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31.
The asymmetric syntheses of the C-1 sidechains of zaragozic acid A and C are described. Aldol reaction defines the chirality at C-4′and C-5′in two independent routes. Multigram preparation as well as a route amenable to derivatization are highlights of these approaches. 相似文献
32.
Todorov E Evans M Lee S Rousseau R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(12):2652-2662
The total electronic energies of the six electrons per atom (e per atom) alloys W, TaRe, HfOs, and YIr and the seven electrons per atom alloys Re, WOs, TaIr, HfPt, and YAu have been calculated in the local density approximation of density functional theory. When one considers common alloy structures such as atomically ordered variants of the body-centered cubic, face-centered cubic, or hexagonally closest packed structures and plots the total electronic energy as a function of the unit cell parameter, one finds for both the six and seven electrons per atom series energetic isosbestic points. An energetic isosbestic point corresponds to a critical value of the size parameter for which all members of the 6 or 7 e per atom series of compounds have nearly identical total electronic energy. Just as in spectroscopy, where the existence of such isosbestic points is the hallmark of two compounds present in the mixture, an energy isosbestic point implies there are just two separate energy curves. For both series it is found that the total electronic energy can be viewed as the weighted sum of a purely covalent term and a purely ionic term. Two semi-quantitative models are proposed to account for these two separate energies. In the first model the total energy is viewed as the sum of the elemental structural energy plus an ionic energy based on the Born-Mayer ionic model. In the second model one considers within the confines of mu2-Hückel theory the evolution of the total electronic energy as the Coulombic Hii integrals change in value. 相似文献
33.
Evans PA Sawyer JR Lai KW Huffman JC 《Chemical communications (Cambridge, England)》2005,(31):3971-3973
The crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. 相似文献
34.
Siya Ram William Evans Dean S. Wise Leroy B. Townsend John W. Mccall 《Journal of heterocyclic chemistry》1989,26(4):1053-1059
A series of methyl 2-substituted purine 8-carbamates was prepared and evaluated for antifilarial activity. These purines were synthesized as aza congeners of benzimidazole carbamates which have shown significant anthelmintic activity to determine the effect that this modification might have on anthelmintic activity. The compounds were tested against the filarial infection, B. pahangi, in jirds. None of the compounds prepared in this study demonstrated antifilarial activity. 相似文献
35.
Robert J. Evans Thomas A. Milne Michael N. Soltys Hans-Rolf Schulten 《Journal of Analytical and Applied Pyrolysis》1984,6(3):273-283
Pyrolysis-mass spectrometric studies of cellulose indicate low abundances of levoglucosan in the product spectrum compared to the yield values determined in more conventional types of pyrolysis studies. To examine the reason for these conflicting observation, levoglucosan was examined under different ion source conditions and ionization modes to ascertain the relative contributions of thermal degradation and ionization fragmention to the low abundances of the levoglucosan molecular ion. Low-energy electron ionization using conventional sample volatilization and molecular-beam sampling is compared to chemical ionization using methane, isobutane, and ammonia as reagent gases, and to field ionization and desorption. The mass spectrometric fragmentation patterns under the various systems indicate that studies of cellulose pyrolysis underestimate the amount of levoglucosan formed due to ionization fragmentation and thermal rearrangement reactions in the ion source. Several peaks, including m/z 126 and 144, are dominated by the contribution from the fragmentation of levoglucosan. 相似文献
36.
The displacements of the methyl substituents away from the metal and out of the cyclopentadienyl ring plane are compared in sterically crowded (C(5)Me(5))(3)M complexes vs sterically normal f-element complexes in an attempt to evaluate the utility of this parameter in predicting unusual (C(5)Me(5))(1-) ring reactivity. The out-of-plane displacements of 16 sterically crowded tris(cyclopentadienyl) complexes of general formula (C(5)Me(5))(3)M, (C(5)Me(4)R)(3)M (R = Et, (i)Pr, (t)()Bu, SiMe(3)), (C(5)Me(5))(3)MX (X = anion), and (C(5)Me(5))(3)ML (L = neutral ligand) are compared with [(C(5)Me(5))(2)U](2)(C(6)H(6)), (C(5)Me(5))(2)Sm(PC(4)H(2)(t)Bu(2)), and 33 representative examples of f-element bis(cyclopentadienyl) complexes with normal cyclopentadienyl behavior and coordination numbers ranging from 6 to 10. In general, the methyl displacement values of sterically crowded complexes overlap with those in the other complexes, which demonstrates that the basis of the structural distortions is complex. However, if the most extreme out-of-plane displacement in each of the sterically crowded complexes is examined vs the analogous maximum out-of-plane displacement in less crowded systems, there appears to be a basis for predicting cyclopentadienyl reactivity. 相似文献
37.
D. Fennell Evans Martin Allen B. W. Ninham Abdel Fouda 《Journal of solution chemistry》1984,13(2):87-101
Critical micelle concentrations were determined by conductance measurements for decyl-, dodecyl-, tetradecyl- and hexadecyltrimethylammonium bromide in water at 25, 60, 95, 130, and 160°C. The results are discussed in terms of the equilibrium model and the nonlinear Poisson-Boltzmann model for micelle formation. The free energies of transferring a methylene group from water to the oil-like interior of the micelle are found to be –781 at 25°C, –796 at 60°C, –819 at 95°C, –815 at 130°C, and –787 at 160°C cal-mol–1. 相似文献
38.
39.
Heterogeneous fluorescence immunoassays have been automated using flow injection manifolds incorporating thiophilic gel solid phase reactors to separate antibody-bound and unbound analyte molecules. Antibody elution is achieved by changes in ionic strength, thus allowing the use of pH sensitive fluorescent labels. This facilitates the development of dual analyte systems, in which two competitive immunoassays with separate labels are monitored in parallel. Detection of the fluorophores by high speed synchronous fluorescence scanning while the flow is briefly stopped utilises either one synchronous interval which detects both fluorophores, or two separate scans at different wavelength intervals, one for each fluorophore. Simultaneous analyses of serum albumin and transferrin exemplify these novel approaches. Spectroscopic interferences are very small, analyte recoveries are close to 100%, with a relative standard deviation of 5-6% and a sampling rate of 20 h-1. 相似文献
40.
Christopher H. Evans Morgan Partyka Jan Van Stam 《Journal of inclusion phenomena and macrocyclic chemistry》2000,38(1-4):381-396
Naphthalene forms 1 : 1 complexes with -cyclodextrin (-CD)in water. The binding constant is 377 ± 35 M-1. Addition of linear or branched alcohols causes a reduction in the apparent strength of naphthalene binding (Kapp) compared to the value in the absence of additives. For example, 1% 1-pentanol reduces Kapp to 184 ± 31 M-1. Branching does not alter Kapp much for a given number of carbon atoms, e.g., it is 113 ± 9 M-1for 2-pentanol and 116 ± 8 M-1for 3-pentanol. The exception to this is tert-butanol for which Kapp is 577 ± 40 M-1. The variation in Kapp as a function of [1-pentanol] yields values for the individual equilibrium constants contributing to Kapp. This reveals that a ternary complex forms involving naphthalene, the CD and 1-pentanol. The constant for formation of the ternary complex is 99 ± 29 M-2. NaI quenching of naphthalene fluorescence indicates that the CD cavity partially protects the naphthalene excited state fromthis water phase quencher. Interestingly, the Stern–Volmer constant is lower in the presence of 1-pentanol than in its absence, although there should be more unbound (and therefore more NaI accessible) naphthalene in the former system than in the latter. These apparently contradictory results are discussed in terms of ternary complex formation. 相似文献