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The crystal structures of α-UF5 and U2F9 were refined with high-resolution neutron powder diffraction data from an mixture. Refinement was achieved by a multiphase Rietveld profile refinement technique. The results are compared with previous X-ray and neutron powder studies. 相似文献
3.
High resolution 13C and 15N NMR spectra have been obtained for powdered CH3CN. The presence of resolved dipolar structure in the 13C spectra permits the conclusion that the symmetry axis of the 13C shielding tensor lies along the CN bond direction. 相似文献
4.
Sulfur hexafluoride has a body-centered cubic phase (a = 5.915(3) Å) between its melting point (222.4°K) and 93°K, below which a lower symmetry phase exists. NMR studies show that in both phases there is rapid reorientation of the sulfur hexafluoride molecules. From a neutron diffraction pattern collected at 193°K with λ = 1.086 Å, the data were not satisfied by a model with a spherically symmetrical fluorine density nor by a refinement with conventional ellipsoidal-shaped atoms. The latter gave systematically low S-F distances and abnormally high βij thermal factors. Good agreement was obtained by a combination of Kubic Harmonics with full-matrix least-squares analysis of the neutron profile pattern. The refinement was made with one variable Kubic Harmonic coefficient a2 = 5.94(11), with and . Only four least-squares variables were required with 225 observations in the range of one or more hkl reflections to 2θ = 58.3°. AS-F distance of 1.542(4) Å, obtained from the neutron diffraction data, is in good agreement with the reported value of 1.564(10) Å found from electron diffraction measurements of the vapor. The disordered fluorine distribution has broad maxima on the cell edges similar to those found in the plastic cubic phases of MoF6 and WF6. 相似文献
5.
Russell J. Waugh John H. Bowie Roger N. Hayes 《Journal of mass spectrometry : JMS》1991,26(4):250-256
Deprotonated dipeptides, on collisional activation, fragment by the characteristic process NH2CH(R1) CONHCH(R2)CO2? → NH2?C(R1)CONHCH(R2)CO2H → ?NHCH(R2)CO2H + NH2C(R1)?C?O, when R1 and R2 = H or alkyl. However, when one of the constituent amino acids is either aspartic acid or glutamic acid, the standard cleavage becomes minor in comparison with fragmentation through the α-side-chain of Asp or Glu. For example, [Asp-Leu - H]? and [Leu-Asp - H]? both fragment principally by loss of water, a fragmentation not normally noted for peptides. In addition, [Leu-Asp - H]? loses CO2 and also forms HO2CCH?CHCO2?˙. These fragmentations establish that Asp is the C-terminal amino acid. In contrast, isomeric Glu dipeptides, e.g. [Glu-Ala - H]? and [Ala-Glu - H]? undergo similar fragmentation, both competitively losing H2O and CO2. Both spectra also contain a product ion at m/z 128, identified as the pyroglutamate anion. Product ion and deuterium-labelling studies have been used in an attempt to elucidate the complex fragmentation mechanisms in these systems. 相似文献
6.
F. FRÉZARD A. GARNIER-SUILLEROT C. DEMICHELI 《Journal of inclusion phenomena and macrocyclic chemistry》1997,28(1):51-62
The recent discovery that mithramycin(MTR) in aqueous solution forms a high affinity[Ca(MTR)4]2- complex led us to the idea thatCa2+-loaded liposomes might be able to accumulateMTR in their aqueous internal compartment. Wetherefore investigated the uptake of MTR into largeunilamellar vesicles (LUV) containing NaCl orCaCl2. Our data show that MTR was efficientlyaccumulated within LUV made fromdipalmitoylphosphatidylcholine and cholesterol, onlywhen the liposomes contained Ca2+ and wereresuspended in a Ca2+-free medium. A drugencapsulation efficiency as high as 60% was achieved,at a drug to lipid molar ratio of 1/18. The circulardichroism and fluorescence excitation spectra ofliposome-encapsulated MTR (LMTR) displayed strongsimilarities with those of the [Ca(MTR)4]2-complex. LMTR was found to be stable, when submittedto conditions that destabilized the[Ca(MTR)4]2- complex. Upon dilution andincubation for 24 h at 37 °C, MTR-containingliposomes did not release a significant amount of MTR.These properties were attributed to the formation ofa high affinity complex between MTR and Ca2+inthe aqueous compartment of liposomes. 相似文献
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Verónica de la Fuente Dipl.‐Chem. Mark Waugh Dr. Graham R. Eastham Dr. Jonathan A. Iggo Dr. Sergio Castillón Prof. Dr. Carmen Claver Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):6919-6932
Novel cis‐1,2‐bis(di‐tert‐butyl‐phosphinomethyl) carbocyclic ligands 6 – 9 have been prepared and the corresponding palladium complexes [Pd(O3SCH3)(L‐L)][O3SCH3] (L‐ L=diphosphine) 32 – 35 synthesised and characterised by NMR spectroscopy and X‐ray diffraction. These diphosphine ligands give very active catalysts for the palladium‐catalysed methoxycarbonylation of ethene. The activity varies with the size of the carbocyclic backbone, ligands 7 and 9 , containing four‐ and six‐membered ring backbones giving more active systems. The acid used as co‐catalyst has a strong influence on the activity, with excess trifluoroacetic acid affording the highest conversion, whereas excess methyl sulfonic acid inhibits the catalytic system. An in operando NMR spectroscopic mechanistic study has established the catalytic cycle and resting state of the catalyst under operating reaction conditions. Although the catalysis follows the hydride pathway, the resting state is shown to be the hydride precursor complex [Pd(O3SCH3)(L‐ L)][O3SCH3], which demonstrates that an isolable/detectable hydride complex is not a prerequisite for this mechanism. 相似文献
10.
R. Waugh 《Journal of sound and vibration》1984,93(2):289-305
A computer was programmed to model the distributions of dB(A) levels reaching the ears of an imaginary workforce wearing hearing protectors selected on the basis of either octave band attenuation values or various simplified ratings in use in Australia, Germany, Poland, Spain or the U.S.A. Both multi-valued and single-valued versions of dB(A) reduction and sound level conversion ratings were considered. Ratings were compared in terms of precision and protection rate and the comparisons were replicated for different samples of noise spectra (N = 400) and hearing protectors (N = 70) to establish the generality of the conclusions. Different countries adopt different approaches to the measurement of octave band attenuation values and the consequences of these differences were investigated. All rating systems have built-in correction factors to account for hearing protector performance variability and the merits of these were determined in the light of their ultimate effects on the distribution of dB(A) levels reaching wearers' ears. It was concluded that the optimum rating is one that enables the dB(A) level reaching wearers to be estimated by subtracting a single rating value from the dB(C) level of the noise environment, the rating value to be determined for a pink noise spectrum from mean minus one standard deviation octave band attenuation values with further protection rate adjustments being achieved by the use of a constant correction factor. 相似文献