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981.
Absorption spectra of closed-shell Na(2), Na(3) (+), Na(4), Na(5) (+), Na(6), Na(7) (+), and Na(8) clusters are calculated using a complex Bethe-Salpeter equation derived using a conserving linear response method. In the framework of a quasiparticle approach, we determine electron-hole correlations in the presence of an external field. The calculated results are in excellent agreement with experimental spectra, and some possible cluster geometries that occur in experiments are analyzed. The position and the broadening of the resonances in the spectra arise from a consistent treatment of the scattering and dephasing contributions in the linear response calculation. Comparison between the experimental and the theoretical results yields information about the cluster geometry, which is not accessible experimentally. 相似文献
982.
Amiri S Reisenauer HP Schreiner PR 《Journal of the American Chemical Society》2010,132(45):15902-15904
We present the first generation and spectroscopic identification of the higher-lying E conformer of the simplest aromatic carboxylic acid, benzoic acid (1a), as its O-deuterated isotopologue (E)-d(1)-1a using matrix-isolation techniques; the parent (E)-1a could not be observed because of fast H-tunneling to the more stable conformer (Z)-1a. Even deuterated (E)-d(1)-1a converts quickly back to (Z)-d(1)-1a through D-tunneling with a half-life (τ) of ~12 min in Ar at 11 K. Tunneling computations using an Eckart barrier in conjunction with a CCSD(T)/cc-pVTZ//MP2/cc-pVDZ + ZPVE intrinsic reaction path revealed that τ of (E)-1a is only ~10(-5) min, in marked contrast to those of simple aliphatic acids, which are in the range of minutes. The electronic substituent effects on D-tunneling in para-substituted benzoic acid derivatives (p-X-PhCOOD, d(1)-1) were systematically studied in Ar matrices at 11 K to derive the first Hammett relationships for atom tunneling. σ-Electron donors (X = alkyl) increase the half-life of d(1)-1, while σ-acceptor/π-donor groups (X = OD, NH(2), halogen) and to an even greater extent a σ-/π-acceptor group (X = NO(2)) decrease τ. The latter finding is in line with the smaller E-to-Z reaction barriers and narrower reaction widths for the isomerization. Tunneling substituent constants (σ(t)) for this conformational isomerization were derived experimentally and computationally. 相似文献
983.
Ulf H. Strasser Beate Neumann Hans‐Georg Stammler Norbert W. Mitzel Prof. Dr. 《无机化学与普通化学杂志》2010,636(7):1249-1254
The tetrasilyl ethers calix[4]areneOSiMe2R (R = Me, H, vinyl, allyl) were prepared by salt elimination; the calix[4]arene was deprotonated with sodium hydride and subsequently reacted with chlorosilanes ClSiMe2R. In general, DMF was chosen as solvent in order to steer the reactions in terms of a preference for the cone‐conformation of the products. In the case of calix[4]areneOSiMe3 both, partial‐cone‐ and cone‐conformers, were synthesised. All products were characterised by NMR (1H, 13C, 29Si) spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction. 相似文献
984.
985.
986.
Hans J. Breunig Tim Koehne Ana Maria Preda Cristian Silvestru Luis F. Piedra-Garza 《Journal of organometallic chemistry》2010,695(9):1307-1313
The syntheses and spectroscopic (NMR, MS) investigations of the antimonates [Ph4P]+[Me2SbCl4]− (1), [Me4Sb]+[Me2SbCl4]− (2), [Et4N]+[Ph2SbCl4]− (3), [Bu4N]+[Ph2SbCl4]− (4), [Me4Sb]+[Ph2SbCl4]− (5), [Et3MeSb]+[Ph2SbCl4]− (6), [Et4N]+[Ph2SbF4]− (7) and [Et4N]+[Ph2SbBr4]− (8) are reported. Halogen scrambling reactions of Et4NBr or Ph4EBr (E = P, Sb) with R2SbCl3 (R = Me, Ph) produce mixtures of compounds from which crystals of [Et4N]+[Ph2SbBr1.24Cl2.76]− (9), [Et4N]+[Ph2SbBr2.92Cl1.08]− (10) or [Ph4Sb]+[Me2SbCl4]− (11) were isolated. The crystal and molecular structures of 1 and 3-11 are reported. 相似文献
987.
Mario Barbatti Jiří Pittner Marek Pederzoli Ute Werner Roland Mitrić Vlasta Bonačić-Koutecký Hans Lischka 《Chemical physics》2010
Non-adiabatic dynamics simulations were performed for pyrrole at time-dependent density functional theory level using the trajectory surface hopping approach. Initial conditions were prepared based on the UV-absorption spectrum so as to simulate monochromatic absorption in three distinct spectral regions. The results showed predominance of the NH-stretch mechanism for excited-state relaxation. With increasing initial energy, however, other mechanisms are activated as well, even though they still occurred for a minor fraction of the trajectories. Dynamics starting at the origin of the absorption spectrum exhibited internal conversion to the ground state with a time constant of 20 fs. In contrast, dynamics starting at higher energies gave rise to much longer time constants for internal conversion near 200 fs. 相似文献
988.
989.
WilliamJ. Griffiths Therese Koal Yuqin Wang Matthias Kohl DavidP. Enot Hans‐Peter Deigner 《Angewandte Chemie (International ed. in English)》2010,49(32):5426-5445
Metabolomics is a truly interdisciplinary field of science, which combines analytical chemistry, platform technology, mass spectrometry, and NMR spectroscopy with sophisticated data analysis. Applied to biomarker discovery, it includes aspects of pathobiochemistry, systems biology/medicine, and molecular diagnostics and requires bioinformatics and multivariate statistics. While successfully established in the screening of inborn errors in neonates, metabolomics is now widely used in the characterization and diagnostic research of an ever increasing number of diseases. In this Review we highlight important technical prerequisites as well as recent developments in metabolomics and metabolomics data analysis with special emphasis on their utility in biomarker identification and qualification, as well as targeted metabolomics by employing high‐throughput mass spectrometry. 相似文献
990.
Markus R. Meyer Jens Wilhelm Frank T. Peters Hans H. Maurer 《Analytical and bioanalytical chemistry》2010,397(3):1225-1233
In recent years, a new class of designer drugs has appeared on the drugs of abuse market in many countries, namely, the so-called
beta-keto (bk) designer drugs such as mephedrone (bk-4-methylmethamphetamine), butylone (bk-MBDB), and methylone (bk-MDMA).
The aim of the present study was to identify the metabolites of mephedrone in rat and human urine using GC-MS techniques and
to include mephedrone, butylone, and methylone within the authors’ systematic toxicological analysis (STA) procedure. Six
phase I metabolites of mephedrone were detected in rat urine and seven in human urine suggesting the following metabolic steps:
N-demethylation to the primary amine, reduction of the keto moiety to the respective alcohol, and oxidation of the tolyl moiety
to the corresponding alcohols and carboxylic acid. The STA procedure allowed the detection of mephedrone, butylone, methylone,
and their metabolites in urine of rats treated with doses corresponding to those reported for abuse of amphetamines. Besides
macro-based data evaluation, an automated evaluation using the automated mass spectral deconvolution and identification system
was performed. Mephedrone and butylone could be detected also in human urine samples submitted for drug testing. Assuming
similar kinetics in humans, the described STA procedure should be suitable for proof of an intake of the bk-designer drugs
in human urine. 相似文献