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排序方式: 共有137条查询结果,搜索用时 15 毫秒
1.
Khoury JT Rodriguez-Cruz SE Parks JH 《Journal of the American Society for Mass Spectrometry》2002,13(6):696-708
Sensitive methods have been developed to measure laser-induced fluorescence from trapped ions by reducing the detection of background scattering to zero levels during the laser excitation pulse. The laser beam diameter has been reduced to approximately 150 microm to eliminate scattering on trap apertures and the resulting laser-ion interaction is limited to a volume of approximately 10(-5) cm which is approximately 0.03-0.15 of the total ion cloud volume depending on experimental conditions. The detection optics collected fluorescence only from within the solid angle defined by laser-ion interaction volume. Rhodamine 640 and Alexa Fluor 350 ions, commonly used as fluorescence resonance energy transfer (FRET) fluorophores, were generated in the gas phase by using electrospray ionization and injected into a radiofrequency Paul trap where they were stored and exposed to Nd:YAG laser pulses at 532 and 355 nm for times up to 10 m. Fluorescence emitted by these ions was investigated for several trap q(z) values and ion cloud temperatures. Analysis of photon statistics indicated an average of approximately 10 photons were incident on the PMT detector per 15 ns pulse for approximately 10(3) trapped ions in the interaction volume. Fluorescence measurements displayed a dependence on trapped ion number which were consistent with calculations of the space charge limited ion density. To investigate the quantitative capability of these fluorescence techniques, the laser-induced fragmentation of trapped Alexa Fluor 350 ions was measured and compared with a rate equation model of the dynamics. Decay of the fluorescence signal as well as the parent ion number compared closely with quantitative predictions of the photofragmentation model. 相似文献
2.
Vezmar I M.M. Alvarez J.T. Khoury B.E. Salisbury M.N. Shafigullin R.L. Whetten 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,40(1):147-151
Stable, intense beams of large metal clusters (from 102 to 103 Au or Ag atoms) can be produced by laser desorption of molecular films of passivated nanocrystals that have undergone fractionation by size and a separate structural characterization. The mass onset of the desorbed species corresponds directly to the dimensions of the nanocrystal core, indicating that only the surfactant shell is lost during desorption. Photofragmentation, photoionization, and photodetachment from beams of large metal clusters, generated in this way, have all been observed. 相似文献
3.
Ring strain energies (RSEs) are predicted using homodesmotic reactions at the B3LYP/6-31G* level of theory. Substituents are conserved in the acyclic reference and any difference in energy between the ring and the acyclic reference corresponds exclusively to RSE. Small rings are stabilized by alkyl substituents and this stabilization decreases as the size of the ring increases. There is a destabilization of medium sized rings. Greater stabilization is found upon alkyl substitution at a double bond in an unsaturated ring and this stabilization decreases as ring size increases. The effects of cis-1,2-disubstitution on RSEs have been evaluated and indicate stabilization for both small and medium sized rings. RSEs of saturated and unsaturated polycyclic systems agree well with the RSEs derived from experimental thermochemical data. RSEs are reported for substituted norbornanes, norbornenes, and norbornadienes to complement experimental studies. 相似文献
4.
Spatially complex, temporally chaotic dynamics of N-coupled impact oscillators connected by a string are studied experimentally using a discrete measure of the motion for each of the masses. For N=8, a binary assignment of symbols, corresponding to whether or not the masses impact an amplitude constraint, is used to code the spatial pattern as a binary number and to store its change in time in a computer. A spatial pattern return map is then used to observe the change in spatial patterns with time. Bifurcations in spatial impact patterns are observed in this experiment. An entropy measure is also used to characterize the dynamics. Numerical simulation shows behavior similar to the experimental system. 相似文献
5.
Stephen D. Pastor David N. Rahni Nancy Khoury Stephen A. Koch 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1951-1956
The X-ray crystallographic analysis of 6,6-dimethyl-2,4,8,10-tetra-tert-octyl-dibenzo[d,f][1,3,2]dioxagermepin, 1 is reported. In the solid-state conformation of 1, the dihedral angle about the C─C sp2-sp 2 σ bond connecting the two aryl rings is 50.1°. The observed C2 symmetry in the solid-state conformation of 1 is consistent with the previously suggested solution conformation. 相似文献
6.
Chadi Khoury François Le Goffic Marie‐Noëlle Rager 《Journal of carbohydrate chemistry》2013,32(7):395-409
The synthesis of 2‐acetamido‐2‐deoxy‐6‐O‐octanoyl‐D‐glucono‐1,5‐lactone 9 and 2‐acetamido‐2‐deoxy‐6‐O‐octanoyl‐α‐D‐glucopyranose 7 from 2‐acetamido‐2‐deoxy‐α‐D‐glucopyranose is reported. For both targets, the key intermediate was allyl 2‐acetamido‐3,4‐di‐O‐benzyl‐2‐deoxy‐6‐O‐octanoyl‐α‐D‐glucopyranoside 5. Surface tension measurements (critical micellar concentration of 22.3 mM and 5 mM for 9 and 7, respectively) showed up the surface activity of both compounds, while enzyme inhibition assays indicated that 9 could inhibit bovine β‐N‐acetylglucosaminidase (Ki=6.5 µM) but not Serratia marcescens chitobiase nor hen egg‐white lysozyme. Moreover, 7 was shown to induce chitinase production of S. marcescens and to be readily metabolized by these bacteria. 相似文献
7.
Igor A. Kaltashov Anton El Khoury Chengfeng Ren Sergey N. Savinov 《Journal of mass spectrometry : JMS》2020,55(2)
Ruthenium is a platinoid that exhibits a range of unique chemical properties in solution, which are exploited in a variety of applications, including luminescent probes, anticancer therapies, and artificial photosynthesis. This paper focuses on a recently demonstrated ability of this metal in its +3 oxidation state to form highly stable complexes with tris (hydroxymethyl)aminomethane (H2NC(CH2OH)3, Tris‐base or T) and imidazole (Im) ligands, where a single RuIII cation is coordinated by two molecules of each T and Im. High‐resolution electrospray ionization mass spectrometry (ESI MS) is used to characterize RuIII complexes formed by placing a RuII complex [(NH3)5RuIICl]Cl in a Tris buffer under aerobic conditions. The most abundant ionic species in ESI MS represent mononuclear complexes containing an oxidized form of the metal, ie, [XnRuIIIT2 – 2H]+, where X could be an additional T (n = 1) or NH3 (n = 0‐2). Di‐ and tri‐metal complexes also give rise to a series of abundant ions, with the highest mass ion representing a metal complex with an empirical formula Ru3C24O21N6H66 (interpreted as cyclo(T2RuO)3, a cyclic oxo‐bridged structure, where the coordination sphere of each metal is completed by two T ligands). The empirical formulae of the binuclear species are consistent with the structures representing acyclic fragments of cyclo(T2RuO)3 with addition of various combinations of ammonia and dioxygen as ligands. Addition of histidine in large molar excess to this solution results in complete disassembly of poly‐nuclear complexes and gives rise to a variety of ionic species in the ESI mass spectrum with a general formula [RuIIIHiskTm (NH3)n ? 2H]+, where k = 0 to 2, m = 0 to 3, and n = 0 to 4. Ammonia adducts are present for all observed combinations of k and m, except k = m = 2, suggesting that [His2RuIIIT2 ? 2H]+ represents a complex with a fully completed coordination sphere. The observed cornucopia of RuIII complexes formed in the presence of histidine is in stark contrast to the previously reported selective reactivity of imidazole, which interacts with the metal by preserving the RuT2 core and giving rise to a single abundant ruthenium complex (represented by [Im2RuIIIT2 ? 2H]+ in ESI mass spectra). Surprisingly, the behavior of a hexa‐histidine peptide (HHHHHH) is similar to that of a single imidazole, rather than a single histidine amino acid: The RuT2 core is preserved, with the following ionic species observed in ESI mass spectra: [HHHHHH·(RuIIIT2)m ? (3m‐1)H]+ (m = 1‐3). The remarkable selectivity of the imidazole interaction with the RuIIIT2 core is rationalized using energetic considerations at the quantum mechanical level of theory. 相似文献
8.
Mustafa Barri George K. El Khoury Helge I. Andersson Bjrnar Pettersen 《国际流体数值方法杂志》2010,64(7):777-792
Direct numerical simulation (DNS) has been performed to study the channel flow over a backward‐facing step at a Reynolds number Reb=5600 based on the step height h and the inflow bulk velocity Ub. A dynamic method has been used in order to generate realistic turbulent inflow conditions. The results upstream of the step compared well with the fully developed channel flow. Downstream of the step our results show excellent agreement with experimental data. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
9.
Bramati A Hermier JP Khoury AZ Giacobino E Schnitzer P Michalzik R Ebeling KJ Poizat JP Grangier P 《Optics letters》1999,24(13):893-895
We studied anticorrelated quantum fluctuations between the TEM(00) and the TEM(01) transverse modes of a vertical-cavity surface-emitting semiconductor laser by measuring the transverse spatial distribution of the laser beam intensity noise. Our experimental results are found to be in good agreement with the predictions of a phenomenological model that accounts for quantum correlations between transverse modes in a light beam. 相似文献
10.
We present a nearly model-independent estimate that yields the predictions of a class of simple inflationary and ekpyrotic or cyclic models for the spectral tilt of the primordial density inhomogeneities that enables us to compare the two scenarios. Remarkably, we find that the two produce an identical result, n(s) approximately 0.95. For inflation, the same estimate predicts a ratio of tensor to scalar contributions to the low l multipoles of the microwave background anisotropy of T/S approximately 20%; the tensor contribution is negligible for ekpyrotic or cyclic models, as shown in earlier papers. 相似文献