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371.
Aitala EM Amato S Anjos JC Appel JA Ashery D Banerjee S Bediaga I Blaylock G Bracker SB Burchat PR Burnstein RA Carter T Carvalho HS Costa I Cremaldi LM Darling C Denisenko K Fernandez A Gagnon P Gerzon S Gobel C Gounder K Granite D Halling AM Herrera G Hurvits G James C Kasper PA Kondakis N Kwan S Langs DC Leslie J Lichtenstadt J Lundberg B Manacero A MayTal-Beck S Meadows B de Mello Neto JR Milburn RH de Miranda JM Napier A Nguyen A d'Oliveira AB O'Shaughnessy K Peng KC Perera LP Purohit MV 《Physical review letters》1996,76(3):364-367
372.
Multidimensional cosmological models with a space-time consisting ofn (n 2) Einstein spaces are investigated for a special class of multicomponent perfect fluid as a matter source. The dynamical behaviour of the universe is described. In the case of static internal spaces the external space evolves like a Friedmann universe with changing effective equation of state. Some of the models considered are integrable and classical as well as quantum solutions are found. Some of them represent wormholes. Quantum wormholes have a discrete spectrum. 相似文献
373.
David Fuchs Charlotte Gabel-Jensen Henrik Jensen Kasper D. Rand Stig Pedersen-Bjergaard Steen Honoré Hansen Nickolaj Jacob Petersen 《Analytica chimica acta》2016
A fully integrated and automated electromembrane extraction LC-MS (EME-LC-MS) system has been developed and characterized. Hyphenation of a flow–flow EME probe to LC-MS was accomplished by using an in-built 10-port switching valve of the LC-MS system. The 10-port switching valve decoupled the high pressure of the UHPLC-system from the low pressure required for operation of the EME-probe by automated switching between a sample extraction/analysis and a sample load position. In the sample load position the extracted analytes were loaded into a HPLC sample loop. By switching the valve to the sample extraction/analysis position the setup allowed simultaneous analysis of previously loaded analytes while extracting a new sample. Performance of the system was characterized with respect to precision and linearity (RSD < 2.5%, R2: 0.998) and the setup was applied for studying the in-vitro metabolism of methadone by rat liver microsomes. As the metabolic reaction proceeded, methadone and its metabolites were extracted and analyzed in parallel by LC-MS using either isocratic or gradient elution. Compared to a conventional in-vitro metabolism analysis based on protein precipitation followed by LC-MS analysis the fully automated EME-LC-MS system offers a significant time saving and in addition demonstrates increased sensitivity as the analytes were automatically enriched during the extraction process. The experiment revealed 6 to 16 times higher S/N ratios of the EME-LC-MS method compared to protein precipitation followed by LC-MS and thus concomitantly lower LOD and LOQ. The setup integrates a complete analytical workflow of rapid extraction, enrichment, separation and detection of analytes in a fully automated manner. These attributes make the developed system a powerful alternative approach for a wide range of analytical applications. 相似文献
374.
Online coupling of capillary electrophoresis (CE) to electrospray ionization mass spectrometry (MS) has shown considerable potential, however, technical challenges have limited its use. In this study, we have developed a simple and sensitive sheathless CE-MS interface based on the novel concept of forming a sub-micrometer fracture directly in the capillary. The simple interface design allowed the generation of a stable ESI spray capable of ionization at low nanoliter flow-rates (45–90 nL/min) for high sensitivity MS analysis of challenging samples like those containing proteins and peptides. By analysis of a model peptide (leucine enkephalin), a limit of detection (LOD) of 0.045 pmol/μL (corresponding to 67 attomol in a sample volume of ∼15 nL) was obtained. The merit of the CE-MS approach was demonstrated by analysis of bovine serum albumin (BSA) tryptic peptides. A well-resolved separation profile was achieved and comparable sequence coverage was obtained by the CE-MS method (73%) compared to a representative UPLC-MS method (77%). The CE-MS interface was subsequently used to analyse a more complex sample of pharmaceutically relevant human proteins including insulin, tissue factor and α-synuclein. Efficient separation and protein ESI mass spectra of adequate quality could be achieved using only a small amount of sample (30 fmol). In addition, analysis of ubiquitin samples under both native and denatured conditions, indicate that the CE-MS setup can facilitate native MS applications to probe the conformational properties of proteins. Thus, the described CE-MS setup should be useful for a wide range of high-sensitivity applications in protein research. 相似文献
375.
Celik L Sinning S Severinsen K Hansen CG Møller MS Bols M Wiborg O Schiøtt B 《Journal of the American Chemical Society》2008,130(12):3853-3865
Molecular modeling and structure-activity relationship studies were performed to propose a model for binding of the neurotransmitter serotonin (5-HT) to the human serotonin transporter (hSERT). Homology models were constructed using the crystal structure of a bacterial homologue, the leucine transporter from Aquifex aeolicus, as the template and three slightly different sequence alignments. Induced fit docking of 5-HT into hSERT homology models resulted in two different binding modes. Both show a salt bridge between Asp98 and the charged primary amine of 5-HT, and both have the 5-HT C6 position of the indole ring pointing toward Ala173. The difference between the two orientations of 5-HT is an enantiofacial discrimination of the indole ring, resulting in the 5-hydroxyl group of 5-HT being vicinal to either Ser438/Thr439 or Ala169/Ile172/Ala173. To assess the binding experimentally, binding affinities for 5-HT and 17 analogues toward wild type and 13 single point mutants of hSERT were measured using an approach termed paired mutant-ligand analogue complementation (PaMLAC). The proposed ligand-protein interaction was systematically examined by disrupting it through site-directed mutagenesis and re-establishing another interaction via a ligand analogue matching the mutated residue, thereby minimizing the risk of identifying indirect effects. The interactions between Asp98 and the primary amine of 5-HT and the interaction between the C6-position of 5-HT and hSERT position 173 was confirmed using PaMLAC. The measured binding affinities of various mutants and 5-HT analogues allowed for a distinction between the two proposed binding modes of 5-HT and biochemically support the model for 5-HT binding in hSERT where the 5-hydroxyl group is in close proximity to Thr439. 相似文献
376.
The joint computational (TD-DFT) experimental study of the UV-vis spectroscopy of alkoxychromium(0) carbene complexes accurately assigns the vertical transitions responsible for the observed spectra of these compounds. Both the LF and the MLCT band have a remarkably pi-pi* character, which has been demonstrated by the strong dependence of the absorptions with the donor/acceptor nature of the substituent in p-substituted styrylchromium(0) carbene complexes. The effect of the substituent is also related with the equilibrium geometry of the complexes and the occupations of the p atomic orbital of the carbene carbon atom. Additionally, the ferrocenyl moiety behaves in chromium(0) (Fischer) carbene complexes as a pi-donor group. 相似文献
377.
Bache N Rand KD Roepstorff P Ploug M Jørgensen TJ 《Journal of the American Society for Mass Spectrometry》2008,19(12):1719-1725
We have previously shown that peptide amide hydrogens undergo extensive intramolecular migration (i.e., complete hydrogen scrambling) upon collisional activation of protonated peptides (Jørgensen et al. J. Am. Chem. Soc. 2005, 127, 2785–2793). The occurrence of hydrogen scrambling enforces severe limitations on the application of gas-phase fragmentation as a convenient method to obtain information about the site-specific deuterium uptake for proteins and peptides in solution. To investigate whether deprotonated peptides exhibit a lower level of scrambling relative to their protonated counterparts, we have now measured the level of hydrogen scrambling in a deprotonated, selectively labeled peptide using MALDI tandem time-of-flight mass spectrometry. Our results conclusively show that hydrogen scrambling is prevalent in the deprotonated peptide upon collisional activation. The amide hydrogens (1H/2H) have migrated extensively in the anionic peptide, thereby erasing the original regioselective deuteration pattern obtained in solution. 相似文献
378.
Bernigaud V Drenck K Huber BA Hvelplund P Jabot T Kadhane U Kirketerp MB Liu B Lykkegaard MK Manil B Nielsen SB 《Journal of the American Society for Mass Spectrometry》2008,19(6):809-813
Electron-capture induced dissociation of protoporphyrin cations and anions has been studied. The cations captured two electrons in two successive collisions and were converted to the corresponding even-electron anions. About one fifth of the ions lost a hydrogen atom to become radical anions but otherwise very little fragmentation was observed. The anions captured an electron to become dianions. No hydrogen loss occurred, and the only fragmentation channel observed was loss of CO2H, to give a doubly charged carbanion. Our results indicate that protoporphyrin ions are very efficient in accommodating one or even two electrons in the lowest unoccupied molecular orbital of the porphyrin macrocycle, and that electron capture induces only limited dissociation. 相似文献
379.
Thomas Bierkandt Patrick Hemberger Patrick Oßwald Dominik Krüger Markus Köhler Tina Kasper 《Proceedings of the Combustion Institute》2019,37(2):1579-1587
Two laminar, premixed, fuel-rich flames fueled by anisole-oxygen-argon mixtures with the same cold gas velocity and pressure were investigated by molecular-beam mass spectrometry at two synchrotron sources where tunable vacuum-ultraviolet radiation enables isomer-resolved photoionization. Decomposition of the very weak O–CH3 bond in anisole (C6H5OCH3) by unimolecular decomposition yields the resonantly-stabilized phenoxy radical (C6H5O). This key intermediate species opens reaction routes to five-membered ring species, such as cyclopentadiene (C5H6) and cyclopentadienyl radicals (C5H5). Anisole is often discussed as model compound for lignin to study the phenolic-carbon structure in this natural polymer. Measured temperature profiles and mole fractions of many combustion intermediates give detailed information on the flame structure. A very comprehensive reaction mechanism from the literature which includes a sub-scheme for anisole combustion is used for species modeling. Species with the highest measured mole fractions (on the order of 10?3–10?2) are CH3, CH4, C2H2, C2H4, C2H6, CH2O, C5H5 (cyclopentadienyl radical), C5H6 (cyclopentadiene), C6H6 (benzene), C6H5OH (phenol), and C6H5CHO (benzaldehyde). Some are formed in the first destruction steps of anisole, e.g., phenol and benzaldehyde, and their formation will be discussed and with regard to the modeling results. There are three major routes for the fuel destruction: (1) formation of benzaldehyde (C6H5CHO), (2) formation of phenol (C6H5OH), and (3) unimolecular decomposition of anisole to phenoxy (C6H5O) and CH3 radicals. In the experiment, the phenoxy radical could be measured directly. The phenoxy radical decomposes via a bicyclic structure into the soot precursor C5H5 and CO. Formation of larger oxygenated species was observed in both flames. One of them is guaiacol (2-methoxyphenol), which decomposes into fulvenone. The presented speciation data, which contain more than 60 species mole fraction profiles of each flame, give insights into the combustion kinetics of anisole. 相似文献
380.
Pablo Baudin Dmytro Bykov Dmitry Liakh Patrick Ettenhuber Kasper Kristensen 《Molecular physics》2017,115(17-18):2135-2144
ABSTRACTThe recently developed Local Framework for calculating Excitation energies (LoFEx) is extended to the coupled cluster singles and doubles (CCSD) model. In the new scheme, a standard CCSD excitation energy calculation is carried out within a reduced excitation orbital space (XOS), which is composed of localised molecular orbitals and natural transition orbitals determined from time-dependent Hartree–Fock theory. The presented algorithm uses a series of reduced second-order approximate coupled cluster singles and doubles (CC2) calculations to optimise the XOS in a black-box manner. This ensures that the requested CCSD excitation energies have been determined to a predefined accuracy compared to a conventional CCSD calculation. We present numerical LoFEx-CCSD results for a set of medium-sized organic molecules, which illustrate the black-box nature of the approach and the computational savings obtained for transitions that are local compared to the size of the molecule. In fact, for such local transitions, the LoFEx-CCSD scheme can be applied to molecular systems where a conventional CCSD implementation is intractable. 相似文献