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141.
Chung MK Orlova G Goddard JD Schlaf M Harris R Beveridge TJ White G Hallett FR 《Journal of the American Chemical Society》2002,124(35):10508-10518
Palladium(0)-catalyzed silane alcoholysis was applied to sugars for the first time using tert-butyldimethylsilane (TBDMS-H) and Ph(3)SiH as the silanes. The catalyst is a colloidal solution of Pd(0) generated in situ from PdX(2) (X = Cl(-), OAc(-)) and TBDMS-H in N,N-dimethylacetamide. The colloid has been characterized by dynamic light scattering and transmission electron microscopy and consists of catalytically highly active nanoparticles of approximately 2 nm diameter. The silane alcoholysis reaction is an effective method for the regioselective silylation of methyl and phenyl glycosides and generates hydrogen gas as the only side product. For many of the sugar substrates investigated, the distribution of regioisomers obtained is complementary to that of the traditional R(3)SiCl/base (base = pyridine, imidazole) methodology and gives convenient access to the 3,6- rather than the 2,6-silylated pyranosides, obtained as the main product by the silyl chloride method. The method also allows a selective axial silylation of levoglucosan and 1,3,5-O-methylidene-myo-inositol. In an attempt to rationalize the observed regioselectivities, ab initio predictions (HF/3-21G) have been made on the relative energies of some of the silylated products. They suggest that the observed regioselectivities do not reflect a kinetic vs thermodynamic product distribution but are induced by the silylation agent employed. Models for the possible origin of the observed regioselectivity in both silylation methods (silane- and silyl chloride-based) are discussed. 相似文献
142.
Bai JZ Ban Y Bian JG Chen AD Chen HF Chen HS Chen JC Chen XD Chen YB Cheng BS Chi SP Chu YP Choi JB Cui XZ Dai YS Dong LY Du ZZ Dunwoodie W Fu HY Fu LP Gao CS Gu SD Guo YN Guo ZJ Han SW Han Y Harris FA He J He JT He KL He M He X Hong T Heng YK Hu GY Hu HM Hu QH Hu T Huang GS Huang XP Huang YZ Izen JM Ji XB Jiang CH Jin Y Jones BD Kang JS Ke ZJ Kim HJ Kim SK Kim TY Kong D Lai YF Li D Li HB Li HH Li J Li JC Li PQ Li QJ Li RY Li W Li WG Li XN Li XQ Liu B Liu F Liu F Liu HM Liu J Liu JP Liu TR 《Physical review letters》2002,88(10):101802
We report values of R = sigma(e(+)e(-)-->hadrons)/sigma(e(+)e(-)-->mu(+)mu(-)) for 85 center-of-mass energies between 2 and 5 GeV measured with the upgraded Beijing Spectrometer at the Beijing Electron-Positron Collider. 相似文献
143.
Several representative examples are given of the successful application of negative staining across the holes of holey carbon support films using 5% (w/v) ammonium molybdate solution containing trehalose. The inclusion of 0.1% (w/v) trehalose is considered to be most satisfactory, although good data have also been obtained in the presence of 0.01 and 1.0% (w/v) trehalose. The examples given fall into the following groups: protein molecules in the absence of polyethylene glycol (PEG), protein molecules in the presence of PEG (Mr 1000), lipoproteins, lipids and membranes, filaments and tubules, viruses in the absence of PEG, viruses in the presence of PEG, aqueous polymer solutions, and finally for comparison purposes, four unstained samples studied in the presence of trehalose alone. In all these cases, and many others not documented here, successful spreading of the sample across holes has been achieved, with the sample embedded within a thin film of air-dried ammonium molybdate+trehalose. These specimens can be rapidly produced and provide an alternative to negatively stained specimens on carbon support films. Specimen stability in the electron bean is good and such specimens can usually generate superior negatively stained TEM images without flattening and adsorption artefacts. The formation of 2-D arrays/crystals of protein molecules and viruses, suspended across holes in the presence of ammonium molbybdate+trehalose, and trehalose alone, is also demonstrated. 相似文献
144.
Two nitrogen ceramic phases, the oxynitride LiSiON and the nitride LiSi2N3, have been studied by 6Li and 7Li NMR. Magic angle spinning (MAS) NMR experiments have been carried out at two magnetic field strengths (7.05 and 14.1 T). The spectra give evidence of the relative effects of the quadrupolar and chemical shift interactions. The electric field gradient tensor of both phases has been determined accurately by iterative fitting of the 6Li and 7Li MAS NMR line shapes at the two magnetic field strengths. Due to the fact that for 7Li the quadrupolar interaction is much larger than the chemical shift interaction, it is shown that neither the small chemical shift anisotropy nor the relative orientation of the two interaction tensors can be determined accurately by 7Li MAS NMR. For 6Li, the two interactions are comparable and the value of these parameters obtained from the fits of the 6Li experimental MAS line shapes are therefore much more reliable. 相似文献
145.
A flow system has been developed to study relative rate coefficients of hydroxyl radicals reacting with alkanes under conditions relating to tropospheric chemistry. Relative Arrhenius parameters have been measured over the temperature range 243–328 K for pairs of alkanes from a list consisting of n-butane, 2-methylpropane, n-pentane, n-hexane, 2,2- and 2,3-dimethylbutane, 2,3,3-trimethylbutane, and 2,3,4-trimethylpentane. The results have been incorporated into a Structure-Activity Relation for hydroxylalkane reactions which leads to the following group rate coefficients for a temperature range of 240–500 K. 相似文献
146.
147.
Semi-empirical molecular orbital calculations were performed for CrF3?6 and FeF3?6. The method of calculation is derived from the HF SCF equations using approximations appropriate to the highly ionic transition metal halides. The results of these calculations are shown to be in better agreement than previous semis-empirical calculations with X-ray emission line shifts and atom charges and populations estimated from these shifts. 相似文献
148.
149.
We describe the operating characteristics of a compact, frequency tunable, electron-beam-controlled, 15 atmosphere CO2 laser. Two intracavity Fabry-Perot etalons have been used to obtain laser line narrowing and continuous tuning within the 10.4 μm and 9.4μm bands of the CO2 gain spectrum. The laser output consists of a 100 nsec pulse (fwhm) with energy up to 100 mJ. The overall laser tuning range is 70 cm-1 and we have measured a laser linewidth of 0.03 cm-1. 相似文献
150.
NMR measurements on In115 in B2-type PdIn from RT to 4.2°K are reported The low Knight shift is attributed to a reduction of the amount of s- character in wave functions at the In sites and not the density of states at the the Fermi level. The existence of a localized moment is considered. 相似文献