安徽贝母生物碱的分离和结构鉴定

从安徽贝母(fritillaria anhuiensis S.C.Chen et S.F.Yin)鳞茎中分离出四个生物碱Ⅰ,Ⅱ,Ⅲ及Ⅳ,通过光谱数据及与标准品对照,碱Ⅰ为浙贝乙素(verticinone,peiminine),碱Ⅱ为贝母辛(peimisine),碱Ⅲ为异浙贝甲素(isoverticine)。碱Ⅳ是一种新的生物碱,定名为皖贝甲素(wanpeinine A)。根据IR,MS,¹HNMR以及¹³CNMR光谱解析和衍生物制备,推定其结构为5α,14α,22β-cevanine-3β,6α,20β-triol。     

西洋参茎叶总皂苷氧化裂解产物中的新侧链环合型达玛烷型三萜

为了研究西洋参茎叶总皂苷氧化碱解产物的组成，对加拿大产西洋参茎叶总皂苷进行氧化碱解后，其产物通过硅胶柱色谱、Sephadex LH-20柱色谱、重结晶等方法进行分离纯化得到2个化合物。根据化合物的理化性质和光谱数据，鉴定其结构为：(12R,20S,24R)-20,24;12,24-diepoxy-24-deisopropyl-dammarane-3β-ol (1)和(20S,24R)-20,24-epoxydammarane-3β,12β,25-triol (2)。化合物1，2均为首次从西洋参茎叶总皂苷碱解产物中分离得到侧链环合的达玛烷型三萜，其中化合物1为新化合物。     

白木通中一个新的三萜皂苷类化合物

目的研究木通科植物白木通藤茎的化学成分。方法通过反复硅胶柱色谱、ODS柱色谱和重结晶等方法进行分离纯化，根据化合物的理化性质和波谱数据鉴定结构。结果从白木通藤茎70%乙醇提取物中分离得到6个化合物。分别鉴定为2α,3β,23-trihydroxyolean-12-en-28-oic acid =O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl ester (I), 2α,3β,23-trihydroxyurs-12-en-28-oic acid O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl ester (II), 2α,3β,23-trihydroxyolean-12-en-28-oic acid O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl ester (III), 2α,3β,23-trihydroxyurs-12-en-28-oic acid O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl ester (IV), 2α,3β,23-trihydroxyolean-12-en-28-oic acid O-β-D-glucopyranosyl ester (V), 2α,3β,23-trihydroxyurs-12-en-28-oic acid O-β-D-glucopyranosyl ester (VI)。结论化合物II为新化合物，命名为mutongsaponin C，其他均为首次从该植物藤茎中分离得到。     

向日葵二萜化学成分及其细胞毒活性研究

为了研究向日葵(Helianthus annuus L.)的生物活性成分。本文采用色谱法系统研究向日葵的化学成分，根据波谱学分析鉴定了化合物的结构，用MTT法评价其细胞毒活性。从成熟的向日葵花盘中分离鉴定了11个化合物，分别为：对映贝壳杉-2α,16α-二醇(1)，对映贝壳杉-15α,16α-环氧-17-醛-19-酸(2)，对映贝壳杉-16β-醇(3)，phyllocladan-16β-ol (4)，ent-atisan-16α-ol (5)，15-羟基-对映贝壳杉-16-烯-19酸(6)，对映贝壳-15-当归酰氧基-16-烯-19-酸(7)，对映贝壳杉-16-烯-19酸(8)，对映贝壳杉-17-羟基-15-烯-19酸(9)，对映贝壳杉-16β，17-二羟基-19酸(10)和ciliaric acid (11)。其中化合物1和2为新化合物，部分化合物显示一定的细胞毒活性。     

人工栽培的南方红豆杉化学成分研究(III)

从人工栽培的南方红豆杉全株乙醇提取物的氯仿萃取部位通过反复硅胶和凝胶柱层析分离得到4个化合物，采用波谱解析(IR，ESI-MS，¹H NMR和¹³C NMR)等方法确定了其结构，4个化合物分别鉴定为taxamairin K (1), 2α,4α-dideacetoxy-7β-benzoyloxy-5β,20-epoxy-9α,10β,13α,15-tetrahydroxy-11(15→1)abeotaxa-11-ene (2), 7β-xylosyl-taxol (3), 10-deacetoxy-7-xylosyl-taxol (4)，其中化合物1为新化合物。     

红蓼果实中的一个新三萜皂苷

为了研究红蓼果实的化学成分，利用硅胶和反相柱色谱方法进行分离纯化，根据理化性质和光谱数据鉴定其化合物结构，分离并鉴定了3个化合物：28-O-β-D-glucopyranosyl-3β,7β-dihydroxy-lup-20(29)-en-28-oate (1)，5,7-二羟基色原酮(2)和柚皮素(3)。化合物1为新化合物，化合物2，3为首次从该植物中分离得到。     

5α-△9(11)-16β-甲基-3β,17α,21-三羟基-孕甾烯-3β,21-双醋酸酯-20酮和5α,17α-甲基-17β-羟基-雄甾-3酮的微生物转化

用诺卡氏菌与节杆菌混合菌种转化从蕃麻皂素制得的中间体5α-△⁹⁽¹¹⁾-16-16β-甲基-3β,17α,21三羟基孕甾烯-3β,21-双醋酸酯-20酮(Ⅰ)得50%的16β-甲基-△^1,4,9(11)-孕甾三烯-20酮(Ⅱ)和少量的16β-甲基-9,11α环氧-△¹,4孕甾二烯-20酮(Ⅲ)。另外,又用同样的混合菌种转化从剑麻皂素制得的中间体5α,17α甲基-17β羟基-雄甾-3酮(Ⅳ)得50%17α甲基-17β羟基-△^1,4-雄甾二烯-3酮(Ⅴ)。如改变培养基则得3,17β-羟基-17α-甲基-9酮基-9,10开环-1,3,5(10)雄甾三烯化合物。     

2β-(4′-甲基- 1′-哌嗪基)- 3α-羟基-16,17-取代-5α-雄甾烷的合成

为了寻找心血管系统药物,以表雄酮为原料,合成了7个16,17位取代的目标化合物:2β-(4’-甲基-1’-哌嗪基)-3α-羟基-5α-雄甾-17-酮、2β-(4’-甲基-1’-哌嗪基)-3α,17β-二羟基-5α-雄甾烷、2β-(4’-甲基-1’-哌嗪基)-3α-羟基-16α-溴-5α-雄甾-17-酮、2β-(4’-甲基-1’-哌嗪基)-3α,16α-二羟基-17-氧-5α-雄甾烷、2β-(4’-甲基-1’-哌嗪基)-3α,16α-二羟基-17-肟-5α-雄甾烷、2β-(4’-甲基-1’-哌嗪基)-3α,16α-二羟基-17β-氨基-5α-雄甾烷和2β—(4’-甲基-1’-哌嗪基)-3α,17β-二羟基-16β-氨基-5α-雄甾烷。初步药理试验结果表明它们都有不同程度的抗心律失常活性。     

山莓中两个新二萜的分离与鉴定

为研究山莓(Rubus corchorifolius L.f)的化学成分，应用硅胶柱色谱进行分离纯化，根据化合物的理化性质和波谱数据鉴定结构。本文分离鉴定了2个贝壳杉烷二萜化合物，其结构分别为对映-贝壳杉烷-3α，16α，17，19-四醇(1)，对映-2-羰基-16α-羟基-贝壳杉烷-17-β-D-葡糖苷(2)。化合物1、2均为新化合物。     

Structures of two new diterpenoid dimers from bulbs of Fritillaria ebeiensis

Two new ent-kauranoid diterpenoid dimers, fritillebin C (1) and fritillebin D (2), were isolated from the bulbs of Fritillaria ebeiensis G.D. Yu and G.Q. Ji. Their structures were determined to be ent-16beta-hydroxy-kauran-17-yl ent-16beta3-kauran-17-oate (1); ent-16alpha-hydroxy-kauran-17-yl ent-16beta-kauran-17-oate (2) by means of spectral analysis and chemical evidence.     

Steroidal alkaloids from bulbs of Fritillaria lichuanensis

A new steroidal alkaloid, hupehenizioiside (1), together with four known steroidal alkaloids hupehenizine (2), hupehenirine (3), peiminine (4) and hupeheninoside (5), were isolated and identified from the bulbs of Fritillaria lichuanensis. The structure of hupehenizioiside (1) was determined to be (20R,25S)-5alpha,14alpha,17beta-cevanine-6-oxo-3beta-O-beta-D-glucoside by spectral analysis and chemical evidence. Compounds (2)-(5) were isolated from Fritillaria lichuanensis for the first time.     

Molecular diversity of 5S-rRNA spacer domain in Fritillaria species revealed by PCR analysis.

Beimu (bulbs of Fritillaria) is an important traditional Chinese herbal medicine commonly used as an antitussive and expectorant. There are about 25 species and varieties of Fritillaria that carry the name Beimu on commercial markets. The price for each Beimu may differ by more than 100-fold. However, the identification of the origin of a particular species on the market is difficult. Here, a molecular method was used to identify various species of Fritillaria regardless of their geographical origin. The 5S-rRNA coding sequence is highly conserved in higher eukaryotes, but the spacer sequence of the 5S-rRNA gene is variable among different species. Total genomic DNA from fresh leaves and bulbs of Fritillaria cirrhosa, F. puqiensis, F. anhuiensis, and F. thunbergii was extracted. The 5S-rRNA spacer region of the extracted DNAs was amplified by PCR with a pair of primers located within the conserved coding region. The isolated cDNA clones (approximately 600 bp) covering the 5S-rRNA spacer domain were sequenced. By aligning the isolated nucleotide sequences of the four Fritillaria species, sequence diversity was found in the spacer region. Furthermore, a unique EcoR I site was used for the rapid identification of different species of Fritillaria. To our knowledge, this is the first report on the detection of 5S-rRNA spacer domain sequences of Fritillaria and their use to identify species.     

Identification of bulb from Fritillaria cirrhosa by PCR with specific primers

Bulb of Fritillaria cirrhosa is an important traditional Chinese herbal medicine. According to the Chinese Pharmacopoeia (1995), it is commonly used as an antitussive and expectorant. Many young bulbs from species of Fritillaria are similar to those of F. cirrhosa, but they are different in price and quality. Therefore, there are many young bulbs from species of Fritillaria that could fake those of F. cirrhosa on the commercial market. The coding region of 5S-rRNA is highly conserved in higher eukaryotes. The 5S-rRNA spacer region sequences of F. thunbergii, F. pallidiflora, F. ussuriensi, F. delavayi, F.cirrhosa, F. anhuiensis, F. puqiensis were cloned by PCR with a pair of primers located within the conserved coding region. Based on sequences analyses of the 5S-rRNA spacer region from the 7 species, a specific sequence was found in F. cirrhosa. A pair of specific primers was designed for differentiating the bulbs of F. cirrhosa from each other by PCR.This result indicated that the method is rapid, more accurate and applicable in identification of the bulbs of F. cirrhosa at the DNA level.     

彭泽贝母中二萜类成分

为了研究彭泽贝母的化学成分。利用多种柱色谱方法进行分离纯化，根据光谱数据和理化性质进行结构鉴定。共分离并鉴定了6个对映-贝壳杉类二萜化合物： ent-kauran-15-en-17-ol (I)， ent--kauran-15-en-3α,17-diol (II)， 鄂贝新醇(III)， ent--kauran-16α,17-diol (IV)， ent--kauran-3α，16α,17-triol (V)， ent--16,17-epoxy-kauran-3α-ol (VI)。6个化合物均为首次从彭泽贝母中分得，其中ent--16,17-epoxy-kauran-3α-ol (VI)为新化合物。     

Angiotensin converting enzyme (ACE) inhibitory alkaloids from Fritillaria ussuriensis

Bioassay-guided fractionation of the BuOH-soluble extract of Fritillaria ussuriensis afforded verticinone ( 1), verticine ( 2), and peimisine ( 3). Purification of these compounds was achieved with the use of various chromatographic methods. The structures of the compounds were identified on the basis of MS and NMR data analysis. Compounds 1 - 3 inhibited angiotensin I converting enzyme activity in a dose-dependent manner, displaying 50 % inhibitory concentration values of 165.0 microM, 312.8 microM, 526.5 microM, respectively. The presence of these active substances may be responsible, at least in part, for the antihypertensive action of the bulbs of Fritillaria ussuriensis.     

Steroidal alkaloids from the bulbs of Fritillaria unibracteata

Two new steroidal alkaloids peimisine-3-O-β-D-glucopyranoside (1) and puqiedinone-3-O-β-D-glucopyranoside (3), together with three known compounds peimisine (2), puqiedinone (4), and puqiedine (5), were isolated and characterized from the bulbs of Fritillaria unibracteata. Their structures were fully elucidated by spectroscopic and chemical methods. Compound 1 showed moderate protection effect on neurotoxicity of PC12 cell lines induced by rotenone.     

异浙贝甲素氮氧化物的分离和结构鉴定异浙贝甲素氮氧化物的分离和结构鉴定

目的研究川贝母的化学成分。方法运用色谱方法进行分离纯化,用氢谱、碳谱、DEPT谱及质谱鉴定其结构。结果从四川家种贝母新种——瓦布贝母(Bulbus fritillaria wabuensis S.Y.Tang et S.C.Yueh)鳞茎中分得3个甾体生物碱,分别为:西贝素(imperialine,I),西贝素氮氧化物(imperialine-β-N-oxside,II),异浙贝甲素氮氧化物(isoverticine-β-N-oxide,III)。结论化合物III为一种新的异甾体生物碱,命名为异浙贝甲素氮氧化物(isoverticine-β-N-oxide)。     

A novel steroidal alkaloid from Fritillaria shuchengensis

A novel steroidal alkaloid, suchengbeisine (1), along with two known steroidal alkaloids, N-oxide of verticinone (2) and zhebeininoside (3), were isolated from the bulbs of Fritillaria shuchengensis S. C. Chen et S. F. Yin. The structures of these compounds were elucidated by intensive spectroscopic methods, including NMR, IR, CD and MS.     

Cytotoxic diterpenoids from the roots of Euphorbia ebracteolata

Three new diterpenoids, yuexiandajisu D (1), E (2) and F were isolated from the roots of Euphorbia ebracteolata, along with eight known diterpenoids, jolkinolide B (4), jolkinolide A, ent-11alpha-hydroxyabieta-8(14),13(15)-dien-16,12alpha-olide (6), ent-(13S)-hydroxyatis-16-ene-3,14-dione, ent-3beta,(13S)-dihydroxyatis-16-en-14-one, ent-3-oxokaurane-16alpha,17-diol, ent-16alpha,17-dihydroxyatisan-3-one and ent-atisane-3beta,16alpha,17-triol. The structures of all compounds were deduced using spectroscopic methods and confirmed for 1 and 2 by single-crystal X-ray diffraction. A biogenetic pathway for the formation of 1 and 2 is proposed briefly. Cytotoxic activities were evaluated against ANA-1, B 16 and Jurkat tumor cells. Jolkinolide B (4) displayed modest activity on ANA-1, B 16 and Jurkat tumor cells with IC50 values 4.46 x 10(-2), 4.48 x 10(-2), 6.47 x 10(-2) microM, and ent-11alpha-hydroxyabieta-8(14),13(15)-dien-16,12alpha-olide (6) showed significant activity against ANA-1 and Jurkat cells with IC50 values 7.12 x 10(-3) and 1.79 x 10(-2) microM. Compound 1 was found to be slightly active against ANA-1 cells with an IC50 value 2.88 x 10(-1)microM. Structure-activity relationships of isolated compounds are also discussed.