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51.
Bryantsev VS de Jong WA Cossel KC Diallo MS Goddard WA Groenewold GS Chien W Van Stipdonk MJ 《The journal of physical chemistry. A》2008,112(26):5777-5780
Theoretical calculations suggest a novel two-electron three-atom bonding scheme for complexation of O 2 with U(V) compounds, leading to the stabilization of superoxo complexes in the side-on (eta (2)) configuration. This binding motif is likely to play an important role in the oxidative processes involving trans-uranium compounds having valence 5f phi electrons. 相似文献
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Groenewold GS Gianotto AK Cossel KC Van Stipdonk MJ Moore DT Polfer N Oomens J de Jong WA Visscher L 《Journal of the American Chemical Society》2006,128(14):4802-4813
The gas-phase infrared spectra of discrete uranyl ([UO2]2+) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the O=U=O stretch and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric O=U=O stretching frequency was measured at 1017 cm(-1) for [UO2(CH3COCH3)2]2+ and was systematically red shifted to 1000 and 988 cm(-1) by the addition of a third and fourth acetone ligand, respectively, which was consistent with increased donation of electron density to the uranium center in complexes with higher coordination number. The values generated computationally using LDA, B3LYP, and ZORA-PW91 were in good agreement with experimental measurements. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from two to four and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO2(CH3CN)n]2+ complexes, although the uranyl asymmetric stretching frequencies were greater than those measured for acetone complexes having equivalent coordination, which is consistent with the fact that acetonitrile is a weaker nucleophile than is acetone. This conclusion was confirmed by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3-6 cm(-1). 相似文献
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Leavitt CM Wolk AB Kamrath MZ Garand E Van Stipdonk MJ Johnson MA 《Journal of the American Society for Mass Spectrometry》2011,22(11):1941-1952
We report vibrational predissociation spectra of the four protonated dipeptides derived from glycine and sarcosine, GlyGlyH+•(H2)1,2, GlySarH+•(D2)2, SarGlyH+•(H2)2, and SarSarH+•(D2)2, generated in a cryogenic ion trap. Sharp bands were recovered by monitoring photoevaporation of the weakly bound H2 (D2) molecules in a linear action regime throughout the 700–4200 cm–1 range using a table-top laser system. The spectral patterns were analyzed in the context of the low energy structures obtained
from electronic structure calculations. These results indicate that all four species are protonated on the N-terminus, and
feature an intramolecular H-bond involving the amino group. The large blue-shift in the H-bonded N–H fundamental upon incorporation
of a methyl group at the N-terminus indicates that this modification significantly lowers the strength of the intramolecular
H-bond. Methylation at the amide nitrogen, on the other hand, induces a significant rotation (~110o) about the peptide backbone. 相似文献
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Schoendorff G de Jong WA Van Stipdonk MJ Gibson JK Rios D Gordon MS Windus TL 《Inorganic chemistry》2011,50(17):8490-8493
Recent gas-phase experimental studies suggest the presence of hypercoordinated uranyl complexes. Coordination of acetone (Ace) to uranyl to form hypercoordinated species is examined using density functional theory (DFT) with a range of functionals and second-order perturbation theory (MP2). Complexes with up to eight acetones were studied. It is shown that no more than six acetones can bind directly to uranium and that the observed uranyl complexes are not hypercoordinated. In addition, other more exotic species involving proton transfer between acetones and species involving enol tautomers of acetone are high-energy species that are unlikely to form. 相似文献
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中国环流器新一号装置总体联调 总被引:2,自引:1,他引:1
谈满秋 《核聚变与等离子体物理》1997,17(2):1-8
本文介绍中国环流器新一号装置工程总体联合调试的内容和主要结果。该装置总体联调是非常成功的,获得了重复性很好,环电流平顶宽的稳定平稳的放电波形,这对物理实验的开展非常有利。 相似文献
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Perera BA Gallardo AL Barr JM Tekarli SM Anbalagan V Talaty ER Van Stipdonk MJ 《Journal of mass spectrometry : JMS》2002,37(4):401-413
In a previous report we showed that certain binary Ag(+)-amino acid complexes formed adduct ions by the attachment of a single water and methanol molecule when stored in an ion trap mass spectrometer: complexes with aliphatic amino acids and with 4-fluorophenylalanine formed the adduct ions whereas complexes with phenylalanine and tryptophan did not. In this study we compared the tendency of the Ag(+) complexes derived from phenylalanine, 4-fluorophenylalanine, 4-hydroxyphenylalanine (tyrosine), 4-bromophenylalanine, 4-nitrophenylalanine and aminocyclohexanepropionic acid to form water adducts when stored, without further activation, in the ion trap for times ranging from 1 to 500 ms. Because the donation of pi electron density to the Ag(+) ion is a likely determining factor in complex reactivity, our aim in the present study was to determine qualitatively the influence of para-position substituents on the aromatic ring on the formation of the water adducts. Our results show that the reactivity of the complexes is influenced significantly by the presence of the various substituents. Decreases in [M + Ag](+) ion abundance, and increases in adduct ion abundance, both measured as a function of storage time, follow the trend -NO(2) > -Br > -F > -OH > -H. The complex of Ag(+) with 4-nitrophenylalanine was nearly as reactive towards water as the Ag(+) complex with aminocyclohexanepropionic acid, the last being an amino acid devoid of pi character in the ring system. Collision induced dissociation of the [M + Ag](+) species derived from the amino acids produces, among other products, Ag(+) complexes with a para-substituted phenylacetaldehyde: complexes that also form adduct species when stored in the ion trap. The trends in adduct ion formation exhibited by the aldehyde-Ag(+) complex ions were similar to those observed for the precursor complexes of Ag(+) and the amino acids, confirming the influence of the ring substituent. 相似文献