electrostatic modes within an electron plasma. We also show how this technique can be used to measure the cyclotron resonance of the electron plasma, which can potentially serve as a non-destructive measurement of plasma temperature. 相似文献
110.
Aaij R Abellan Beteta C Adeva B Adinolfi M Adrover C Affolder A Ajaltouni Z Albrecht J Alessio F Alexander M Alkhazov G Alvarez Cartelle P Alves AA Amato S Amhis Y Anderson J Appleby RB Aquines Gutierrez O Archilli F Arrabito L Artamonov A Artuso M Aslanides E Auriemma G Bachmann S Back JJ Bailey DS Balagura V Baldini W Barlow RJ Barschel C Barsuk S Barter W Bates A Bauer C Bauer T Bay A Bediaga I Belogurov S Belous K Belyaev I Ben-Haim E Benayoun M Bencivenni G Benson S Benton J Bernet R 《Physical review letters》2012,108(18):181806
The angular distributions and the partial branching fraction of the decay B0 → K*0 μ+ μ- are studied by using an integrated luminosity of 0.37 fb(-1) of data collected with the LHCb detector. The forward-backward asymmetry of the muons, A(FB), the fraction of longitudinal polarization, F(L), and the partial branching fraction dB/dq2 are determined as a function of the dimuon invariant mass. The measurements are in good agreement with the standard model predictions and are the most precise to date. In the dimuon invariant mass squared range 1.00-6.00 GeV2/c4, the results are A(FB)=-0.06(-0.14)(+0.13)±0.04, F(L)=0.55±0.10±0.03, and dB/dq2=(0.42±0.06±0.03)×10(-7) c4/GeV2. In each case, the first error is statistical and the second systematic. 相似文献