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1.
Andrew L. Sargent Mark E. Rollog Cassandra T. Eagle 《Theoretical chemistry accounts》1997,97(1-4):283-288
Fenske-Hall molecular orbital calculations have been applied to a new, structurally isolable analog of the intermediate involved
in catalytic rhodium carboxylate carbenoid transformations. Results from the structural characterization of axially ligated
rhodium acetate phenylisonitrile complexes have been utilized in approximate molecular orbital calculations. The results from
the calculations suggest that a significant degree of π back-bonding exists between the metal and isonitrile fragments which,
by analogy, implies that π back-bonding should also exist in the rhodium carbenoid intermediate. Sensitivity of the Fenske-Hall
method to the magnitude of π back-donation in these complexes was gauged through calculations involving different phenylisonitrile
groups in which the π back-bonding ability was modulated through derivativization. The reliability of the Fenske-Hall method
was evaluated through a comparison to a high-level calculation.
Received: 13 December 1996 / Accepted: 18 March 1997 相似文献
2.
V. E. Noshkin W. L. Robison K. M. Wong R. J. Eagle 《Journal of Radioanalytical and Nuclear Chemistry》1998,234(1-2):243-249
There continue to be reports in the literature that suggest a difference in the behavior of239+240Pu and238Pu in some aquatic environments. Plutonium isotopes have been measured in marine samples collected over 3 decades from Enewetak
atoll, one of the sites in the Marshall Islands used by the United States between 1946 and 1958 to test nuclear devices. The
plutonium isotopes originated from a variety of complex sources and could possibly coexist in this environment as different
physical-chemical species. However results indicate little difference in the mobility and biological availability of239+240Pu and238Pu. 相似文献
3.
A 1H MRS study of probable Alzheimer's disease and normal aging: implications for longitudinal monitoring of dementia progression 总被引:10,自引:0,他引:10
Rose SE de Zubicaray GI Wang D Galloway GJ Chalk JB Eagle SC Semple J Doddrell DM 《Magnetic resonance imaging》1999,17(2):291-299
In order to evaluate the capability of 1H MRS to monitor longitudinal changes in subjects with probable Alzheimer's disease (AD), the temporal stability of the metabolite measures N-acetylaspartate and N-acetylaspartylglutamate (NA), total Creatine (Cr), myo-Inositol (mI), total Choline (Chol), NA/Cr, mI/Cr, Chol/Cr and NA/mI were investigated in a cohort of normal older adults. Only the metabolite measures NA, mI, Cr, NA/Cr, mI/Cr, and NA/mI were found to be stable after a mean interval of 260 days. Relative and absolute metabolite measures from a cohort of patients with probable AD were subsequently compared with data from a sample of normal older adult control subjects, and correlated with mental status and the degree of atrophy in the localized voxel. Concentrations of NA, NA/Cr, and NA/mI were significantly reduced in the AD group with concomitant significant increases in mI and mI/Cr. There were no differences between the two groups in measures of Cr, Chol, or Chol/Cr. Significant correlations between mental status as measured by the Mini-Mental State Examination and NA/mI, mI/Cr and NA were found. These metabolite measures were also significantly correlated with the extent of atrophy (as measured by CSF and GM composition) in the spectroscopy voxel. 相似文献
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5.
C. T. Eagle D. G. Farrar G. N. Holder D. M. Gooden A. B. Goodman S. W. Wyatt 《The Chemical Educator》1999,4(3):105-107
The synthesis of tris(diethyldithiocarbamato) cobalt(III) by the reaction of sodium diethyldithio-carbamate and cobaltous chloride is described. The recovered crystals of the cobalt complex are characterized by magnetic susceptibility, IR and NMR spectroscopy, and cyclic voltammetry. 相似文献
6.
Self-injection length in La0.7Ca0.3MnO3-YBa2Cu3O7-δ ferromagnet-superconductor multilayer thin films
We have carried out extensive studies on the self-injection problem in barrierless heterojunctions between La0.7Ca0.3MnO3 (LCMO) and YBa2Cu3O7-δ (YBCO) thin films. The heterojunctions were formed in situ by sequentially growing LCMO and YBCO films on 〈100〉 LaAlO3 (LAO) substrate using a pulsed laser deposition (PLD) system. YBCO micro-bridges with 64 μm width were patterned both on
the LAO (control) and LCMO side of the substrate. Critical current, I
c, was measured at 77 K on both the control side as well as the LCMO side for different YBCO film thickness. It was observed
that while the control side showed a J
c of ∼ 2 × 106 A/cm2, the LCMO side showed about half the value for the same thickness (1800 ?). The difference in J
c indicates that a certain thickness of YBCO has become ‘effectively’ normal due to self-injection. From the measurement of
J
c at two different thicknesses (1800 ? and 1500 ?) of YBCO films both on the LAO as well as the LCMO side, the value of self-injection
length (at 77 K) was estimated to be ∼ 900 ?. To the authors’ best knowledge, this is the first time that self-injection length
has been quantified. A control experiment carried out with LaNiO3 deposited by PLD on YBCO did not show any evidence of self-injection. 相似文献
7.
The complexes TpWO2X react with sulfiding agents such as B2S3 or P4S10 to give the oxothio- and bis(thio)tungsten(VI) complexes TpWOSX (X = Cl(-)) and TpWS2X [X = Cl(-), S2PPh2(-); Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate]. The reaction of TpWS2Cl with (i) PPh3 in pyridine and (ii) dimethyl sulfoxide affords TpWOSCl in good overall yield. The chloro complexes undergo metathesis with alkali metal salts to yield species of the type TpWOSX and TpWS2X [X = OPh(-), SPh(-), SePh(-), (-)-mentholate]. The diamagnetic complexes exhibit NMR spectra indicative of C(1) (TpWOSX) or C(s) (TpWS2X) symmetry and IR spectra consistent with terminal oxo and thio ligation (nu(W=O), 940-925 cm(-1); nu(W=S) or nu(WS2), 495-475 cm(-1)). Crystals of (R,S)-TpWOS[(-)-mentholate] are monoclinic, space group P2(1), with a = 11.983(2) A, b = 18.100(3) A, c = 13.859(3) A, beta = 91.60(2) degrees, V = 3004.6(8) A(3), and Z = 4. Crystals of TpWS2(OPh)-CH2Cl2 are orthorhombic, space group Pbca, with a = 16.961(4) A, b = 33.098(7) A, c = 9.555(2) A, V = 5364(2) A(3), and Z = 8. The mononuclear, distorted-octahedral tungsten centers are coordinated by a tridentate Tp ligand, an alkoxy or aryloxy ligand, and two terminal chalcogenide ligands. The average W=O and W=S distances are 1.726(7) and 2.125(2) A, respectively, and the O=W=S and S=W=S angles 102.9(3) and 102.9(1) degrees, respectively. The tungsten and sulfur X-ray absorption spectra of TpWOSCl and TpWS2Cl are consistent with the presence of terminal pi-bonded thio ligands in both complexes. The thio complexes generally undergo a reversible one-electron reduction at potentials significantly more positive than their oxo analogues. The chemical, spectroscopic, and electrochemical properties of the complexes are heavily influenced by the presence of W=S pi frontier orbitals. 相似文献
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9.
V. J. Harding Th. F. Nicholson G. A. Grant G. Hern C. E. Downs A. Castellani F. E. Taylor A. I. Kendall G. C. Linder D. D. van Slyke Eagle M. Somogyi A. L. Raymond J. G. Blanco Margrethe Sorensen G. Haugaard S. Fränkel C. Jellinek P. A. Levene T. Mori H. Bierry Cl. Rimington B. Lustig S. P. L. Sorensen Margrethe Høyrup W. M. Dehn K. E. Jackson D. A. Ballard V. Boulez Spannuth und Power 《Analytical and bioanalytical chemistry》1935,101(5-6):204-214
10.
V. J. Harding Th. F. Nicholson G. A. Grant G. Hern C. E. Downs A. Castellani F. E. Taylor A. I. Kendall G. C. Linder D. D. van Slyke Eagle M. Somogyi A. L. Raymond J. G. Blanco Spannuth und Power Margrethe Sorensen G. Haugaard S. Fränkel C. Jellinek P. A. Levene T. Mori H. Bierry Cl. Rimington B. Lustig S. P. L. Sorensen Margrethe Høyrup W. M. Dehn K. E. Jackson D. A. Ballard und V. Boulez 《Fresenius' Journal of Analytical Chemistry》1935,101(5-6):204-214
Ohne Zusammenfassung 相似文献