Umwandlung von Cardenoliden durch Mikroorganismen VI. 7β, 11α-Dihydroxydigitoxigenin und Abbau von 7β-Hydroxy-digitoxigenin zum 3β, 7β-Diacetoxy-14-hydroxy-5β, 14β, 17αH-ätiansäure-methylester. Mitteilung über Reaktionen mit Mikroorganismen [1]

Digitoxigenin ( 3 ) was transformed by a Fusarium spec. to 7β-hydroxydigitoxigenin ( 1 ) 1β, 7β-dihydroxydigitoxigenin ( 4 ) and to the hitherto unknown 7β, 11α-dihydroxydigitoxigenin ( 9 ). 7β-acetoxy-digitoxigenin ( 2 ) was degraded to methyl 3β, 7β-diacetoxy-14-hydroxy-5β, 14β, 17αH-etianate ( 11 ).     

长梗千里光呋喃雅槛兰型倍半萜的结构研究

我们曾从甘肃省漳县采集的长梗千里光全草中分离并鉴定出两个呋喃雅槛兰型倍半萜. 在此基础上, 本文对其脂溶性化学成分进行深入研究, 除了发现倍半萜外, 又分离并鉴定出2个呋喃雅槛兰型倍半萜. 通过IR， UV， MS， CD和NMR等数据分析, 确定了4个化合物的结构, 其中, 化合物3首次在长梗千里光中分离得到, 化合物4是一种新化合物, 通过圆二光谱及核磁共振和NOE差谱研究其立体化学结构, 并按Dreiding models构筑该化合物分子的立体化学结构, 确定该化合物为Non-steroid型构象.     

A new glycoside from Polygala tenuifolia Willd

A new tdterpenoid glycoside, 3-β-O-β-D-glucopyranosyl presenegenin 28-O-α-L-arabipyranosyl（1 → 3）-6-β- xylopyranosyl（1 → 4）-[β-D-apiofuranosyl（1 → 3）]-Ct-L-rhamnopyranosyl（1 → 2）-[α-L-rhamnopyranosyl（1 → 3）]-β-D-fucopyranosyl ester （1） was isolated from the Polygala tenuifolia Willd., together with two known saponins, including polygalasaponinXXIV （2） and polygalasaponinXXVIII （3）. The structure of new compound was elucidated by spectroscopic methods.     

Structural determination of two new triterpenoid saponins acylated with monoterpenic acid from Gymnocladus chinensis Baill

Two new triterpenoid saponins acylated with monoterpenic acid, 2β,23-dihydroxy-3-O-α-L-rhamnopyranosyl-21-O-{(6S)-2-trans-2,6-dimethyl-6-O-[3-O-(β-D-glucopyranosyl)-4-O-(2-methylbutanoyl)-β-L-arabinopyranosyl]-2,7-octadienoyl)-acacic acid 28-O-β-D-xylopyranosyl-(1?→?3)-β-D-xylopyranosyl-(1?→?4)-[β-D-glucopyranosyl-(1?→?3)]-α-L-rhamnopyranosyl-(1?→?2)-[α-L-rhamnopyranosyl-(1?→?6)]-β-D-glucopyranosyl ester and 2β,23-dihydroxy-3-O-α-L-rhamnopyranosyl-21-O-{(6S)-2-trans-2,6-dimethyl-6-O-[4-O-((6S)-2-trans-2,6-dimethyl-6-O-(β-L-arabinopyranosyl)-2,7-octadienoyl)]-β-L-arabinopyranosyl]-2,7-octadienoyl}-acacic acid 28-O-β-D-xylopyranosyl-(1?→?3)-β-D-xylopyranosyl-(1?→?4)-[β-D-glucopyranosyl-(1?→?3)]-α-L-rhamnopyranosyl-(1?→?2)-[α-L-rhamnopyranosyl-(1?→?6)]-β-D-glucopyranosyl ester were isolated from the fruit of Gymnocladus chinensis Baill. and the structural elucidation of both the compounds was accomplished by extensive studies of their spectroscopic (1D and 2D NMR, TOF-MS, QFT-MS) and chemical methods.     

黄褐毛忍冬中主皂苷成分的结构解析

报道了黄褐毛忍冬中的两个皂苷主成分, 其中化合物1为新化合物, 并对另一个含量最高的皂苷结构进行了修正.     

A new flavonol glycoside from the seeds of Nigella glandulifera

A new flavonol glycoside, kaempferol 3-O-α-L-rhamnopyranosyl (1?→?6)-O-[β-D-glucopyranosyl (1?→?2)-O-β-D-galactopyranosyl (1→2)]-O-β-D-glucopyranoside (1), together with a known compound, kaempferol 3-O-β-D-glucopyranosyl (1?→?2)-O-β-D-galactopyranosyl (1?→?2)-O-β-D-glucopyranoside (2) was isolated from the seeds of Nigella glandulifera. Their structures were elucidated on the basis of spectral analysis, including ESI-MS, ESI-MS/MS, HR-ESI-MS, DQF-COSY, TOCSY, HSQC and HMBC techniques.     

UCHP Method for Oligosaccharide Combinatorial Library Synthesis

A new methodology for oligosaccharide combinatorial library synthesis using a special hydroxy protecting group, the uni-chemo hydroxy protection (UCHP) group, was developed. The UCHP group was composed of oligomeric amino acid derivatives. The amino terminals of UCHP groups were protected by either Boc or Fmoc groups. By using these two types of UCHP, five kinds of trigalactoses [Galβ1-3Galβ1-3Gal, Galβ1-3(Galβ1-4)Gal, Galβ1-4Galβ1-3Gal, Galβ1-3Galβ1-4Gal, and Galβ1-4Galβ1-4Gal] were successfully synthesized on a solid support as a model of oligosaccharide combinatorial library. Each step of all reactions was also successfully monitored using a combination of two colorimetric tests, chloranil and methyl red-DIC.     

断节参甙的结构

从断节参根的粗甙中分离得到一个新甙——断节参甙(wallicoside,6).经光谱数据及降解反应证明其结构为告达庭-3-O-β-D-葡萄吡喃糖基-(1→4)-β-D-葡萄吡喃糖基-(1→4)-β-D-夹竹桃吡喃糖基-(1→4)-β-D-加拿大麻吡喃糖基-(1→4)-β-D-加拿大麻吡喃糖甙.     

海枫藤中C21甾体苷的分离和结构测定

从萝摩科植物海枫藤[Marsdenia officinalis Tsiang et P.T.Li.]的藤茎中分离得到四个C21甾体去氧糖苷(1)～(4). 通过化学降解和波谱技术, 确定它们的化学结构依次为: 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6-烯-3β,5α,8β,12β,14β, 17β,20-庚醇 3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-夹竹桃吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(1), 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6-烯-3β,5α,8β,12β,14β,17β,20-庚醇3-O-β-D-葡萄吡喃糖基-(1→4)-3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(2), 12-O-桂皮酰基-20-O-乙酰基(20S)-孕甾烷-6- 烯-3β,5α,8β,12β,14β,17β,20-庚醇3-O-β-D-黄夹吡喃糖基-(1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(3), 12-O-烟酰基-肉珊瑚苷元3-O-β-D-葡萄吡喃糖基-(1→4)-3-O-甲基-6-去氧-β-D-阿洛吡喃糖基-(1→4)-β-D-夹竹桃吡喃糖基- (1→4)-β-D-磁麻吡喃糖基-(1→4)-β-D-磁麻吡喃糖苷(4). 其中1和2为新化合物, 分别命名为haifengtenoside A, haifengtenoside B, 3和4分别为已知化合物mucronatoside H 和 hainaneosides A, 系首次从该植物中分离得到.     

云南重楼中的新甾体皂苷

从云南重楼Paris polyphylla Sm. var. yunnanensis(France. )Hand.-Mazz.的干燥根茎中分离鉴定了4个甾体皂苷(1~4), 其中化合物1是新化合物, 采用波谱技术鉴定其结构为24-O-β-D-吡喃半乳糖基-(23S,24S)-螺甾-5, 25(27)-二烯-1β,3β,23,24-四醇-1-O-β-D-吡喃木糖基(1→6)-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.     

Steroid saponins and sapogenins ofAllium. XVI. Turoside C fromAllium turcomanicum

From a methanolic extract of the bulbs ofAllium turcomanicum Rgl. we have isolated a new furostanol glycoside, turoside C (I). An acid hydrolysate was found to contain the aglycone — neoagigenin (II) — and the sugars D-xylose, D-glucose, and D-galactose in a ratio of 1:4:1. The structure of the furostanol (I) has been established by methylation, enzymatic hydrolysis, and oxidative cleavage, and also by the oxidative cleavage of (II), as (25S)-5α-furostan-2α,3β,6β,22α,26-pentaol 26-O-β-D-glucopyranoside 3-O-{[O-β-D-xylopyranosyl-(1→3)]-[O-β-D-glucopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→2)]-O-β-D-glucopyranosyl-(1→4)-β-D-galacto-pyranoside}.     

虫草素与羟丙基-β-环糊精的包合行为及性能研究

通过饱和溶液方法制备了虫草素(COR)与羟丙基-β-环糊精(HPβCD)形成的包合物.采用紫外-可见光谱法对水溶液中HPβCD与虫草素(COR)的包合行为进行研究,利用Job曲线法确定COR/HPβCD包合物的包合比,通过1 H NMR和2D NMR、DSC、TG、XRD、FTIR和SEM对COR/HPβCD包合物进行表征和性能测定.结果表明,COR/HPβCD包合物的包合比为1:1,虫草素与HPβCD形成包合物后,其水溶性、热稳定性及生物环境稳定性都得到明显提高.COR/HPβCD包合物在医药领域具有潜在的应用前景.     

A new C21 steroid glycoside from Marsdenia tenacissima

A new C21 steroid glycoside,11α-O-tigloyl-12-β-O-acetyl tenacigenin B 3-O-β-D-glucopyranosyl-（1→4）-β-D-glucopyr- anosyl-（1→4）-3-O-methyl-6-deoxy-β-D-allopyranosyl-（1→4）-β-D-oleandropyranoside（1）,named tenacissoside N was isolated from the stems of Marsdenia tenacissima.The structure of the glycoside was identified by HR-ESI-MS and NMR spectra.     

Structural characterisation of a water-soluble polysaccharide from tissue-cultured Dendrobium huoshanense C.Z. Tang et S.J. Cheng

A water-soluble polysaccharide TC-DHPA4 with a molecular weight of 8.0 × 10⁵ Da was isolated from tissue-cultured Dendrobium huoshanense by anion exchange and gel permeation chromatography. Monosaccharide analysis revealed that the homogeneous polysaccharide was made up of rhamnose, arabinose, mannose, glucose, galactose and glucuronic acid with a molar ratio of 1.28:1:1.67:4.71:10.43:1.42. The sugar residue sequence analysis based on the GC-MS files and NMR spectra indicated that the backbone of TC-DHPA4 consisted of the repeated units:→6)-β-Galp-(1→6)-β-Galp-(1→4)-β-GlcpA-(1→6)-β-Glcp-(1→6)-β-Glcp-(→. The sugar residue sequences β-Glcp-(1→)-α-Rhap-(1→3)-β-Galp-(1→, β-Glcp-(1→4)-α-Rhap-(1→3)-β-Galp-(1→, β-Galp-(1→6)-β-Manp-(1→3)-β-Galp-(1→, and α-l-Araf-(1→2)-β-Manp-(1→3)-β-Galp-(1→ were identified as the branches attached to the C-3 position of (1→6)-linked galactose in the backbone.     

Platycoside O, a new triterpenoid saponin from the roots of Platycodon grandiflorum

A new unusual minor triterpenoid saponin, platycoside O (1), was isolated from the 75% EtOH extract obtained from the roots of Platycodon grandiflorum, together with four known saponins: platycoside M-3 (2), platycoside J (3), platycoside F (4) and platycoside B (5). The structure of 1 was determined as 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl-2β,3β,16α,23-tetrahydroxyolean-12-en-24-methoxyl, 24-oxo-28-oic acid 28-O-β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside on the basis of spectral analysis and chemical evidence.     

Antigenotoxic ketosteroid from the red algae Jania adhaerens

A new ketosteroid, 6β,16β-dihydroxycholest-4-en-3-one (1), in addition to the known 6β-hydroxycholest-4-en-3-one (2), 6β-hydroxycholest-4,22-dien-3-one (3) and 16β-hydroxy-5α-cholestan-3,6-dione (4), was isolated from the red alga Jania adhaerens. The structures were assigned on the basis of (1)H- and (13)C-NMR experiments. The new compound (1) was evaluated for its genotoxic and cytotoxic activities and found to possess protective antigenotoxicity in human peripheral blood cells.     

A new steroidal glycoside from the Ophiopogon japonicus Ker-Gawler (Liliaceae)

A new steroidal glycoside (1), (25R)-14α, 17α-hydroxyspirost-5-en-3β-yl 3-O-α-L-rhamnpyranosyl-(1 → 2)-β-D-glucopyranosyl-(1 → 3)-β-D-glucopyranoside, together with three known steroidal glycosides, (25R)-3β-hydroxyspirost-5-en-1β-yl-3-O-α-L-rhamnopyranosyl-(1 → 2)-O-β-D-xylopyranosyl-(1 → 3)-α-L-arabinopyranoside (2), Cixi-ophiopogon B (3) and Cixi-ophiopogon A (4), were obtained from the tuberous roots of Ophiopogon japonicus (Liliaceae). Compound 2 was isolated from the Ophiopogon genus for the first time. Their structures were identified on the basis of extensive mass and nuclear magnetic resonance spectroscopic analysis.     

The synthesis of some 5-methoxypyrimidine nucleosides

The synthesis of 5-methoxyuridine ( 3 ), 5-methoxycytidine ( 6 ), 1-(2-deoxy-β-D-erythropento-furanosyl)-5-methoxyuracil ( 14 ), 5-methoxy-1-β-D-ribofuranosyl-4-thiopyrimidin-2-one ( 5 ), 1-β-D-arabinofuranosyl-5-methoxycytosine ( 12 ), 1-β-D-arabinofuranosyl-5-methoxyuracil ( 8 ) and 1-β-D-arabinofuranosyl-5-methoxy-4-thiopyrimidin-2-one ( 11 ) have been accomplished. Both 3 and 14 were synthesized by alkylation of 2,4-bis(trimethyIsilyI)-5-methoxyuracil ( 1 ) with the appropriately blocked halosugars. Synthesis of the corresponding 5-methoxy-1-β-D-arabinofuranosyl derivatives was accomplished through the intermediate 2,2 -anhydro-1-β-D-arabinofuranosyl-5-methoxyuracil ( 7 ). The cytosine and 4-thiouracil derivatives in both the arabino- and ribo- series were prepared by thiation followed by amination.     

Electrospinning of polymer-free nanofibers from cyclodextrin inclusion complexes

The electrospinning of polymer-free nanofibers from highly concentrated (160%, w/v) aqueous solutions of hydroxypropyl-β-cyclodextrin (HPβCD) and its inclusion complexes with triclosan (HPβCD/triclosan-IC) was achieved successfully. The dynamic light scattering (DLS) and rheology measurements indicated that the presence of considerable HPβCD aggregates and the high solution viscosity were the key factors in obtaining electrospun HPβCD and HPβCD/triclosan-IC nanofibers without the use of any polymeric carrier. The HPβCD and HPβCD/triclosan-IC solutions containing 20% (w/w) urea yielded no fibers but only beads and splashes because of the depression of the self-aggregation of the HPβCD. The inclusion complexation of triclosan with HPβCD was studied by isothermal titration calorimetry (ITC) and turbidity measurements. The characteristics of the HPβCD and HPβCD/triclosan-IC nanofibers were investigated by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). It was found that the electrospinning of HPβCD/triclosan-IC solution having a 1:1 molar ratio was optimal for obtaining nanofibers without any uncomplexed guest molecules.     

九子参中三个糖链上带乙酰基的新三萜皂苷-九子参苷B,C, D

从石竹科植物九子参(Silene rubicunda)根中得到四个糖链上带乙酰基的新的三萜皂苷-九子参苷A, B, C, D(rubicunosides A~D, 1~4)。前文已详细报道了九子参苷A的结构研究, 本文报道九子参苷B, C, D的结构。通过FAB-MS和NMR,分别确定九子参苷B, C, D为糖链上带单乙酰基的三萜九糖苷、七糖苷和糖链上带双乙酰基的三萜八糖苷, 分别命名为皂树酸-3-O-β-D-吡喃半乳糖-(1→2)-[β-D-吡喃木糖-(1→3)]-β-D-吡喃葡萄糖醛酸-28-O-β-D-吡喃木糖-(1→3)-β-D-吡喃木糖-(1→4)-α-L-吡喃鼠李糖-(1→4)-[β-D-吡喃葡萄糖-(1→4')-β-D-吡喃鸡纳糖-(1→2)]-[3'-O-乙酰基]-β-D-吡喃夫糖苷(九子参苷B, 2), 皂树酸-3-O-β-D-吡喃半乳糖-(1→2)-[β-D-吡喃木糖-(1→3)]-β-D-吡喃萄淘糖醛酸-28-O-β-D-吡喃木糖-(1→4)-α-L-吡喃鼠李糖-(1→4)-[4"-O-乙酰基-β-D-吡喃葡萄糖-(1→2)]-β-D-吡喃夫糖苷(九子参苷C, 3), 皂树酸-3-O-β-D－吡喃半乳糖-(1→2)-[β-D-吡喃半乳糖-(1→2)-[β-D-吡喃木糖-(1→3)]-[6'-O-正丁基]-β-D-吡喃葡萄糖醛酸-28-O-β-D-吡喃木糖-(1→3)-β-D-吡喃木糖-(1→4)-α-L-吡喃鼠李糖-(1→4)-[2"-O-乙酰基-β-D-吡喃鸡纳糖-(3'-O-乙酰基]-β-D-吡喃夫糖苷(九子参苷D, 4)。