磺酸化β-环糊精聚合物的合成及其在毛细管电泳手性拆分中的应用

用三氧化硫吡啶复合物将β-环糊精与环氧氯丙烷反应得到的β-环糊精聚合物进行磺酸化,得到磺酸化的β-环糊精聚合物,并对其进行了红外光谱和1H NMR表征。将磺酸化β-环糊精聚合物作为手性添加剂,用于毛细管电泳手性药物拆分中,在区带电泳模式下,对5种药物特布他林、山莨菪碱、奥美拉唑、扑尔敏、氧氟沙星进行拆分,并考察了缓冲溶液pH值、运行电压、手性添加剂浓度、有机溶剂对手性拆分的影响。1H NMR分析结果表明:此聚合物为不均一取代的磺酸化β-环糊精;毛细管电泳结果表明,此聚合物具有良好的拆分效果,在磺酸化β-环糊精聚合物浓度为5 g/L,运行电压15 kV条件下,对特布他林、扑尔敏的分离度达到3.0以上;对于山莨菪碱的两对对映体均可实现良好拆分,分离度达到2.0以上。     

Vibrational Spectroscopic Investigation and DFT Calculations on the Decabromodiphenyl Ether

Decabromodiphenyl ether (BDE-209), the major congener in the high volume industrial flame retardant mixture "DecaBDE", has become a ubiquitous environmental contaminant. In the present work, combined experimental and theoretical studies have been undertaken on the structure and vibrational spectra of BDE-209. The FT-IR (400-4000 cm-1) and FT-Raman spectra (100-4000 cm-1) of BDE-209 were recorded, while density functional B3LYP calculations were employed in conjunction with the 6-31G(d) basis set for investigating the corresponding geometric structure and vibrational spectroscopic properties. Besides, the detailed interpretations of fundamental vibrations were performed on the basis of experimental results and potential energy distribution (PED) of the vibrational modes. Optimized structures of the title compound were interpreted and compared with the earlier reported experimental values, which yield good agreement. Finally, the measured and calculated harmonic vibrational wavenumbers were compared with each other, and they were found to be in good accordance.     

手性双核Salen配合物的合成与谱学性质

Six novel chiral dinuclear Salen complexes [Cu₂L₁·H₂O (3a), Cu₂L₂(3b), Ni₂L₁·2H₂O (4a), Ni₂L₂(4b), Mn₂Cl₂L₁·H₂O (5a), Mn₂Cl₂L₂ (5b)] have been synthesized(L₁ and L₂ are chiral dimeric Salen ligands with different chain length which were synthesized from (R,R)-diaminocyclohexane, salicylaldehyde, 4,4′-(1,10-decaneoxy)salicylaldehyde, 4,4′-(1,6-hexyloxy)salicylaldehyde). These compounds were charactered by elemental analysis, ¹H NMR, FT-IR, UV-Vis and CD spectra. The FT-IR, UV-Vis and CD spectra were discussed and compared with those of monomeric ligand and complex in detail. It was found that the spectra properties of compounds of different chain length were almost alike, and the properties of dimeric and monomeric compound were similar too. Furthermore Cotton effect and Cotton split of CD spectra of these chiral compounds were explained by the exciton interaction theory. It seemed that the direction of Cotton split depend on the configuration of diaminohexane. (R,R)-diaminohexane determine the chirality of Salen compounds as negative, and the positive and negative component of Cotton split lie at higher and lower energy respectively.     

The smart precursors of energetic–energetic cocrystals from eutectic precursors

The selected 18 energetic compounds were theoretically investigated by using the density functional theory（DFT） quantum mechanical code,DMol3,and the Hansen solubility parameters（HSPs） analyses.The results showed that 4-nitrotoluene,4-nitrophenol,N N0-dimethyl-N N0-diphenylurea and N N0-diethyl-N N0-diphenylurea contain relatively electron-rich aromatic rings.Four satisfactory energetic precursors with electron-rich rings were quickly and effectively found by electrostatic potential（ESP）surfaces and HSPs analyses.The results also indicated that the absolute value of the lowest unoccupied molecular orbital（LUMO） of the energetic precursors with electron-rich rings often was less than3.00 eV,and the absolute value of LUMO of the energetic precursors with electron deficient rings was often more than 3.00 eV.Additionally,we found that with at least two eutectic points was a prerequisite for two precursors to form a cocrystal.