Electrospray ionization tandem mass spectrometric study of the aconitines in the roots of aconite

Fragmentation pathways of aconitine-type alkaloids were investigated by electrospray ionization/ion trap multistage tandem mass spectrometry. Low-energy collision-induced dissociation of protonated aconitines follows a dominant first step, the elimination of the C(8)-substituent as acetic acid or fatty acid in MS(2) spectra. Successive losses of 1-4 CH(3)OH molecules, 1-3 H(2)O, CO, benzoic acid, and CH(3) or C(2)H(5) (N-substituents) are all fragmentation pathways observed in MS(3) and MS(4) spectra. By applying knowledge of these fragmentation pathways to the aconitines in the ethanolic extract of aconite roots, all the known aconitines were detected and also 23 unknown aconitine-type alkaloids, in which the lipo-alkaloids containing residues of 15C, 17C and 19C saturated or unsaturated fatty acids were characterized. These odd-carbon-number fatty acid substituents have not been reported previously.     

肝素化聚甲基硅氧烷-聚氧乙烯接枝物的合成及其体外抗凝血性能评价

以二甲基硅油接枝端羟基聚氧乙烯（ＰＤＭＳ ｇ ＰＥＯ ＯＨ）为基材，用二环己基碳二亚胺（ＤＣＣＩ）作脱剂，研究了羟基（ＯＨ）与肝素上的羧基（—ＣＯＯＨ）之间的脱水缩合反应，制备出肝素化的抗血栓材料ＰＤＭＳ ｇ ＰＥＯ Ｈｅｐ，并对其涂覆表面的肝素含量和体外抗凝血性能进行了初步评价．实验结果表明，肝素接枝的共聚物具有优良的抗凝血性能和一定的应用前景．     

多孔岩心的渗透性

The relaxation properties of water saturated in porous core are discussed and the distribution of proton transverse relaxation time and bi-exponential model of longitudiual relaxation time are obtained, which provide an illustration for two-model of fluids saturated in porous media. The cutoff value of T_1 based on relaxation specific property of fluids in porous core is adopted to improve the correlation between permeability and ?4T1b2.     

Two New Xanthone Glycosides from Polygala tenuifolia

Two new xanthone glycosides,polygalaxanthone IV and V were isolated from the roots of Polygala tenuifolia Willd. Their structures were established as 6-O-[α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranosyl]-1-hydroxy-3,7-dimethoxyxanthone(polygalaxanthone IV), and 6-O-[α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranosyl]-1,3-dihydroxyl-7-methoxyxanthone (polyga-laxanthone V),respectively, on the basis of chemical and spectral evidence.     

L-proline promoted Ullmann-type reaction of vinyl bromides with imidazoles in ionic liquids

The Ullmann-type coupling reaction of vinyl bromides and imidazoles in ILs at 90-110 degrees C gave the corresponding N-vinylimidazoles in good to excellent yields by using L-proline as the ligand; the double bond geometry of the vinyl bromides was retained under the reaction conditions.     

联萘冠醚的合成新方法

一种用于合成含联萘基冠醚的新方法。以消旋，手性联萘酚为起始原料，先与氯乙醇反应制得2,2'-二（2－羟基乙氧基）－1,1'－联二苯，再与二甘醇或三甘醇对二对甲苯磺酸酯反应，成功制得了4种联萘冠醚。     

An improved method for constructing a full-length enriched cDNA library using small amounts of total RNA as a starting material

We have developed an improved method for constructing a full-length cDNA library using small quantity of material by modifying the original oligo-capping method. In our devised method, total RNAs are used in sequential oligo-capping steps directly without preliminary mRNA purification. Using this method, we constructed full- length cDNA libraries from 100 mg of total RNA. These libraries contained 8x10(5) to 8x10(6) independent clones with average insert sizes of 2.0 kb. Moreover, the number of full-length cDNAs containing the translation initiation codon ATG in the constructed libraries was estimated to 60-70%. In addition, 54% of the known cDNAs had a longer 5' end than the corresponding genes in the public database. Our results show that the method can be effectively used to construct full-length enriched cDNA libraries, especially, if starting material is limited.     

Synthesis of Novel Benzo-15-Crown-5-Tethered β-Cyclodextrins and Their Enhanced Molecular Binding Abilities by Alkali Metal Cation Coordination

Two novel benzo-15-crown-5 tethered β-cyclodextrins 1 and 2have been synthesized by coupling substituted benzo-15-crown-5 with correspondingβ-cyclodextrin derivatives. Their inclusion complexation behavior withrepresentative guests, such as cyclohexanol, cyclohexane carboxylic acid, cyclohexaneacetic acid, sodium cyclohexane carboxylate, and potassium cyclohexane carboxylate,was investigated in aqueous solution by means of fluorescence spectrometry. As compared with parent β-cyclodextrin, benzo-15-crown-5 tethered β-cyclodextrins 1–2 display significantly enhanced molecular binding abilities and selectivities towards model substrates, especially towards substrates containing alkali-metal cations. These results indicate that, bearing two recognition sites in a single molecule, these supramolecular architectures can strongly enhance the molecular binding ability of parent β-cyclodextrin by the cooperative binding of the β-cyclodextrin cavity and the crown ether moiety. Possessing a shorter linker, crown ether-β-cyclodextrin 2 shows much higher binding affinity with guest molecules than crown ether-β-cyclodextrin 1, which may be attributed to the binding size and molecular multiple recognition behavior between host and guest.     

Efficient Debromination of Vicinal α，β—Dibromo Carboxylic Acid Derivatives with the Sm／HOAc System

The α，β vicinal dibrome carboxylic acid and its derivatives were debrominated with Sm/HOAc system to afford the corresponding cinnamic acid and its derivatives in good yields under mild conditions.     

Concise synthesis of acyl migration-blocked 1,1-difluorinated analogues of lysophosphatidic acid

Lysophosphatidic acid (LPA, 1- or 2-acyl-sn-glycerol 3-phosphate) is an important phospholipid mediator produced by activated platelets and by ovarian cancer cells. Efforts to understand LPA signaling through G-protein-coupled receptors are hampered by the facile acyl migration that results in equilibration to a mixture of the 1- or 2-acyl species under physiological conditions. We describe a new and efficient route to enantiomerically homogeneous lysophospholipid analogues from D-mannitol 1,2:5,6-bis-acetonide to give two 1,1-difluorodeoxy analogues of (2R)-acyl-sn-glycerol 3-phosphate. These compounds are migration-blocked analogues of the labile sn-2 LPA species. The (19)F NMR of diastereotopic fluorines of the difluoromethyl group shows an unexpected solvent dependence.