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41.
Ground state rotation and quartic distortion constants were obtained for 11B2D6 from the analysis of high resolution (~0.05 cm?1) Fourier transform infrared spectra. The bands studied comprised the ν17, ν18 type A, and ν14, ν9 + ν15 type C bands of 11B2H6 and the ν16, ν17, ν18 type A, ν8 type B, and ν14 type C bands of 11B2D6. In the case of 11B2H6, the authors' ground state data were combined with those of Lafferty et al. obtained from a previous study (J. Mol. Spectrosc.33, 345–367 (1970)) at comparable resolution of the ν16 type A and ν8 type B fundamentals. Information on the ground state rotational energy manifold of 11B2H6 was accumulated up to J = 23, Ka = 18, and of 11B2D6 up to J = 32, Ka = 22. This permitted rather precise determination of the distortion constants ΔJ0, ΔJK0, ΔK0, although δJ0 and δK0 proved to be too small (< 10?7 cm?1) and were constrained to values calculated from the force field. Sets of upper state parameters were determined for all vibrational levels studied. Although these appear to be essentially unperturbed globally, several localized perturbations were observed and identified. 相似文献
42.
Further experiments in doped InSb are reported on the anomalous NMR relaxation peak, the B-peak, first reported by Bridges and Clark. Data on the peak now extends up to donor concentrations of 8 × 1021 m?3 and permits a sharp reduction in the number of possible explanations of the peak which remain plausible.The peak occurs well above the critical field required for magnetic freeze-out, and appears to follow a dependence of magnetic field at the peak, BB, against density, nD, of BB ∝ n0.60±0.01D at constant temperature. The possibility that the peak is due to the tuning of the ESR frequency through the typical electron hopping frequency ωH in the crystal is explored; a consequence of this model is that ωH must be dominated by nearest-neighbour hops, involving only a very small minority of the donor centres. 相似文献
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44.
A rate process model is developed to interpret the experimental results of Smith, Schmid, Tablas and Kompa on the time and intensity dependence of the infrared absorption of SF6. In this model incoherent excitation of the λ3 molecular mode by the processes of absorption and stimulated emission is followed by radiationless energy transfer from a maximum level to an inactive mode heatbath. This achieves control of the level population by an empirical transfer rate parameter. Good theoretical fits of the experiment absorption decays are obtained with values of approximately 0.1 ns. 相似文献
45.
46.
Menard LD Gao SP Xu H Twesten RD Harper AS Song Y Wang G Douglas AD Yang JC Frenkel AI Nuzzo RG Murray RW 《The journal of physical chemistry. B》2006,110(26):12874-12883
The synthesis and characterization of the clusters Au13[PPh3]4[S(CH2)11CH3]2Cl2 (1) and Au13[PPh3]4[S(CH2)11CH3]4 (2) are described. These mixed-ligand, sub-nanometer clusters, prepared via exchange of dodecanethiol onto phosphine-halide gold clusters, show enhanced stability relative to the parent. The characterization of these clusters features the precise determination of the number of gold atoms in the cluster cores using high-angle annular dark-field scanning transmission electron microscopy, allowing the assignment of 13 gold atoms (+/-3 atoms) to the composition of both cluster molecules. Electrochemical and optical measurements reveal discrete molecular orbital levels and apparent energy gaps of 1.6-1.7 eV for the two cluster molecules. The electrochemical measurements further indicate that the Au13[PPh3]4[S(CH2)11CH3]2Cl2 cluster undergoes an overall two-electron reduction. The electrochemical and spectroscopic properties of the two Au13 cluster molecules are compared with those of a secondary synthetic product, which proved to be larger Au thiolate-derivatized monolayer-protected clusters with an average core of Au180. The latter shows behavior fully consistent with the adoption of metallic-like properties. 相似文献
47.
Aharmim B Ahmed SN Amsbaugh JF Anthony AE Banar J Barros N Beier EW Bellerive A Beltran B Bergevin M Biller SD Boudjemline K Boulay MG Bowles TJ Browne MC Bullard TV Burritt TH Cai B Chan YD Chauhan D Chen M Cleveland BT Cox-Mobrand GA Currat CA Dai X Deng H Detwiler J DiMarco M Doe PJ Doucas G Drouin PL Duba CA Duncan FA Dunford M Earle ED Elliott SR Evans HC Ewan GT Farine J Fergani H Fleurot F Ford RJ Formaggio JA Fowler MM Gagnon N Germani JV Goldschmidt A Goon JT Graham K Guillian E 《Physical review letters》2008,101(11):111301
The Sudbury Neutrino Observatory (SNO) used an array of 3He proportional counters to measure the rate of neutral-current interactions in heavy water and precisely determined the total active (nu_x) 8B solar neutrino flux. This technique is independent of previous methods employed by SNO. The total flux is found to be 5.54_-0.31;+0.33(stat)-0.34+0.36(syst)x10(6) cm(-2) s(-1), in agreement with previous measurements and standard solar models. A global analysis of solar and reactor neutrino results yields Deltam2=7.59_-0.21;+0.19x10(-5) eV2 and theta=34.4_-1.2;+1.3 degrees. The uncertainty on the mixing angle has been reduced from SNO's previous results. 相似文献
48.
Headspace quantification of pure and aqueous solutions of binary mixtures of key volatile organic compounds in Swiss cheeses using selected ion flow tube mass spectrometry 下载免费PDF全文
49.
Ruthenium‐Containing Linear Helicates and Mesocates with Tuneable p53‐Selective Cytotoxicity in Colorectal Cancer Cells 下载免费PDF全文
Dr. Simon J. Allison Dr. David Cooke Francesca S. Davidson Prof. Paul I. P. Elliott Dr. Robert A. Faulkner Hollie B. S. Griffiths Owen J. Harper Omar Hussain Prof. P. Jane Owen‐Lynch Prof. Roger M. Phillips Prof. Craig R. Rice Samantha L. Shepherd Dr. Richard T. Wheelhouse 《Angewandte Chemie (International ed. in English)》2018,57(31):9799-9804
The ligands L1 and L2 both form separable dinuclear double‐stranded helicate and mesocate complexes with RuII. In contrast to clinically approved platinates, the helicate isomer of [Ru2( L1 )2]4+ was preferentially cytotoxic to isogenic cells (HCT116 p53?/?), which lack the critical tumour suppressor gene. The mesocate isomer shows the reverse selectivity, with the achiral isomer being preferentially cytotoxic towards HCT116 p53+/+. Other structurally similar RuII‐containing dinuclear complexes showed very little cytotoxic activity. This study demonstrates that alterations in ligand or isomer can have profound effects on cytotoxicity towards cancer cells of different p53 status and suggests that selectivity can be “tuned” to either genotype. In the search for compounds that can target difficult‐to‐treat tumours that lack the p53 tumour suppressor gene, [Ru2( L1 )2]4+ is a promising compound for further development. 相似文献
50.
Ma Z Halling MD Solum MS Harper JK Orendt AM Facelli JC Pugmire RJ Grant DM Amick AW Scott LT 《The journal of physical chemistry. A》2007,111(10):2020-2027
13C chemical shift tensor data from 2D FIREMAT spectra are reported for 4,7-di-t-butylacenaphthene and 4,7-di-t-butylacenaphthylene. In addition, calculations of the chemical shielding tensors were completed at the B3LYP/6-311G** level of theory. While the experimental tensor data on 4,7-di-t-butylacenaphthylene are in agreement with theory and with previous data on polycyclic aromatic hydrocarbons, the experimental and theoretical data on 4,7-di-t-butylacenaphthene lack agreement. Instead, larger than usual differences are observed between the experimental chemical shift components and the chemical shielding tensor components calculated on a single molecule of 4,7-di-t-butylacenaphthene, with a root mean square (rms) error of +/-7.0 ppm. The greatest deviation is concentrated in the component perpendicular to the aromatic plane, with the largest value being a 23 ppm difference between experiment and theory for the 13CH2 carbon delta11 component. These differences are attributed to an intermolecular chemical shift that arises from the graphitelike, stacked arrangement of molecules found in the crystal structure of 4,7-di-t-butylacenaphthene. This conclusion is supported by a calculation on a trimer of molecules, which improves the agreement between experiment and theory for this component by 14 ppm and reduces the overall rms error between experiment and theory to 4.0 ppm. This intermolecular effect may be modeled with the use of nuclei independent chemical shieldings (NICS) calculations and is also observed in the isotropic 1H chemical shift of the CH2 protons as a 4.2 ppm difference between the solution value and the solid-state chemical shift measured via a 13C-1H heteronuclear correlation experiment. 相似文献