[reaction: see text]. The total synthesis of the potent immunosuppressant FR901483 is described. In a key step, the intermolecular Diels-Alder cycloaddition of an amidoacrolein with 2-(triisopropylsilyloxy)-1,3-butadiene produced the desired 3-cyclohexene-1-carboxaldehyde. This compound was subjected to basic followed by acidic conditions which effected two sequential aldol cyclizations to deliver the tricyclic ring system of the natural product, suitably functionalized for completion of the total synthesis. 相似文献
The double metallation of 6-bromo-3H-benzothiazol-2-one and 6-bromo-3H-benzoxazol-2-one with methyl magnesium bromide and alkyllithium bases is described. Alkylation with a variety of electrophiles occurs at the 6-position of the heterocycles in good yields. 相似文献
In this study, we utilized picosecond pulses from an Nd:YAG laser to investigate the nonlinear optical characteristics of monolayer MoSe2. Two‐step growth involving the selenization of pulsed‐laser‐deposited MoO3 film was employed to yield the MoSe2 monolayer on a SiO2/Si substrate. Raman scattering, photoluminescence (PL) spectroscopy, and atomic force microscopy verified the high optical quality of the monolayer. The second‐order susceptibility χ(2) was calculated to be ~50 pm V?1 at the second harmonic wavelength ~810 nm, which is near the optical gap of the monolayer. Interestingly, our wavelength‐dependent second harmonic scan can identify the bound excitonic states including negatively charged excitons much more efficiently, compared with the PL method at room temperature. Additionally, the MoSe2 monolayer exhibits a strong laser‐induced damage threshold ~16 GW cm?2 under picosecond‐pulse excitation. Our findings suggest that monolayer MoSe2 can be considered as a promising candidate for high‐power, thin‐film‐based nonlinear optical devices and applications. 相似文献
Summary: The phase behavior of poly(p‐phenylene terephthalate)s (PPT) with pendant side groups, N‐(4‐nitrophenyl)ethylaminoethanol (NPE) and N‐(4‐nitrophenyl)‐L ‐prolinol (NPP) has been studied by using differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), and second harmonic generation (SHG). PPT‐NPE showed a layered liquid crystalline morphology while PPT‐NPP showed a completely amorphous structure. Compressive or shear stress applied on the polymer melt surface at 210 °C induced a more prominent layered structure of PPT‐NPE whereas the amorphous structure of PPT‐NPP remained unchanged under the stress. In order to understand this phase difference in terms of the repeat structure, we attempted theoretical ab initio Hartree‐Fock, and DFT calculations for the monomers and molecular dynamics for the bulk state. The results indicated that molecular configurations are a good way of microscopically understanding the phases of rigid backbone polymers with functional side groups: The NPT (constant particle number, pressure, and temperature) simulation data at 210 °C agree qualitatively with the experimental data and the difference between PPT‐NPE and PPT‐NPP could be understood using rotational energy barrier, steric hindrance and inter‐chain interactions. X‐ray diffractometer (XRD) simulation patterns for the oligomers are also in qualitative agreement with the experimental WAXS data and the structural parameters of stacks of PPT‐NPE chains are estimated to be layer distance (4.6 Å), backbone distance (21.5 Å), and side distance (12 Å).
We considered a Bak-Sneppen model on a Sierpinski gasket fractal. We calculated the avalanche size distribution and the distribution of distances between subsequent minimal sites. To observe the temporal correlations of the avalanche, we estimated the return time distribution, the first-return time, and the all-return time distribution. The avalanche size distribution follows the power law, P(s)∼s−τ, with the exponent τ=1.004(7). The distribution of jumping sites also follows the power law, P(r)∼r−π, with the critical exponent π=4.12(4). We observe the periodic oscillation of the distribution of the jumping distances which originated from the jumps of the level when the minimal site crosses the stage of the fractal. The first-return time distribution shows the power law, Pf(t)∼t−τf, with the critical exponent τf=1.418(7). The all-return time distribution is also characterized by the power law, Pa(t)∼t−τa, with the exponent τa=0.522(4). The exponents of the return time satisfy the scaling relation τf+τa=2 for τf?2. 相似文献
Hydrous Fe and Mn oxides (HFO and HMO) are important sinks for heavy metals and Pb(II) is one of the more prevalent metal contaminants in the environment. In this work, Pb(II) sorption to HFO (Fe(2)O(3) x nH(2)O, n=1-3) and HMO (MnO(2)) surfaces has been studied with EXAFS: mononuclear bidentate surface complexes were observed on FeO(6) (MnO(6)) octahedra with PbO distance of 2.25-2.35 Angstrom and PbFe(Mn) distances of 3.29-3.36 (3.65-3.76) Angstrom. These surface complexes were invariant of pH 5 and 6, ionic strength 2.8 x 10(-3) to 1.5 x 10(-2), loading 2.03 x 10(-4) to 9.1 x 10(-3) mol Pb/g, and reaction time up to 21 months. EXAFS data at the Fe K-edge revealed that freshly precipitated HFO exhibits short-range order; the sorbed Pb(II) ions do not substitute for Fe but may inhibit crystallization of HFO. Pb(II) sorbed to HFO through a rapid initial uptake ( approximately 77%) followed by a slow intraparticle diffusion step ( approximately 23%) resulting in a surface diffusivity of 2.5 x 10(-15) cm(2)/s. Results from this study suggest that mechanistic investigations provide a solid basis for successful adsorption modeling and that inclusion of intraparticle surface diffusion may lead to improved geochemical transport depiction. 相似文献
Journal of Radioanalytical and Nuclear Chemistry - Comparisons of statistical analysis results between five methods using gamma spectrometry and a control group for measuring the radioactivity of... 相似文献