氢键缔合主链超分子液晶聚合物:间隔基及扩展介晶元长度的影响研究

采用慢挥发溶剂组装方法制备了一系列羧酸/吡啶氢键缔合的主链型超分子复合物,并采用FTIR,DSC以及偏光显微镜等对其相转变与热致液晶相行为进行了比较研究.研究表明,分别具有较短的6或10个亚甲基的烷烃间隔基的双苯甲酸衍生物4',4'-二羧酸-1,6-二酚氧基己烷(C6-2COOH)和4',4'-二羧酸-1,10-二酚氧基癸烷(C10-2COOH)的系列复合物具有较高的熔点和清亮点,一般都只出现结晶近晶相和多晶型转变现象.而具有柔顺性较好的四甘醇醚链间隔基的4,4'-二羧酸-α,ω-二酚氧基四甘醇醚(C8O4-2COOH)得到的系列复合物均在降温过程生成单致的流体近晶SA和/或向列N液晶相.可见,间隔基增长,相转变温度降低,最终导致真正的流体液晶相的产生.另一方面,对于从同一种二元羧酸得到的组装体系,从4,4'-联吡啶(4,4'-BPy)、4,4'-联吡啶乙烯撑(4,4'-BPyE)到对苯二酚二异烟酸酯(p-PhBPy),由于双键或酯基的引入,可变形性和极性增大,刚性依次减弱,尽管中心核部分持续长度增大,所得复合物的各向同性化温度降低,形成流体液晶相的趋势增强,液晶有序性降低,流动性增加.指出了早期文献报道的一些不一致甚至矛盾的结果.通过不同系列的对比研究,得出的一些规律性对氢键组装尤其对羧基/吡啶氢键缔合超分子体系设计与构筑具有一定指导意义.     

Structure activity relationship of bergenin,p-hydroxybenzoyl bergenin, 11-O-galloylbergenin as potent antioxidant and urease inhibitor isolated from Bergenia ligulata

Ethanol extract of the aerial parts of Bergenia ligulata was subjected to solvent–solvent separation followed by various chromatographic techniques that lead to isolation of bergenine (1), p-hydroxybenzoyl bergenin (2), 11-O-galloylbergenin (3) and methyl gallate (4) as major constituents. Ethyl acetate fraction showed a dose-dependent urease inhibitory pattern with IC₅₀ value of 54μg/mL. Structures of compounds 1 and 3 were established by XRD and 2, 4 by NMR. All these compounds were subjected to DPPH scavenging activity, reducing power assay and urease inhibitory activity. The EC₅₀ 7.45 ± 0.2 μg/mL and 5.39 ± 0.28 μg/mL values in terms of antioxidant and reducing power, respectively, were less for 3. Compounds 1–3 showed moderate to significant urease inhibitory potential with IC₅₀ 57.1 ± 0.7, IC₅₀ 48.4 ± 0.3 and 38.6 ± 1.5. Antioxidant activities and urease inhibitory potential were investigated and compound 3 was found to be the most active.     

Ab initio potential energy surface and quantum dynamics for the H + CH4 → H2 + CH3 reaction

A new full-dimensional potential energy surface for the title reaction has been constructed using the modified Shepard interpolation scheme. Energies and derivatives were calculated using the UCCSD(T) method with aug-cc-pVTZ and 6-311++G(3df,2pd) basis sets, respectively. A total number of 30,000 data points were selected from a huge number of molecular configurations sampled by trajectory method. Quantum dynamical calculations showed that the potential energy surface is well converged for the number of data points for collision energy up to 2.5 eV. Total reaction probabilities and integral cross sections were calculated on the present surface, as well as on the ZBB3 and EG-2008 surfaces for the title reaction. Satisfactory agreements were achieved between the present and the ZBB3 potential energy surfaces, indicating we are approaching the final stage to obtain a global potential energy surface of quantitative accuracy for this benchmark polyatomic system. Our calculations also showed that the EG-2008 surface is less accurate than the present and ZBB3 surfaces, particularly in high energy region.     

New anthraquinones from the stem of Morinda citrifolia Linn

Studies on the chemical constituents of the stem of Morinda citrifolia, Linn. have led to the isolation of two new compounds, morindicinone (=2-hydroxy-1,8-dimethoxy-7-methoxymethylanthraquinone, 1) and morindicininone (=4-hydroxymethyl-1,3-dimethoxyanthraquinone, 2), as well as two known constituents, 2-hydroxyanthraquinone (3) and 2-methoxyanthraquinone (4). Their structures were elucidated by spectral analysis including 2D-NMR techniques.     

A new flavanoid from the flowers of Azadirachta indica

Studies on the chemical constituents of the flowers of Azadirachta indica have led to the isolation of one new flavanone named as azharone (5,7,4'-trihydroxy-3'-(3'-methyl-2',3'-epoxybutyl)flavan-4-one (3)) along with two known constituents azadirone (1), and isoazadironolide (2). Their structures have been elucidated through spectral studies including 2D-NMR (COSY-45, NOESY, J-resolved, HMQC, HMBC) experiments.     

Molecular Ordering in Liquid Crystals and the Effect of End-Chains on the Even-Odd Effect

The second and fourth orientational order parameters [Pbar]₂, [Pbar]₄ of the homologous series of 4-n-alkyl-4′-cyanobiphenyls (nCB, n = 5 ～ 8) in the nematic liquid crystalline state have been determined from the Raman depolarization ratios by the resonance Raman probe method. It was found out that not only [Pbar]₂ but also [Pbar]₄ exhibits evident even-odd effect when they are compared at the same reduced temperature. For understanding the mechanism of the even-odd effect, a theoretical calculation has been carried out on the basis of the mean field theory of Marcelja, in which the effect of the end alkyl-chain on the liquid crystalline state is taken explicitly into consideration. The observed trend in [Pbar]₂, [Pbar]₄, nematic-isotropic transition temperature were well reproduced. Detailed inspection of the results shows that the presence of anisotropic molecular field plays an important role in the appearance of the even-odd effect. The anisotropic molecular field produces redistribution of the statistical weight of various conformers in such a way that the end chains of odd-members align better along the direction of the rigid core part than those of even-members.     

吸附树脂对紫背天葵的水溶性色素精制研究

研究吸附树脂吸附精制紫背天葵红色素的方法和工艺。以吸附量、解吸量为指标,在pH=7时吸附,确定出S-8极性树脂和盐酸-乙醇溶液为最佳吸附剂和解吸剂。正交动态吸附和解吸实验结果表明,当原花液浓度3g/L,吸附流速3ml/min,树脂床层径高比1:1时,树脂对色素的吸附量最大;以盐酸-乙醇为解吸剂,解吸液用量30ml/g,解吸流速是1/5BV。经树脂吸附精制后的色素色价是未精制色素的3.74倍。