New reactivities of deltaline analogs: an efficient O-demethylation at C-1 and an unusual extrusion of the C-14 atom

O-Demethylation at C-1 in the C₁₉-diterpenoid alkaloids is very challenging. In this paper, it was firstly observed that 10-OH group in deltaline (1) is a determining factor for the O-demethylation reaction. After removal of this hydroxyl group, 1-O-methyl group in the corresponding deltaline analogs can be readily removed by treatment with HBr–HOAc. Meanwhile, the C-14 atom in bromides 18 or 20 can be extruded under basic condition probably via a sequence, including Grob fragmentation, aerobic oxidation, deformylation, and S_N2 nucleophilic substitution, to give enone 21 (70%) and oxetane 22 (14%). The structure of compound 22 was confirmed by X-ray crystallographic analysis of its derivative 21.     

Polystyrene-bound diethanolamine based ionic liquids for chemical fixation of CO2

Polystyrene-bound diethanolamine based ionic liquids (PS-DHEEAB and PS-THEAB) were synthesized and applied for the chemical fixation of CO₂ into cyclic carbonates without any additional co-catalyst and solvent. The effect of the catalysts with different number of hydroxyl group in the cation of the IL on the reaction was systematically investigated. Highest activity and selectivity were achieved in the presence of polystyrene supported diethanolamine ethyl bromide (PS-DHEEAB) in comparison with other catalysts employed. The catalyst was tough in stability and also found to be extended to a variety of terminal epoxides and aziridines. The relationship between high catalytic reactivity and the –OH functional groups was proposed.     

Effect of Vacancy Defects on the Young's Modulus and Fracture Strength of Graphene: A Molecular Dynamics Study

The Young's modulus of graphene with various rectangular and circular vacancy defects is investigated by molecular dynamics simulation. By comparing with the results calculated from an effective spring model, it is demonstrated that the Young's modulus of graphene is largely correlated to the size of vacancy defects perpendicular to the stretching direction. And a linear reduction of Young's modulus with the increasing concentration of mono‐atomic‐vacancy defects (i.e., the slope of ?0.03) is also observed. The fracture behavior of graphene, including the fracture strength, crack initiation and propagation are then studied by the molecular dynamics simulation, the effective spring model, and the quantized fracture mechanics. The blunting effect of vacancy edges is demonstrated, and the characterized crack tip radius of 4.44 Å is observed.     

An environmentally benign benzylic oxidation catalyzed by hypervalent iodine intermediate in water

An effective and environmentally benign benzylic oxidation for transition of alkylarenes into the corresponding carbonyl compounds was reported.Alkylarenes were mixed and stirred with potassium bromide,m-chloroperbenzoic acid and a catalytic amount of iodobenzene in water at 60 8C for several hours,a series of the corresponding carbonyl compounds was obtained in moderate to good yields.In the reaction,iodobenzene was first oxidized by m-chloroperbenzoic acid into the hypervalent iodine intermediate which then reacted with potassium bromide to form the key radical initiator for the benzylic oxidation.     

Synthesis and Properties of Novel Luminescent Compounds Containing Triphenylamine and Bipyridine Units

Blue luminescent compounds T1-T4 containing triphenylamine donors,bipyridine acceptors and olefinic linkers were synthesized and characterized by 1H NMR,13C NMR and high resolution mass spectrometry(HR...     

A DOUBLE-TEMPERATURE-GRADIENT TECHNIQUE FOR THE GROWTH OF PURE C60 SINGLE CRYSTALS FROM THE VAPOR PHASE

Pure C₆₀ single crystals were grown by a sublimation-condensation method in an evacuated dosed quartz tube situated in a double-temperature-gradient furnace. Large C₆₀ single crystals, up to a size of 0.6 mm×1.0 mm×2.0 mm with quite smooth and shiny faces, were obtained. X-ray diffraction, electron diffraction and X-ray morphology were carried out and showed that the quality of large C₆₀ single crystals grown by the double-temperature-gradient technique is excellent. In this paper the experimental results of the growth of large C₆₀ single crystals are reported and the morphological and structural characterizations are discussed in detail.     

“PPAS” X-RAY ABSORPTION SPECTROSCOPY IN LASER-PRODUCED ALUMINUM PLASMA

We have developed and successfully demonstrated the "point projection absorption spectroscopy (hereafter abbreviated to PPAS)" technique to record keV X-ray absorption spectra in the coronal region of laser produced aluminum plasma which provides spatial information in the corona. Absorption spectrum of the Al Ⅻ 1s²-1s2p resonant line for time delays up to 250, 500 and 750 ps after the peak of the incident laser pulse have been observed. Analysis of an absorption spectrum should allow a high spatial resolution (< 25μm) history of the absorbing ion population density to be determined. The 1-D hydro-code JB19 has been used to simulate the experiment and the predictions are compared to the observations. Such comparison can be useful in validating parts of the codes used for gain prediction on recombination X-ray laser transitions.     

基于激发态吸收的C60分子全光开关特性研究

用５３２．０ｎｍ的脉冲Ｎｄ：ＹＡＧ激光作为泵浦光，７４７．０ｎｍ的连续半导体激光作为探测光，在Ｃ₆₀甲苯溶液中，利用Ｃ₆₀分子的三重态－三重态非线性吸收效应，获得Ｃ₆₀分子的全光开关和全光调制特性，并用速率方程进行了动力学数值模拟，得到与实验相一致的结果。 关键词：