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11.
The formation of the XeF+ ion by ion-molecule reaction has been observed in an ionized mixture of Xe and NF3 by ion cyclotron resonance mass spectrometry. The excited 2P state of the xenon ion has unambiguously been identified as the major precursor by photoionization mass spectrometry. The NF+3 ion makes an additional minor contribution. Evidence suggests that the excited 2P xenon ion radiatively decays to the 2P ground state on the time scale of the experiment. The transition probability deduced for this dipole forbidden emission, 18 ± 4 s?1, is in good agreement with the theoretical value of 21 s?1 for the sum of the magnetic dipole and electric quadrupole transition rates. 相似文献
12.
Chaozhong Cai Fu-An Kang Derek A. Beauchamp Zhihua Sui Ronald K. Russell Christopher A. Teleha 《Tetrahedron: Asymmetry》2013,24(11):651-656
Two cycloaddition methods were applied to chiral protected aminocyclopentenes 2 and 9 and provided novel bicyclic products 3 and 4 in good yields. The explanation for the observed stereochemistry was based on the sterically encumbered β-face forcing the cycloadditions to occur on the α-face of the cyclopentene ring. The stereochemistry of 4 was confirmed by X-ray of the fumarate salt 10 and showed the trans-relationship between the newly formed ring and the chiral –NHBoc group. 相似文献
13.
Wen‐Chao Geng Dongmei Zhang Chu Gong Zhihao Li Kevin M. Barraza Jesse L. Beauchamp Dong‐Sheng Guo Xinxing Zhang 《Angewandte Chemie (International ed. in English)》2020,59(31):12684-12688
The oxidation of antioxidants by oxidizers imposes great challenges to both living organisms and the food industry. Here we show that the host–guest complexation of the carefully designed, positively charged, amphiphilic guanidinocalix[5]arene pentadodecyl ether (GC5A‐12C) and negatively charged oleic acid (OA), a well‐known cell membrane antioxidant, prevents the oxidation of the complex monolayers at the air–water interface from two potent oxidizers hydroxyl radicals (OH) and singlet delta oxygen (SDO). OH is generated from the gas phase and attacks from the top of the monolayer, while SDO is generated inside the monolayer and attacks amphiphiles from a lateral direction. Field‐induced droplet ionization mass spectrometry results have demonstrated that the host–guest complexation achieves steric shielding and prevents both types of oxidation as a result of the tight and “sleeved in” physical arrangement, rather than the chemical reactivity, of the complexes. 相似文献
14.
[formula: see text] A triply convergent, highly efficient second-generation synthesis of the potent antimitotic agent (+)-discodermolide (1) has been achieved on a 1-g scale. 相似文献
15.
The time-varying spectra of eight musical instrument sounds were randomly altered by a time-invariant process to determine how detection of spectral alteration varies with degree of alteration, instrument, musical experience, and spectral variation. Sounds were resynthesized with centroids equalized to the original sounds, with frequencies harmonically flattened, and with average spectral error levels of 8%, 16%, 24%, 32%, and 48%. Listeners were asked to discriminate the randomly altered sounds from reference sounds resynthesized from the original data. For all eight instruments, discrimination was very good for the 32% and 48% error levels, moderate for the 16% and 24% error levels, and poor for the 8% error levels. When the error levels were 16%, 24%, and 32%, the scores of musically experienced listeners were found to be significantly better than the scores of listeners with no musical experience. Also, in this same error level range, discrimination was significantly affected by the instrument tested. For error levels of 16% and 24%, discrimination scores were significantly, but negatively correlated with measures of spectral incoherence and normalized centroid deviation on unaltered instrument spectra, suggesting that the presence of dynamic spectral variations tends to increase the difficulty of detecting spectral alterations. Correlation between discrimination and a measure of spectral irregularity was comparatively low. 相似文献
16.
The discovery of several new unusually stable aggregates of arginine that are intermolecularly bound by salt bridges is reported. Quadrupole ion-trap mass spectrometry provides evidence for the stability of arginine in the zwitterionic state, where the protonated guanidinium group of one arginine interacts strongly with the carboxylate of another to form stable noncovalent complexes, coordinated to either a cation or anion. Clusters of arginine with itself, sodium, potassium, lithium, magnesium, chloride, fluoride, bromide, iodide, and nitrate are observed. DFT calculations at the B3LYP/6-31G level are used to assess the structures and energetics of particularly prominent clusters. An examination of mixtures of D-arginine with isotopically labeled L-arginine indicates that the stability of these clusters does not depend on arginine enantiomeric purity. The cyclic trimers of arginine, capped with either Cl(-) or NO(3)(-), possess exceptional stability. 相似文献
17.
The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton. 相似文献
18.
Acoustic performance in ultrasonic transmitters can be improved by means of a suitable electrical driving response and matching/tuning networks. It is important to predict this electrical response, but doing so is not easy because it departs notably from the nominal pattern with the loading probes. In practice, the analysis of HV pulser spikes in NDE applications requires fairly complex models in the transient regime and, in addition, non-linear problems could arise, especially in the case of tuned transmitters. In this paper, the most relevant influences of loading characteristics of NDT ultrasonic probes on the pulser electrical driving responses are evaluated in time and frequency domains. Conventional pulse generators and typical NDE pulsers are considered. Driving responses are analysed across commercial ultrasonic probes and, alternatively, across similar purely electrical loads. Distinct influences on pulser responses from electrical and motional sections of the probes are identified. All these aspects are studied on the basis of experimental and computer results. 相似文献
19.
Evan L. Neidholdt J. L. Beauchamp 《Journal of the American Society for Mass Spectrometry》2009,20(11):2093-2099
We present studies of the ionization mechanism operative in the ambient pressure pyroelectric ionization source (APPIS), along
with applications that include detection of simulants for chemical nerve agents. It is found that ionization by APPIS occurs
in the gas-phase. As the crystal is thermally cycled over a narrow temperature range, electrical discharges near the surface
of the crystal produce energetic species which, through reactions with atmospheric molecules, result in reactant ions such
as protonated water clusters or clusters of hydroxide and water. Reactant ions can be observed directly in the mass spectrometer.
These go on to react with trace neutrals via proton transfer reactions to produce the ions observed in mass spectra, which are usually singly protonated or deprotonated
species. Further implicating gas-phase ionization, observed product distributions are highly dependent on the composition
of ambient gases, especially the concentration of water vapor and oxygen surrounding the source. For example, basic species
such as triethylamine are observed as singly protonated cations at a water partial pressure of 10 torr. At a water pressure
of 4 torr, reactive oxygen species are formed and lead to observation of protonated amine oxides. The ability of the APPIS
source to detect basic molecules with high proton affinities makes it highly suited for the detection of chemical nerve agents.
We demonstrate this application using simulants corresponding to VX and GA (Tabun). With the present source configuration
pyridine is detected readily at a concentration of 4 ppm, indicating ultimate sensitivity in the high ppb range. 相似文献
20.
A convenient, general, and high yielding Pd-catalyzed cross-coupling of methanesulfonamide with aryl bromides and chlorides is reported. The use of this method eliminates concern over genotoxic impurities that can arise when an aniline is reacted with methanesulfonyl chloride. The application of this method to the synthesis of dofetilide is also reported. 相似文献