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61.
62.
Maurice M. Bursey Donald J. Harvan Carol E. Parker Thomas A. Darden J. Ronald Hass 《Journal of mass spectrometry : JMS》1983,18(12):530-533
The methylnitrenium, ethylnitrenium and dimethylnitrenium ions are prepared by charge reversal collisional activation (CR CA) of the corresponding negative ions; their collisional activation mass spectra are shown to support the assigned structures. MINDO/3 energies are used to evaluate relative energies of [CH4N]+ and [C2H6N]+ isomers, and to determine whether unstable forms rearrange spontaneously to stable ones. As in other examples, charge reversal here generates cations that do not exist in an energy well, but their transient existence is established because their fragmentation is more rapid than their rearrangement to a more stable form. 相似文献
63.
The results of allowing tetrahydro-as-triazine-3(2H)-thiones to react with various α,β-diiunctional compounds, such as, α-bromoethyl p-toluenesulfonate, chloroacetaldehyde, α-bromophenylacet-uldehyde, phenaeyl bromide, chloroacetonitrile, α-bromophenylaeelonitrile, and α-cyanobenzyl p-toluenesulfonate are discussed. These condensations give either a 5H-thiazolo[3,2-b]-as-triazine or a 2H-thiazolo[2,3-c]-as-triazine. 相似文献
64.
Donald H. Lemmon 《Journal of Molecular Structure》1978,49(1):71-82
The IR spectra of the vapor, liquid and solid phases of hexafluorohexa-2-diyne, F3C-CC-CC-CF3, were measured. The liquid phase Raman spectrum with polarizations was measured. These vibrational spectra fit D3d selection rules, establishing that the molecule has a linear carbon skeleton. The IR spectra indicate that the -CF3 groups rotate freely in the vapor phase, but that conformers exist in the condensed phases. The electron impact mass spectrum was measured and the molecular ion produced the strongest peak. 相似文献
65.
The isothermal and temperature scanning calorimeters manufactured by Calorimetry Sciences Corporation are briefly described. Applications of calorimetry to determine thermodynamics and kinetics of reactions of interest in biotechnology are described with illustrative examples. 相似文献
66.
Using the Picker flow microcalorimeter, excess heat capacities have been obtained at 25°C throughout the concentration range for 2,2-dimethylbutane,n-hexane, and cyclohexane each mixed with a series of hexadecane isomers of increasing degrees of orientational order, as determined by depolarized Rayleigh scattering. The isomers are 2,2,4,4,6,8,8-heptamethylnonane, 6-, 4-, and 2-methylpentadecane, andn-hexadecane. Thec
p
E
values are negative, increasing rapidly in magnitude with increase of orientational order, and are not predicted by the Prigogine—Flory theory which neglects order. Values ofc
p
E
are obtained at 10, 25, and 55°C for cyclohexane +6-, 4-, and 2-methylpentadecane which with other literature data lead to the temperature dependence of the thermodynamic excess functions for cyclohexane solutions of the five C16 isomers. The excess enthalpy and entropy vary with the C16 isomer and with temperature, but the corresponding variation of the excess free energy is small, indicating a high degree of enthalpy-entropy compensation. This is consistent with a rapid decrease with temperature of orientational order in the C16 isomers. 相似文献
67.
M. G. O. Santana-Marques A. J. V. Ferrer-Correia K. A. Caldwell M. L. Gross 《Journal of the American Society for Mass Spectrometry》1993,4(10):819-827
Aromatic β-hydroxyoximes undergo unusual fragmentation reactions as protonated or cationized species, as radical cations, or as (M - H)? ions, As protonated species, they expel OH ’ from the oxime functionality in violation of the even electron rule. Parallel eliminations of alkyl radicals follow OH’ loss when the aromatic ring is substituted with an alkyl chain. Alkyl radical losses appear to be characteristic of radical cations that can isomerize to ions in which the alkyl chain bears a radical site and the charged site is the conjugate acid of a basic functionality (e.g., oxime or imine). Evidence for the mechanisms was found in the ion chemistry of oxime and imine radical cations. The imine reference compounds were conveniently generated by fast atom bombardment-induced reduction of oximes, removing the requirement for using conventional chemical synthesis. Protonated imines and the (M - H)? ions of oximes fragment extensively via charge-remote processes to eliminate the elements of alkanes. This chemistry is not shared by the protonated oximes. 相似文献
68.
O-GlcNAcylation of serine and threonine residues is a dynamic and essential post-translational modification involved in signaling pathways in eukaryotes. Studies of O-GlcNAcylation would be aided by small-molecule inhibitors of O-GlcNAc transferase (OGT), the sole enzyme know to mediate this modification, but discovery of such molecules has been hampered by poor expression of cloned OGT and lack of suitable high-throughput screens. This Communication describes the development an expression system to access large amounts of the catalytic domain of OGT and the implementation of a fluorescence-based substrate analogue displacement assay that has led to the discovery of a set of OGT inhibitors. This work lays the foundation for both structural and functional analysis of the catalytic domain of OGT. 相似文献
69.
Ho-Shen Lin Ashraff A. Rampersaud Karen Zimmerman Mitchell I. Steinberg Donald B. Boyd 《中国化学会会志》1993,40(3):273-282
A series of nonpeptide angiotensin II receptor antagonists was synthesized via palladium-assisted cross coupling of aryl stannane and cycloalkenyl triflates and subsequent alkylation of silyl-protected imidazole. Our compounds, which have a terminal five- to seven-membered cycloalkenyl ring, are compared to DuPont EXP7711, an N-[(2′-carboxybiphenylyl)methyl]imidazole, which has a terminal phenyl moiety. Physicochemical properties of the compounds, such as lipophilicity, steric bulk, conformation, and the relative spatial proximity of the 2-carboxyl and the middle phenyl, are quantitated by computational chemistry. Potency in terms of binding affinity to AT1 receptors in rat adrenal glomerulosa and rabbit aorta is maximized when the terminal ring is aromatic. 相似文献
70.
Donald L. Hunston 《Journal of polymer science. Part A, Polymer chemistry》1976,14(3):713-727
A reduction of frictional drag in turbulent flow was obtained in benzene by using three monodisperse polystyrene samples having weight-average molecular weights of 1.8, 4.1 and 7.1 × 106. By testing these polymers individually and in mixtures, data were obtained for samples with known molecular weight distributions. The drag reduction of these samples was studied as a function of polymer concentration and flow rate so that a generalized picture of the effects of polydispersity could be obtained. These results are used to help explain much of the behavior that was observed for polystyrene and other polymers. This includes the fact that the polystyrene samples exhibit a remarkably high resistance to the loss of drag reduction via degradation in turbulent flow. Such experiments indicate that drag reduction and degradation depend strongly on molecular weight distribution. Thus a molecular level interpretation of experimental results cannot be made unless the effects of the distribution are considered. 相似文献