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31.
The dipole strengths of the 4A2 → 4T1(F), 4T1(P), d-electron transitions of the cobalt(II) tetrahalides are found to decrease with an increase in temperature, in agreement with a dynamic ligand-polarisation model for the absorption mechanism. The reduction in dipole strength is accounted for by a decrease in the coulombic coupling between the quadrupole moment of the d-electron transition of the metal ion and the transient electric dipole moment induced in the ligands, due to the anharmonic increase in the mean bond length and the progressively larger mean-square amplitudes of the bending modes of the complex ion in its ground electronic state as the temperature is raised. 相似文献
32.
Chris Mussell Céline S. J. Wolff Briche Chris Hopley Gavin O’Connor 《Accreditation and quality assurance》2007,12(9):469-474
The method used at LGC for analysis of “total” 19-norandrosterone (19-norandrosterone glucuronide plus “free” 19-norandrosterone)
in urine for the Comité Consultatif pour la Quantité de Matière Pilot Study (CCQM-P68) is described. The analytical method
used was a modified version of the method developed at the National Measurement Institute of Australia, which used a hydrolysis
and derivatisation procedure first described by the German Sports University. This method is routinely used by World Anti-Doping
Agency-accredited laboratories for sports drug testing. The main modifications made to the method were the use of 19-norandrosterone
glucuronide as a calibration standard and 19-norandrosterone glucuronide-d4 as an isotopically labelled internal standard,
and the use of a bench-top quadrupole gas chromatograph–mass spectrometer. The results produced by LGC (2.14 ± 0.15 ng g−1 expanded uncertainty, coverage factor k = 2) were in excellent agreement with those from other participating national metrology institutes and thus further validates
the exact-matching isotope-dilution mass spectrometric procedures used at LGC for a wide range of reference measurement applications,
including measurement of ng g−1 levels of steroids in a biological matrix. 相似文献
33.
Kean H. Khoo K. Rodney Fernando Richard J. Fereday Chee-Yan Chan 《Journal of solution chemistry》1995,24(10):1039-1048
The solubility of thallium(I) chloride has been determined in aqueous solutions of strontium chloride and barium chloride at concentrations up to 1.5 mol kg–1. The data were analyzed using Pitzer's equations without making explicit assumption of association to ion pairs by assuming =3 instead of =2, with the (1) term for TlCl being equivalent to the (2) term for 2-2 electrolytes. Best values of (0) and (1) for TlCl are recommended together with K
s
, the activity solubility product. These were used to fit the present solubility data and derive the Pitzer model mixture parameters relevant to the systems, fTIN and fTINCl (N=Sr, Ba). Mixture parameters for TlCl+MCl+H2O systems are also derived to complete the parameter base. The fit of the experimental data was found to be worse when higher-order terms for asymmetrical mixing were included in the analysis. Activity coefficients for thallium(I) chloride in the mixtures are derived. 相似文献
34.
Eckers C Monaghan JJ Wolff JC 《European journal of mass spectrometry (Chichester, England)》2005,11(1):73-82
This work describes electrospray ionisation tandem mass spectrometry studies of trimethoprim and a series of structurally similar compounds containing alkoxy-phenyl groups; using accurate mass measurement to confirm the proposed fragmentations. Radical cations were observed in the spectra obtained for some of the compounds, as well as uncommon fragmentations showing losses of CH4 and C2H6, whereas other compounds showed the formation of even electron ions. Possible structures for the fragment ions have been proposed and explanations for the different types of fragmentations based on the structures of the compounds. In addition an alternate structure for a fragment ion previously reported for tandem mass spectrometry of trimethoprim has been proposed, based on accurate mass measurement. 相似文献
35.
Tohru HoriguchiChristopher D Rithner Rodney CroteauRobert M Williams 《Tetrahedron》2003,59(2):267-273
The putative metabolite, 5α-acetoxytaxa-4(20),11-dien-2α,10β-diol (7), which is a promising candidate as a biosynthetic pathway triol in taxol biosynthesis, has been prepared by Barton deoxygenation of the C-14-hydroxyl group of a differentially protected derivative of natural 2α,5α,10β-triacetoxy-14β-(2-methyl)-butyryloxytaxa-4(20),11-diene (8), a major taxoid metabolite isolated from Japanese Yew heart wood. The synthetic protocol devised, is amenable for the preparation of isotopically labeled congeners that will be useful to probe further intermediate steps in the biosynthesis of taxol. 相似文献
36.
D. W. Greeno M. S. Sommers R. N. Wolff 《The Journal of the Operational Research Society》1977,28(4):829-838
A number of transportation demand models have been formulated using the abstract mode concept. Unfortunately, most of these models use a priori economic theory to derive the variables used in the analysis. This study describes an empirical approach for the specification of mode attributes used by purchasers of transportation modes for the movement of commodities. Results reported from a study conducted on the Montreal-Toronto corridor in Canada suggest that a number of important variables have been neglected in models of carrier selection for freight. 相似文献
37.
38.
Results from full fourth-order perturbation theory [SDTQ MBPT(4)], and the coupled-cluster single- and double-excitation model (CCSD). are compared with recent full CI results for BH, HF, NH3, and H2O. For H2O, studies include large symmetric displacements of the OH bonds, which offer a severe test for any single-reference MBPT/CC method. In every case. CCSD plus fourth-order triple-excitation terms provide agreement with the full CI to < 2 kcal/mole. SDTQ MBPT(4) has an error 10 kcal/mole for displaced H2O. 相似文献
39.
The axial single-crystal magnetic circular dichroism spectra of Cs3ZnCl5/Co2+ and Cs3ZnBr5/Co2+ have been measured over the 4000–7000 cm?1 region of the 4A2 → 4T1 (F) transition at ambient and liquid-helium temperature. The B/D and C/D terms obtained give transition moment ratios, 〈t2∥m∥t2〉/〈e∥m∥t2〉, in accord with the value required (?3/2) by a dynamic ligand-polarisation model for d-electron transition probabilities in tetrahedral metal complexes. 相似文献
40.
The lack of reference materials, accurately certified for nitrite, is a problem in view of the importance of this species for environmental and medical reasons. This work outlines a plan for the preparation of nitrite isotopic reference materials (IRMs) in the form of high purity solutions, certified for their nitrite-nitrogen isotopic composition and nitrite concentration. To achieve the desired accuracy (expanded uncertainty U with a coverage factor k=2 of =2%), primary methods of measurement such as isotope dilution mass spectrometry (IDMS), gravimetry, and titrimetry must be used. The main difficulty is the stability of nitrite. Other problems expected in the preparation and certification of nitrite IRMs are described. Results from long term stability studies (up to 1.5 years) and a procedure for the purification of the candidate nitrite IRMs are presented. The purpose is to use these IRMs for high accuracy method calibrations and as anchor points for SI-traceable nitrite concentrations. Reference values linked to the SI system are useful to demonstrate the degree of international comparability of nitrite measurements in intercomparison programmes such as the IRMM-International Measurement Evaluation Programme (IMEP). 相似文献