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We investigated constituent of triterpenoid saponins ofAlbizzia, two new compounds together with two known compounds were isolated from Albizzia julibrissin Durazz. by using column chromatography (macroreticular resin, silica gel, Sephadex gel, reverse phase silica gel),preparative HPLC methods et al.On the basis of spectroscopic analysis, including IR,ESI-MS,~1H-NMR,~(13)C-NMR,HMBC,HMQC,~1H-~1HCOSY and chemical methods, the structure of two new compounds were identified as 3 - O -[β-D-xylopyranosyl(1→2)-β-D-fucopyranosyl (1→6)-β- D -2- deoxy - 2 - acetoamidoglucopyranosyl] -21-O-[(6S)-2- trans- 2,6-dimethyl - 6 - O-β- D - quinovopyranosyl -2,7- octadienoyl] - acacic acid- 28 - O-β-D-glucopyranosyl(1→3)[α-L-arabinofuranosyl(1→4)]-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranoside acacic acid 3- O -β- D- glucopyranosy(1→3)-β- D- fucopyranosl(1→6) [β-D- xylopyranosyl (1→2)]-β-D-glucopyranoside ;two known compounds were acacic acid lactone 3- O -β-D- xylopyranosyl-(1→2)-β-D-fucopyranosl (1→6)- 2-deoxy -2 -acetoamido -β-D- glucopyranoside ; acacic acid lactone 3- O-β-D-xylopyranosyl(1→2)-α-L- arabinopyranosl (1→6)- 2- deoxy - 2- acetoamido -β-D-glucopyranoside . The study lays chemical foundation and chemical reference substance for enhancing quality standard of Albizzia julibrissin Durazz.

本研究论文在综述国内外对合欢属Albizzia三萜皂苷化学成分和药理作用研究进展的基础上,利用传统植化分离手段和现代分离技术,包括大孔树脂、硅胶、葡聚糖凝胶、反相硅胶等柱色谱,制备高效液相色谱法等技术从中药合欢皮中分离得到了4个化合物,其中,2个新化合物和2个己知化合物,并进一步通过现代分析技术IR,ESI-MS,~1H-NMR,~(13C-NMR,HMBC,HMQC,~1H-~1HCOSY等和化学方法鉴定了2个新化合物的结构分别是:3-O-[β-D-吡喃木糖基(1→2)-β-D-吡喃夫糖基(1→6)-β-D-2-去氧-2-乙酰氨基吡喃葡萄糖基]-21-O-[(6S)-2-反式-2,6-二甲基-6-O-β-D-吡喃鸡纳糖基-2,7-辛二烯酸基]-金合欢酸-28-O-α-L-呋喃阿拉伯糖基(1→4)[β-D-吡喃葡萄糖基(1→3)]-α-L-吡喃鼠李糖基(1→2)-β-D-吡喃葡萄糖苷,金合欢酸3-O-β-D-吡喃葡萄糖基(1→3)-β-D-吡喃夫糖基(1→6)[β-D-吡喃木糖基(1→2)]-β-D-吡喃葡萄糖苷;2个已知化合物结构分别是:金和欢酸内酯3-O-β-D-吡喃木糖基(1→2)-β-D-吡喃夫糖基(1→6)-β-D-2-去氧-2-乙酰氨基吡喃葡萄糖苷,金和欢酸内酯3-O-β-D-吡喃木糖基(1→2)-α-L-吡喃阿拉伯糖基(1→6)-β-D-2-去氧-2-乙酰氨基吡喃葡萄糖苷。

Protease treatment of the plasma membranes could abolish the binding but NaIO_4 and glycosidase could not, indicating that nsLTP144 bound to plasma membranes protein without carbohydrate moiety. Using the homobifunctional cross-linking regent bissuberate (BS~3) and rice plasma membranes incubated with ~(125)I-Trx-nsLTP144, we identified, after SDS-polyacrylamide gel electrophoresis and autoradiography, a putative protein receptor on the rice plasma membranes with the molecular mass around 60 kDa. NsLTP144 can not trigger extracelluar alkalization in arabidopsis, but can abolish the extracellular alkalization effect of phytopathogen elicitor cryptogein, suggesting that cryptogein and nsLTP144 may bind to the same membrane protein. In vitro pull-down assay showed that nsLTP144 interacted with OsCaM1, a possible extracellular calmodulin, implying that nsLTP144 and OsCaM1 could function in the same signal transduction pathway. These results shed light on revealing the roles of nsLTP in vivo and make it promising to finally characterize the plasma membranes receptor of nsLTP.

发现~(125)I-Trx-nsLTP144、~(125)I-Trx-nsLTP110与水稻细胞质膜均具有特异性结合,而且结合是饱和性的、可被竞争的,符合配体-受体结合的典型特征,同时用于对照实验的蛋白质~(125)I-Thioredoxin没有此特性,表明水稻细胞质膜上存在nsLTP的受体;利用可氧化糖基的NaIO_4和水解糖基的N\'-糖苷酶F处理水稻细胞质膜,再进行结合实验,结合活性几乎不受影响;而利用胰蛋白酶处理细胞膜则使得结合能力几乎完全丧失,表明其受体为没有经过糖基化修饰的蛋白质;利用交联剂BS~3交联配体一受体后,再进行SDS-PAGE分离和放射自显影,结果显示水稻细胞质膜上的nsLTP受体中有一个60kDa的蛋白质可以与nsLTP144发生特异性的结合,可能是其受体;细胞外碱化实验表明,nsLTP144不能促使拟南芥原生质体细胞培养液的细胞外碱化反应,却能猝灭来自植物病原菌的激发子Cryptogein刺激拟南芥原生质体产生的细胞外碱化反应,表明nsLTP和Cryptogein结合细胞膜上相同的位点,保护了植物细胞免受Cryptogein导致的细胞程序性死亡,并诱导系统获得性抗性的产生;体外Pull-down实验表明,nsLTP144和水稻的OsCaM1具有相互作用,暗示了nsLTP144和OsCaM1可能同在一个信号通路上起作用。

Their structures were identified by chemical and spectral analysis. RESULTS Five compounds were isolated and identified as stigmasterol 3-O-β-D-glucopyranoside, 20β-hydroxy-ecdysone,β-L-thymidine, pennogenin 3-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside and pennogenin 3-O-α-L-rhamnopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→4)-[α-L-rhamnopyranosyl-(1→2)-]-β-D-glucopyranoiside.

结果 分离并鉴定了5个化合物,分别是Δ5,22-豆甾醇3-O-β-D-葡萄吡喃糖苷,20β-羟基蜕皮激素,β-L-脱氧胸腺嘧啶苷,偏诺皂苷元3-O-α-L-鼠李吡喃糖基-(1→2)-β-D-葡萄吡喃糖苷和偏诺皂苷元3-O-α-L-鼠李吡喃糖基-(1→4)-α-L-鼠李吡喃糖基-(1→4)-[α-L-鼠李吡喃糖基-(1→2)-]-β-D-葡萄吡喃糖苷。

Based on the above-mentioned, two kinds of target glycoclusters with different glycoterminus, flexible linkers and different scaffolds were designed, disaccharide glycocluster (including TM1-TM7) and trisaccharide glycocluster (TM8-TM9) respectively, with the purpose of obtaining glycoclusters with high binding affinity to anti-Gal antibody and thus better inhibiting the HAR.

基于上述,针对HAR产生的机制,以人体中天然存在的anti-α-Gal抗体及B细胞表面的相应受体为靶点,以α-Gal抗原末端的二糖Galα1→3Gal和三糖Galα1→3Galβ1-4GluNAc片段为糖基部分,采用柔性的连接臂(氨基保护的2-乙醇胺和3-巯基丙酸)和刚性的芳香骨架及柔性的脂肪链骨架,设计了两类结构新颖的糖簇分子:即氧苷和硫苷键连接的二糖糖簇TM1-TM7)和三糖糖簇(TM8-TM9),目的在于寻找与anti-Gal抗体及B细胞相应受体有较高结合力的糖簇分子,以便有效地抑制HAR反应的发生。

By the partial purification of Arthrobacter nicotinovorus D-97 endocellular enzymes and the results of enzymatic reaction of enzymes of partition collection, it was found that enzymes related to trehalose synthesis were consisted of Trehalose-forming Enzyme and Trehalose-releasing Enzyme . Trehalose-forming Enzyme could convert maltooligosaccharides into non-reducing maltooligosyl trehalose by intramolecular transglycosylation, and Trehalose-releasing Enzyme could hydrolyze α-1, 4 linkage between the trehalose residue and the maltooligosaccharide residue to release trehalose and maltooligosaccharides with two glucose monomer lesser.

将食尼古丁节杆菌D-97胞内酶部分纯化并对各收集组分进行酶反应,发现其海藻糖合成酶系由海藻糖生成酶(Trehalose-forming Enzyme,TFE)和海藻糖释放酶(Trehalose-releasingEnzyme,TRE)组成,前者分子内转糖基将直链麦芽寡糖转化为没有还原性的麦芽寡糖基海藻糖,后者专一切割麦芽寡糖基海藻糖分子上麦芽寡糖基与海藻糖连接的α-1,4糖苷键,从而释放出海藻糖和减少了两个葡萄糖单体的麦芽寡糖。

By means of GPC,IR,GC-MS,~(13)CNMR,~1HNMR,Methylation analysisetc,structural properties of PST-1 were identified as follows:The Mwof PST-1 was 3.44×10~6 Da and its optical rotation was _D~(20)=+0.110°(c0.1, H_2O); PST-1 constituted 8 simple sugars and the molar ratio was 2,4-Dimethoxy-Mannose:Rhamnose:Ara-binose:Xylose:Galactose:D-Galacturonic acid:Mannose:D-glucuronic acid=2%:5%:24%:9%:3%:1%:46%:10%;The chief bone of PST-1 was 1,3,6-linked-β-D-Man residue and the side chains contained Furanoid and Pyranoid residues.

结合GPC、旋光度测定、IR、GC-MS、~(13)CNMR、~1HNMR、高碘酸氧化法、Smith降解以及甲基化方法等分析测试方法,得到PST-1的单糖组成及结构表征,实验结果如下:红豆杉多糖PST-1是重均分子量为3.44×10~6 Da的支链多糖,旋光度为20D=+0.110~0(c0.1,H_2O);PST-1单糖组成为:2,4-Dimethoxy-Mannose:Rhamnose:Arabinose:Xylose:Galactose:D-Galacturonic acid:Mannose:D-glucuronic acid=2%:5%:24%:9%:3%:1%:46%:10%;PST-1的骨架结构为:具有1,3,6-连接的β-D-甘露糖残基骨架,侧链分枝包括非还原末端的呋喃型α-L-阿拉伯糖残基、吡喃型α-L-阿拉伯糖残基、β-D-木糖残基、β-D-甘露糖残基、2,4-二氧甲基-β-D-甘露糖残基和α-D-葡萄糖醛酸残基;侧链的糖残基也可能存在2,5-二氧-取代呋喃型α-L-阿拉伯糖基、3-氧-取代的β-D-木糖残基、6-氧-取代的α-D-半乳糖醛酸残基、6-氧-取代的α-D-半乳糖残基、4-氧-取代的α-D-葡萄糖醛酸残基和2-氧-取代的α-L-鼠李糖残基,同时后者也可能穿插在主链上。

In this paper, the structures and the synthesis methods of glycosyl isothiocyanates are summarized, including the application as intermediates in the preparation of glycosylthioureas, glycosylheterocycles, glycosylguanidins and glycosylconjugates and so on.

本文对糖基异硫氰酸酯的结构、制备方法,以及作为中间体在糖基硫脲、糖基杂环、胍基糖苷、糖基缀合物等重要化合物的合成中的应用作了较详尽阐述。

Objective Through observing the ei'fect of the TCM decoction TangShenHuaYuJian on the kidney weight, index of kidney hypertrophy(kidney weight/body weight), blood glucose , blood urea nitrogen, creatinine, blood advanced glycation end-products, advanced glycation end-products in kidney tissue in the earlier stage of diabetic nephropalhy rats induced by injecting 3 -cytotoxins into abdomen, to explore the relationship between nonenzymatic glycosylation and diabetic nephropathy, and provide an experimental basis for clinical application and for further studying TSHYJ.

目的 通过观察糖肾化瘀煎对长期高血糖所致的早期粮尿病肾病大鼠(腹腔注射链脲佐菌素后诱导所形成)肾重、肾重指数、血糖、血尿素氮、肌酐、血糖基化终末产物AGEs、肾组织糖基化终末产物AGEs等指标的影响,从非酶糖基化角度探讨此制剂对糖尿病肾病早期的作用机理,并为糖肾化瘀煎的临床运用和进一步开发提供实验依据。

This work made preparations for the further in-vitro study on the activity of glycosyltransferase and the usage of different glucosyl.Several important factors for protoplast preparation from Amycolatopsis-orientalis were studied and optimized such as the type of substrate, the concentrations of the addition of glycin, the concentrations of lysozyme and so on.

并且通过酸水解的方法获得了脱去一个糖基的万古霉素假糖苷,可以将其作为酶转化反应的底物,为进一步在宿主菌体外研究糖基转移酶的活性以及不同糖基的生理作用做好准备。

Furthermore, proton singlets of Fmoc group were treated as internal standard because of their station in both starting material and product.

用HR/MAS NMR分析技术不仅跟踪优化了固相羟基氨基酸的糖基化反应条件,而且选择固载在树脂上的糖基化Nα-Fmoc保护羟基氨基酸〓H NMR中最低场,且分辨好的Fmoc保护基信号做为内标,糖上乙酰基的积分面积为标准直接定量了键合在Tenta Gel S NH〓树脂上氨基酸甙化的产率。

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