火绒草的苯丙素类成分

采用含水乙醇提取、三氯甲烷脱色、正丁醇萃取和多种色谱分离方法,从新疆产菊科植物火绒草(Lentopodium lenotopodioides)全草中获得8个苯丙素类化合物。通过波谱数据分析,分别鉴定为二氢去氢二松柏醇4-O-β-D-葡萄糖苷(1)、二氢去氢二松柏醇9′-O-β-D-葡萄糖苷(2)、去氢二松柏醇9′-O-β-D-葡萄糖苷(3)、去氢二松柏醇9′-甲醚-4-O-β-D-葡萄糖苷(4)、(-)-松脂醇4-O-β-D-葡萄糖苷(5)、(-)-杜仲树脂酚4-O-β-D-葡萄糖苷(6)、枸橼苦素C(7)和咖啡酸(8)。化合物2~7为首次从该植物中报道。在500μmol L~(-1)浓度下,这些化合物对α-葡萄糖苷酶的抑制率均低于50%。     

展毛野牡丹酚类化学成分的研究

为了明确展毛野牡丹的化学成分,该研究采用Diaion HP20SS、MCI gel、Sephadex LH-20柱层析和反相高效液相色谱等方法,对展毛野牡丹根和茎的醇提物分别进行了分离纯化。结果表明:从展毛野牡丹中分离得到11个化合物,它们的结构经波谱数据分析和鉴定。它们分别是4-羟基-3-甲氧基苯酚1-O-β-D-(6’-O-没食子酰)-吡喃葡萄糖苷(1)、3,4-二羟基苯乙醇4-O-β-D-(6’-O-没食子酰基)-吡喃葡萄糖苷(2)、龙胆酸5-O-β-D-(6’-O-没食子酰基)-吡喃葡萄糖苷(3)、2,4,6-三甲氧基苯酚1-O-β-D-(6’-O-没食子酰)-吡喃葡萄糖苷(4)、甲基6-O-没食子酰基-β-D-吡喃葡萄糖苷(5)、乙基6-O-没食子酰基-β-D-吡喃葡萄糖苷(6)、6’-O-没食子酰基黑樱苷(7)、没食子酸甲酯(8)、没食子酸乙酯(9)、2,6-二甲氧基对苯二酚4-O-β-D-吡喃葡萄糖苷(10)、2-甲氧基对苯二酚4-O-β-D-吡喃葡萄糖苷(11)。所有化合物均为首次从展毛野牡丹中分离得到,化合物2-7、10和11为首次从该属植物中分离得到。     

菝葜中三个新的二氢山萘酚酰化糖苷(英文)

从菝葜根茎中共分离得到3个新的二氢黄酮醇酰化糖苷(1～3)和1个已知的二氢黄酮醇苷(4),分别被鉴定为:(2R,3R)-二氢山萘酚3-氧-(6″-氧-乙酰基)-β-D-葡萄糖苷(1),(2R,3R)-二氢山萘酚3-氧-(2″-氧-乙酰基)-β-D-葡萄糖苷(2),(2R,3R)-二氢山萘酚3-氧-(3″-氧-乙酰基)-β-D-葡萄糖苷(3)及(2R,3R)-二氢山萘酚3-氧-β-D-葡萄糖苷(4)。其结构通过MS,1D NMR和2D NMR等光谱分析和化学方法确定。研究结果表明,二氢黄酮醇的酰化糖苷可能是菝葜属的特征成分。     

黄花倒水莲化学成分研究

从黄花倒水莲(Polygda aureocauda Dunn．)根中分离得到七个化合物,经理化和光谱分析鉴定为豆甾-7,(反)22-二烯-3-醇(1)、豆甾-7,(反)22-二烯-3-酮(2)、1,8-羟基-3,7-二甲氧基Shan酮(3)、软脂酸单甘油酯(4)和3-O-[4-O-(α-L-吡喃鼠李糖-)-阿魏酰]-β-D-呋喃果糖-(2→1)-(4,6-二-O-苯甲酰)-α-D-吡喃葡萄糖苷(5)、1-O-β-D-吡喃葡萄糖-(2S,3S,4R,8E)-2-[(2’R)-2’-羟基棕榈酰胺]-8-十八烯-1,3,4-三醇(6)和1-O-β-D吡喃葡萄糖-(2S,3S,4R,8E)-2-[(2’R)-2'-羟基二十四烷酰胺]-8-十八烯-1,3,4-三醇(7)。化合物2—4．7为首次从该植物中分离得到。     

杨桃叶的化学成分研究

为阐明酢浆草科植物杨桃(Averrhoa carambola)的化学成分,运用有机溶剂提取、萃取及多种色谱分离技术,从其叶中分离得到11个化合物。经光波谱分析,分别鉴定为苯基β-D-葡萄糖苷(1)、3,4,5-三甲氧基苯基β-D-葡萄糖苷(2)、苄基β-D-葡萄糖苷(3)、2-苯乙基芸香糖苷(4)、1-O-(3,5-二甲氧基-4-羟基苯甲酰)-β-D-葡萄糖(5)、5-羟基麦芽酚(6)、麦芽酚苷(7)、麦芽酚3-O-[6-O-(3-羟基-3-甲基-5-丁基戊二酰)]-β-D-葡萄糖苷(8)、乙基β-D-呋喃果糖苷(9)、丁基β-D-呋喃果糖苷(10)和鲨烯(11)。化合物8是1个新的人工产物,除化合物2和3外均为首次从杨桃属植物中得到。部分化合物与杨桃叶的抗炎、抗氧化和抗肿瘤作用相关。     

扁桃叶的化学成分研究

从芒果属植物扁桃(Mangifera persiciformis C.Y.Wu et T.L.Ming)叶乙醇提取物乙酸乙酯萃取部位中分离得到7个化合物,经波谱鉴定为没食子酸甲酯(1),没食子酸(2),3,4-二羟基苯甲酸(3),槲皮素(4),山奈酚-3-O-β-D-葡萄糖苷(5),槲皮素-3-O-β-D-葡萄糖苷(6)和芒果苷(7).其中化合物1、3、5、6为首次从该植物中分离得到.     

布渣叶中三萜和黄酮类成分的研究

从布渣叶(Microcos paniculata L.)的叶中分离得到10个化合物.通过光谱和波谱分析,分别鉴定为无羁萜(1)、阿江榄仁树葡糖苷Ⅱ(2)、山柰酚-3-O-β-D-[3,6-二(对羟基桂皮酰)]-葡萄糖苷(3)、山柰酚-3-O-β-D-葡萄糖苷(4)、异鼠李素3-O-β-D-葡萄糖苷(5)、异鼠李素3-O-β-D-芸香糖苷(6)、牡荆苷(7)、佛来心苷(8)、异佛来心苷(9)、异牡荆苷(10).10个化合物均为首次从布渣叶中分离得到.     

幌伞枫叶的化学成分研究

为了解幌伞枫(Heteropanax fragrans)的药理活性化学基础,从其叶的乙醇提取物中分离得到8个化合物,经波谱分析分别鉴定为:(7S,8R)-蛇菰脂醛素-4-O-β-D-吡喃葡萄糖苷(1)、4β,10α-香木兰烷二醇(2)、原儿茶酸(3)、3′-甲氧基-槲皮素-3-O-β-D-吡喃葡萄糖苷(4)、山柰酚-3-O-β-D-吡喃葡萄糖苷(5)、槲皮素-3-O-β-D-吡喃葡萄糖苷(6)、槲皮素-3-O-β-D-芸香糖苷(7)和山柰酚-3-O-β-D-芸香糖苷(8)。这8个化合物均为首次从幌伞枫中分离得到。     

红豆树茎枝中黄酮类成分及其抑菌活性研究北大核心CSCD

为了研究红豆树茎枝抑菌活性成分,采用色谱法分离纯化得到16个黄酮类化合物,通过理化性质及波谱技术分别鉴定为圆荚草双糖苷(1)、5,7-二羟基-4'-甲氧基异黄酮-7-O-β-D-葡萄糖苷(2)、4',8-二甲氧基-7-O-β-D-葡萄糖基异黄酮(3)、芒柄花苷(4)、异樱黄素-7-O-β-D-葡萄糖苷(5)、芦丁(6)、山奈酚-3-O-β-D-芸香糖苷(7)、4'-甲氧基异黄酮-7-O-β-D-木糖(1→6)-O-β-D-吡喃葡萄糖苷(8)、4'-甲氧基异黄酮-7-O-β-D-芹糖(1→6)-O-β-D-吡喃葡萄糖苷(9)、染料木素(10)、异樱黄素(11)、2',4',5,7-四羟基异黄酮(12)、大豆素(13)、柚皮素(14)、二氢染料木素(15)、去甲基化美迪紫檀素(16)。其中化合物1～16为首次从红豆树植物中分离得到;化合物1、3、4、6～9、12、15、16首次从红豆属中分离得到;化合物2,5和14对禾谷镰刀菌、西瓜尖镰孢菌、茄病镰刀菌的菌丝生长显示出了中等强度的抑制作用。     

钩枝藤化学成分研究

采用95%乙醇提取,石油醚、乙酸乙酯萃取分部,利用反复硅胶柱和凝胶柱色谱进行分离、纯化,根据波谱技术鉴定结构,研究钩枝藤茎中的化学成分。结果发现:分离得到5个已知二氢黄烷类化合物(-)-表儿茶素-3-没食子酸酯(1)、3,3',5,5',7-五羟基黄烷(2)、(-)-儿茶素(3)、(-)-表儿茶素(4)、(-)-表没食子酸儿茶素(5)和1个酚类化合物(3,5-二甲氧基-4-羟基苯酚)-1-O-β-D-(6-O-没食子酸)葡萄糖苷(6)。其中化合物1、2、4-6均为首次从该植物分离得到。     

羊角椒辣味物质成份分析

用紫外光谱法、红外光谱法和高效液相色谱法分析羊角椒中辣味物质纯度与组成,表明辣味物质由辣椒素、二氢辣椒素和降二氢辣椒素组成。     

Glycosylation of capsaicinoids with Panax ginseng stimulated by salicylic acid

The efficient production of β-glycosides of capsaicin and 8-nordihydrocapsaicin by cultured cells of Panax ginseng is reported. Capsaicin 4-O-(6-O-β-D-xylopyranosyl)-β-D-glucopyranoside (β-primeveroside, 12%) together with capsaicin 4-O-β-D-glucoside (6%) was isolated from the cell suspension of P. ginseng after one week of incubation with capsaicin. On the other hand, 8-nordihydrocapsaicin was glycosylated to 8-nordihydrocapsaicin 4-O-β-D-glucoside (5%) and 8-nordihydrocapsaicin 4-O-β-primeveroside (9%) by P. ginseng. Pretreatment of the cultured cells with salicylic acid greatly enhanced the glucosylation activity toward capsaicinoids. When 500 μM of salicylic acid was added to the cultures prior to the addition of substrate, capsaicin was converted into capsaicin 4-O-β-D-glucoside (17%) and capsaicin β-primeveroside (21%) and 8-nordihydrocapsaicin was glycosylated to 8-nordihydrocapsaicin 4-O-β-D-glucoside (16%) and 8-nordihydrocapsaicin β-primeveroside (15%).     

Enzymatic Synthesis of Sulfated Disaccharides using β-D-Galactosidase-catalyzed Transglycosylation

We have established a unique enzymatic approach for obtaining sulfated disaccharides using Bacillus circulans β-D-galactosidase-catalyzed 6-sulfo galactosylation. When 4-methyl umbelliferyl 6-sulfo β-D-galactopyranoside (S6Galβ-4MU) was used as a donor, the enzyme induced transfer of 6-sulfo galactosyl residue to GlcNAc acceptor. As a result, the desired compound 6'-sulfo N-acetyllactosamine (S6Galβ1-4GlcNAc) and its positional isomer 6'-sulfo N-acetylisolactosamine (S6Gal β1-6GlcNAc) were observed by HPAEC-PAD, in 49% total yield based on the donor added, and in a molar ratio of 1:3.5. With a glucose acceptor, the regioselectivity was substantially changed and S6Galβ1-2Glc was mainly produced along with β-(1-1)α,β-(1-3),β-(1-6) isomers in 74% total yield. When methyl α-D-glucopyranoside (Glcα-OMe) was an acceptor, the enzyme also formed mainly S6Galβ1-2Glcα-OMe with its β-(1-6)-linked isomer in 41% total yield based on the donor added. In both cases, it led to the predominant formation of β-(1-2)-linked disaccharides. In contrast, with the corresponding methyl β-D-glucopyranoside (Glcβ-OMe) acceptor, S6Galβ1-3Glcβ-OMe and S6Galβ1-6Glcβ-OMe were formed in a low total yield of 12%. These results indicate that the regioselectivity and efficiency on the β-D-galactosidase-mediated transfer reaction significantly depend on the anomeric configuration in the glucosyl acceptors.     

Enzymatic synthesis of β-D-Gal-(1→3)-[β-D-GlcNAc-(1→6)]-α-D-GalNAc-OC6H4NO2-p as a carbohydrate unit of mucin-type 2 core

We have established a synthetic method for obtaining β-D-Gal-(1→3)-[β-D-GlcNAc-(1→6)]-α-D-GalNAc-OC6H4NO2 -p (1), which is a carbohydrate unit of mucin-type 2 core. A β-N-acetyl-D-hexosaminidase from Nocardia orientalis catalyzed the synthesis of the desired compound 1 with its isomers β-D-GalNAc-(1→6)-β-D-Gal-(1→3)-α-D-GalNAc-OC6H4NO2-p (2) β-D-GlcNAc-(1→3)-β-D-Glc-(1→3)-α-D-GalNAc-OC6H4NO2-p (3) through N-acetylglucosaminyl transfer from N,N′-diacetylchitobiose and β-D-Gal-(1→3)-α-D-GalNAc-OC6H4NO2-p. The enzyme formed the trisaccharides 1, 2, and 3 in 14% overall yield based on β-D-Gal-(1→3)-α-D-GalNAc-OC6H4NO2-p as an acceptor substrate, and in the ratio of 44:32:24. In this way, N-acetylglucosaminyl transfer favored O-6 of the acceptor rather than O-6′, and occurred to a lesser extent at O-3′. This reaction was efficient enough to allow a one-pot preparation of the desired carbohydrate unit of mucin-type 2 core. When β-D-Gal-(1→3)-β-D-GalNAc-OC6H4NO2-p was used as an acceptor, the enzyme also synthesized three kinds of trisaccharides in the same regioselectivity with respect to O-6 and O-6′ versus O-3′ of the acceptor.     

Archaeobotanic evidence of the preincaic Chiribaya culture. Determination of capsaicinoids in archaeological samples of Capsicum frutescens and votive foods

The lack of Capsicum species or paprika (a basic ingredient of Peruvian foodstuff) in preincaic archaeological samples and votive foods, as evidenced by archaeobotanic studies, has stimulated the chemical analyses of these samples by HPLC methods. The results confirmed the absence of capsaicinoids in these samples whereas they were detected in more ancient fossil fruit.     

Synthesis of blockwise alkylated (1→4) linked trisaccharides as surfactants: influence of configuration of anomeric position on their surface activities

New carbohydrate-based surfactants consisting of hydrophilic cellobiosyl and hydrophobic glucosyl residues, methyl β-d-glucopyranosyl-(1→4)-α-d-glucopyranosyl-(1→4)-2,3,6-tri-O-methyl-α-d-glucopyranoside 1 (GβGαMα, G: glucopyranosyl residue, α and β: α-(1→4)- and β-(1→4) glycosidic bonds, M: methyl group), 2 (G(β)G(β)M(α)), 3 (G(β)G(α)M(β)), 4 (G(β)G(β)M(β)), 5 (G(β)G(α)E(α), E: ethyl group), 6 (G(β)G(β)E(α)), 7 (G(β)G(α)E(β)), 8 (G(β)G(β)E(β)) and eight α-and β-glycoside mixtures (a mixture of 1 and 2: 1/2=62/38 (9), 32/68 (10); a mixture of 3 and 4: 3/4=69/31 (11), 32/68 (12); a mixture of 5 and 6: 5/6=62/38 (13), 33/67 (14); a mixture of 7 and 8: 7/8=59/41 (15), 29/71 (16)) were synthesized via combined methods consisting of acid-catalyzed alcoholysis of cellulose ethers and glycosylation of phenyl thio-cellobioside derivatives. Their surface activities in aqueous solution depended on their chemical structures: α- or β-(1→4) linkage between hydrophilic cellobiosyl and hydrophobic glucosyl blocks, methyl or ethyl groups of hydrophobic glucosyl block, and α- or β-linked ether group at the C-1 of hydrophobic glucosyl block. The mixing effect of α- and β-glycosides on surface activities was also investigated. As a result, ethyl β-d-glucopyranosyl-(1→4)-α-d-glucopyranosyl-(1→4)-2,3,6-tri-O-ethyl-β-d-glucopyranoside 7 (G(β)G(α)E(β)) had the highest surface activity, and its critical micellar concentration (CMC) and γ(CMC) (surface tension at CMC) values of compound 7 were 0.5mM (ca. 0.03wt%) and 34.5mN/m, respectively. The surface tensions of α- and β-glycoside mixtures except for compounds 9 and 10 were almost equal to those of pure compounds. The syntheses of the mixtures of α- and β-glycosides without purification process are easier than those of pure compounds. Thus, the mixtures should be more practical compounds for industrial use as a surfactant.     

Purification and properties of recombinant β-galactosidase from Bacillus circulans

A gene encoding β-galactosidase from Bacillus circulans which had hydrolysis specificity for the β1-3 linkage was expressed in Escherichia coli. The β-galactosidase was purified from crude cell lysates of E. coli by column chromatographies on Resource Q and Sephacryl S-200 HR. The enzyme released galactose with high selectivity from oligosaccharides which had terminal β1-3 linked galactose residues. However it did not hydrolyse β1-4 linked galactooligosaccharides. Moreover, Galβ1-3GlcNAc, Galβ1-3GalNAc, and their p-nitrophenyl glycosides were regioselectively synthesized in 10–46% yield by the transglycosylation reaction using this enzyme.     

Synthesis and stability assay of 4-methylumbelliferyl (1→3)-β-D-pentaglucoside

The synthesis and stability of 4-methylumbelliferyl (1 → 3)-β-D-pentaglucoside 3 are described. The (1 → 3)-β-D-glucan isolated from the cell walls of Saccharomyces cerevisiae was recovered from the aqueous medium as water-insoluble particles by the spray drying (GS) method. The acid-solubilized (1 → 3)-β-D-oligoglucosides were prepared by partial acid hydrolysis of glucan. The peracetylated (1 → 3)-β-D-pentaglucoside 1 was obtained by isolation of peracetylated (1 → 3)-β-D-oligoglucoside mixture. The peracetylated 4-methylumbelliferyl (1 → 3)-β-D-pentaglucoside 2 was synthesized by treating compound 1 with the 4-methylumbelliferone and a Lewis acid (SnCl₄) catalyst. NaOMe in dry methanol was used for the deacetylation of the blocked derivative, to give the target compound 3 in an overall yield of 35%. Activity assays with β-glucosidase indicated that compound 3 was much more stable than the corresponding pentasaccharide.     

在大鼠发育过程中β1,4半乳糖基转移酶的组织分布及其变化的研究

用HPLC纯化了荧光标记的底物（Gnβ1-2Ma1-6（Gnβ1-2Mα1-3）Mβ1-4Goβ1-4Gn-PA）用β-1,4-半乳糖基转移酶的荧光标记底物的HPLC测定方法,测定了在发育过程中大鼠肝,肾,脑中的酶活性的变化,结果表明,（1）在正常成年大鼠中,各组织酶活性具有组织特异性,（2）不同的发育期,其酶活性不同。胎鼠（孕20d,以下同）时最高,以后就渐渐下降,各组织酶活力变化幅度是不一致的,这些变化的生理意义有待子进一步研究．     

细胞诱导分化剂对HL60细胞β-1,4-半乳糖基转移酶活性的影响

用荧光标记的受体底物（Ｇｎβ１－２Ｍα１－６（Ｇｎβ１－２Ｍα１－３）Ｍβ１－４Ｇｎβ１－４（Ｆｕｃα１－６）Ｇｎ－ＰＡ）,结合高效液相层析（ＨＰＬＣ）建立了细胞β－１,４－半乳糖基转移酶的活性检测方法．研究了ＨＬ６０细胞在体外低血清培养后不同的时间其酶活性的变化,发现１２至２４ｈ酶活性达到一个高峰,为５０．１４ｐｍｏｌ／ｍｉｎ（１０６ｃｅｌ）,此时细胞处在分裂间期,其它各测定时间变化不大．用ＰＭＡ,ＲＡ等细胞诱导分化剂处理ＨＬ６０细胞株时,发现其活性发生了较明显的变化,ＰＭＡ诱导的细胞其酶活性在２４ｈ变化最大,升高到对照的１．３２倍;而ＲＡ处理的细胞其酶活性在７２ｈ变化最大,升高到对照的２．１５倍．