稀有抗肿瘤人参皂苷衍生物的制备与分离

目的: 研究稀有抗肿瘤人参皂苷衍生物的制备与分离.方法:采用硅胶柱层析等色谱方法对人参总皂苷酸解产物进行分离,并通过重结晶纯化、理化常数测定和波谱数据进行化合物的结构鉴定.结果:从人参总皂苷酸水解产物中分离得到11个化合物,鉴定出10个化合物的化学结构分别为达玛烷-20(22)-烯-3β,12β,26-三醇(Ⅰ) 、20(S)-25-甲氧基-达玛烷-3β,12β,20-三醇(Ⅱ)、人参二醇(Ⅲ)、20(S)-原人参二醇(Ⅳ)、20(R)-原人参二醇(Ⅴ)、20(S)-人参三醇(Ⅵ)、拟人参皂苷-F11苷元(Ⅶ)、20(R)-原人参三醇(Ⅷ)、20(R)-达玛烷-3β,12β,20,25-四醇(Ⅸ)、20(R)-25-羟基原人参五醇(Ⅹ).结论:化合物Ⅰ、Ⅱ为从西洋参(茎、叶、果、花蕾)中首次发现.化合物Ⅸ为本课题组首次发现和报道的具有显著抗肿瘤活性的原人参二醇型皂苷元衍生物.     

人参茎叶皂苷的Fusarium sacchari转化产物成分研究

目的利用甘蔗镰孢Fusarium sacchari对人参茎叶皂苷进行生物转化。方法转化产物通过硅胶柱色谱进行分离,经理化常数和光谱分析鉴定化合物的结构。结果从人参茎叶皂苷的Fusarium sacchari转化产物中分离鉴定了10个化合物,分别为20(S)-人参二醇(1)、20(S)-原人参二醇(2)、20(R)-原人参二醇(3)、20(S)-人参三醇(4)、20(S)-原人参三醇(5)、20(R)-原人参三醇(6)、20(S)-原人参二醇-20-O-β-D-吡喃葡萄糖苷(CK)(7)、人参皂苷F1(8)、人参皂苷Rh1(9)和人参皂苷Rg1(10)。结论化合物1~10为首次从人参茎叶皂苷的Fusarium sacchari生物转化产物中分离得到,且Fusarium sacchari可转化人参茎叶皂苷生成稀有抗肿瘤皂苷,是一种具有开发价值的稀有活性菌株。     

人参果总皂苷水解产物中稀有活性皂苷元化学研究

目的:研究人参果总皂苷水解产物的化学成分。方法:采用常规水解和硅胶柱层析分离,通过理化常数和光谱分析鉴定化合物的结构。结果:从人参果总皂苷水解产物中分离并鉴定了7个化合物,它们的化学结构分别为20(S)-人参二醇(Ⅰ)、20(R)-原人参二醇(Ⅱ)、20(S)-原人参二醇(Ⅲ)、20(S)-人参三醇(Ⅳ)、20(R)-原人参三醇(Ⅴ)、20(R)-达玛烷-3β,12β,20,25-四醇(Ⅵ)、20(R)-达玛烷-3β,6α,12β,20,25-五醇(Ⅶ)。结论:化合物Ⅰ~Ⅴ为首次从人参果总皂苷酸水解产物中分得的人参皂苷衍生物。Ⅱ、Ⅲ为首次在人参果中发现。化合物Ⅵ为本课题组从人参果皂苷中首次发现的新天然产物,其具有显著的抗肿瘤活性。     

人参皂苷化合物K乙酰化衍生物的合成及分析

目的:研究人参皂苷化合物K乙酰化衍生物的合成及产物结构,建立其高效液相分析方法。方法:采用对葡萄糖基6-位保护-去保护的方法,得到除糖基6-位未乙酰化的化合物K衍生物1c;利用一维核磁(1D NMR)、二维核磁(2D NMR)及质谱(MS)方法对合成产物1c进行结构鉴定;利用反相高效液相色谱,建立了人参皂苷化合物K乙酰化衍生物1c的分析方法。结果:人参皂苷化合物K乙酰化产物1c的得率为46.4%,在高效液相色谱中与其他杂质的分离度较好,分析时间在45 min以内。结论:首次采用人参皂苷化合物K葡萄糖基6-羟基保护的路线,合成其乙酰化衍生物1c,并归属了衍生物的NMR数据。采用HPLC可以快速高效地进行人参皂苷化合物K乙酰化衍生物的分析。     

人参花蕾中的1个新皂苷5,6-二脱氢-20(S)-人参皂苷Rg_3

目的研究人参Panax ginseng花蕾中的人参皂苷类化学成分。方法采用Diaion HP-20、MCI gel、硅胶及半制备高效液相等柱色谱方法进行分离、纯化,根据NMR、MS等谱学数据进行结构鉴定。结果从人参花蕾中分离得到了4个化合物,分别鉴定为6′-乙酰人参皂苷F1(1)、12α-羟基人参皂苷Rd(2)、20(S)-人参皂苷Rg3(3)及5,6-二脱氢-20(S)-人参皂苷Rg3(4)。结论化合物4为1个新的化合物,化合物1和2为新的天然产物。     

人参果中一个新的天然化合物的分离

目的研究人参浆果的化学成分。方法采用溶剂提取和柱色谱分离等方法进行分离和纯化,根据化合物的理化常数和波谱数据鉴定其结构。结果从人参浆果分离得到12个化合物,分别鉴定为:苯甲酸(Ⅰ)、异人参皂苷-Rh3(Ⅱ)、人参皂苷-Rh2(Ⅲ)、人参皂苷-Rh1(Ⅳ)、人参皂苷-Rg1(Ⅴ)、人参皂苷-Re(Ⅵ)、人参皂苷-Rd(Ⅶ)、人参皂苷-Rc(Ⅷ)、人参皂苷-Rb2(Ⅸ)、人参皂苷-Rb1(Ⅹ)、β-谷甾醇(Ⅺ)和20-O-β-D-吡喃葡萄糖基-20(S)-原人参二醇,命名为化合物K(ⅩⅡ)。结论化合物K是一个新的天然产物。     

人参茎叶中1个新皂苷20(S)-人参皂苷Rf_2

目的研究人参Panax ginseng茎叶总皂苷中的化学成分。方法采用硅胶柱色谱及半制备高效液相色谱等方法进行分离、纯化,通过NMR、MS等谱学方法进行化学结构鉴定。结果从人参茎叶的总皂苷中共分离鉴定了39个化合物,报道其中的1个新化合物和16个已知的化合物,分别为人参皂苷Re(1)、20(S)-人参皂苷Rh_1(2)、20(R)-人参皂苷Rh_1(3)、人参皂苷Rh_5(4)、20(E)-人参皂苷F_4(5)、人参皂苷F_2(6)、20(S)-人参皂苷Rg3(7)、20(R)-人参皂苷Rg_3(8)、20(S)-人参皂苷Rf_2(9)、20(R)-人参皂苷Rf_2(10)、20(S)-原人参二醇(11)、20(R)-原人参二醇(12)、20(S)-人参皂苷Rh2(13)、20(R)-人参皂苷Rh2(14)、20(S)-原人参三醇(15)、20(R)-原人参三醇(16)和人参皂苷Rd(17)。结论化合物9为1个新的化合物;2~10、13和14是稀有人参皂苷。     

人参二醇衍生物抗肿瘤活性比较的初步结果

目的：比较人参二醇衍生物和人参二醇的抗肿瘤活性，以寻找抗肿瘤活性更强的化合物。方法：用细胞染色计数法比较人参二醇衍生物人参二醇-驻琥珀酸酯(I)、313，12β，加(R)-三羟基达玛烷(Ⅱ)、3β，12β-二琥珀酸单酰氧基-20(R)-羟基达玛烷(Ⅲ)和人参二醇的抗肿瘤活性，所用癌株为S180肉瘤，Lewis肺癌，阳性对照为5-氟尿嘧啶，阴性对照是含5％新生牛血清的RPMI1640培养基。结果：衍生物Ⅲ抗肿瘤活性最强；其次为Ⅰ，Ⅱ和人参二醇抗肿瘤活性最弱且两者活性相当。结论：人参二醇衍生物抗肿瘤活性较人参二醇增强。     

三七茎叶皂苷酸水解产物中一个新化合物的分离和鉴定

目的 研究三七Panax notoginseng茎叶皂苷水解转化产物的化学成分,以期发现新的苷元.方法 三七茎叶皂苷酸水解产物通过硅胶、凝胶及液相色谱进行分离,分离得到的化合物结构经谱学方法鉴定.结果 从三七茎叶皂苷水解产物中分离得到7个单体化合物,分别鉴定为20(S)-3-甲氧基-人参二醇(1)、20(E)-达玛烷-20(22)-烯-3β,12β,25-三醇(2)、20(R)-达玛烷-3β,6α,12β,20,25-五醇(3)、20(R)-达玛烷-3β,12β,20,25-四醇(4)、拟人参皂苷-F11苷元(5)、20(S)-人参二醇(6)、20(S)-原人参二醇(7).结论 化合物1为一新化合物,命名为三七皂苷元MPD.     

西洋参茎叶皂苷水解产物中稀有抗肿瘤成分的化学研究

目的研究西洋参Panax quinquefolium茎叶皂苷酸水解产物的化学成分。方法利用硅胶柱色谱等各种色谱技术对西洋参茎叶皂苷酸水解产物进行分离纯化,根据化合物的理化性质和光谱数据进行结构鉴定。结果从西洋参茎叶皂苷酸水解产物中分离得到8个化合物,分别鉴定为20(S)-人参二醇[20(S)-panaxadiol,Ⅰ]、20(S)-原人参二醇[20(S)-protopanaxadiol,Ⅱ]、20(R)-原人参二醇[20(R)-protopanaxadiol,Ⅲ]、20(S)-人参三醇[20(S)-panaxatriol,Ⅳ]、24(R)-拟人参皂苷元[24(R)-ocotillol,Ⅴ]、20(R)-原人参三醇[20(R)-protopanaxatriol,Ⅵ]、20(R)-达玛烷-3β,12β,20,25-四醇[20(R)-dammarane-3β,12β,20,25-tetrol,Ⅶ]、20(R)-达玛烷-3β,6α,12β,20,25-五醇[20(R)-dammarane-3β,6α,12β,20,25-pentol,Ⅷ]。结论化合物Ⅰ～Ⅷ为首次从西洋参茎叶皂苷酸水解产物中分得的人参皂苷元衍生物。其中Ⅳ、Ⅶ、Ⅷ为从西洋参根、茎、叶、果、花蕾中首次发现。化合物Ⅶ为本课题组从人参果皂苷中首次发现和报道的具有显著抗肿瘤活性的原人参二醇型皂苷元衍生物。     

Cytotoxic diacetylenic spiroketal enol ethers from Plagius flosculosus

Three new diacetylenic spiroketal enol ethers named flosculins A (1), B (2), and C (3), along with five known compounds (4-8) of the same structural class, were isolated from the leaves of Plagius flosculosus. The structures were deduced by extensive 1D and 2D NMR spectroscopy and mass spectrometry. All isolated compounds exhibited significant cytotoxic activity against leukemia cells (Jurkat T and HL-60). Compounds 5-8 induced apoptosis in HL-60 cells with corresponding IC(50) values ranging from 4 to 6 microM.     

Cytotoxic germacranolides and acyclic diterpenoides from the seeds of Carpesium triste

Four new highly oxygenated germacranolides (1, 4, 6, and 7) and four new acyclic diterpenes (8-11), along with three known germacranolides (2, 3, and 5), were isolated from the seeds of Carpesium triste. The structures of the new compounds were elucidated by spectroscopic methods including IR, HRESIMS, and 1D and 2D NMR experiments, and the absolute configurations of compounds 1 and 8-10 were established by CD and Mosher's methods, respectively. Compounds 1, 2, and 4-10 were evaluated for their in vitro cytotoxic activity against cultured SMMC-7721 (human hepatoma), HL-60 (human promyelocytic leukemia), and L02 (human hepatocyte) cell lines. Compounds 1, 2, and 4-7 exhibited significant cytotoxicity against HL-60 cells, and compound 10 exhibited cytotoxicity against SMMC-7721 cells.     

艾里莫芬烷倍半萜抗白血病构效关系研究

目的 研究艾里莫芬烷倍半萜抗白血病作用构效关系,为该类倍半萜结构修饰和开发利用提供参考依据.方法 对呋喃艾里莫芬烷倍半萜-橐吾酮(ligularone,9)进行结构修饰,采用MTT法对从橐吾属植物中分离得到的艾里莫芬烷倍半萜以及橐吾酮结构修饰物进行体外抑制人早幼粒白血病细胞(HL-60)生长活性评价.结果 以橐吾酮为原料通过光敏氧化得内酯倍半萜(10),鉴定为6-oxo-8β-methoxyeremophilenolide,通过还原和乙酰化反应获得了2个呋喃倍半萜修饰产物,分别为epiligularol(11),epiligularolacetate(12).活性评价实验结果 表明所有内酯艾里莫芬烷倍半萜对HL-60细胞生长有明显的抑制作用,化合物1～6的IC50＜10μg/ml,化合物7,8,10的IC50在10～20μg/ml之间,具有C9和C10位不饱和结构的内酯倍半萜(1～6)活性较强;所有呋喃艾里莫芬烷倍半萜没有抑制活性,而橐吾酮通过光敏氧化转化为内酯倍半萜后有抑制活性.结论 首次研究了橐吾酮的光敏氧化反应,橐吾酮的呋喃环光敏氧化后可转化为内酯环;首次探讨了艾里莫芬烷倍半萜抗白血病作用构效关系.该类倍半萜的12(8)内酯环可能是抗白血病(HL-60)的关键活性基团,具有C9和C10位不饱和结构的内酯倍半萜活性较强.     

Triterpene saponins and lignans from the roots of Pulsatilla chinensis and their cytotoxic activity against HL-60 cells.

Two new triterpene saponins (8 and 9) and seven previously reported triterpene saponins (1-7) based upon oleanolic acid or hederagenin, along with two known lignans, (+)-pinoresinol (10) and beta-peltatin (11), were isolated from a saponin fraction prepared from the MeOH extract of the roots of Pulsatilla chinensis. The structures of the new saponins were determined by spectroscopic analysis, including 2D NMR spectroscopic techniques, and the results of hydrolytic cleavage. The isolated compounds and some derivatives were evaluated for their cytotoxic activity against HL-60 human leukemia cells.     

Triterpene saponins from the roots of Clematis chinensis

A saponin-enriched fraction prepared from the MeOH extract of the roots of Clematis chinensis showed cytotoxic activity against HL-60 promyelocytic leukemia cells, from which five new triterpene saponins based on oleanolic acid, along with three known saponins, were isolated. The structures of the new saponins were determined on the basis of spectroscopic analysis, including extensive 1D and 2D NMR data and hydrolysis followed by chromatographic and spectroscopic analysis. Among the isolated saponins, monodesmosidic saponins exhibited cytotoxic activities against cultured tumor cells.     

Cytotoxic alkaloids and antibiotic nordammarane triterpenoids from the marine-derived fungus Aspergillus sydowi

Three new diketopiperazine alkaloids, 6-methoxyspirotryprostatin B (1), 18-oxotryprostatin A (2), and 14-hydroxyterezine D (3), with an oxaspiro[4.4]lactam moiety, 14-norpseurotin A (4), and the 29-nordammarane triterpenoid 6beta,16beta-diacetoxy-25-hydroxy-3,7-dioxy-29-nordammara-1,17(20)-dien-21-oic acid (5), as well as 12 known compounds (6- 17), were isolated from the ethyl acetate extract of a marine-derived fungal strain, Aspergillus sydowi PFW1-13. The structures of compounds 1- 5 were elucidated by comprehensive spectroscopic analysis. Compounds 1- 3 exhibit weak cytotoxicity against A-549 cells, with IC 50 values of 8.29, 1.28, and 7.31 microM, respectively. Compound 1 also shows slight cytotoxicity against HL-60 cells, with an IC 50 value of 9.71 microM. Compounds 4 and 5 display significant antimicrobial activities against Escherichia coli, Bacillus subtilis, and Micrococcus lysoleikticus with MICs of 3.74, 14.97, and 7.49 microM and 10.65, 5.33, and 10.65 microM, respectively.     

Steroidal saponins from Dracaena surculosa

A phytochemical investigation of the whole plant of Dracaena surculosa resulted in the isolation of nine steroidal saponins, including three new bisdesmosidic spirostanol saponins, named surculosides A (1), B (2), and C (3), and a new bisdesmosidic furostanol saponin (4), which are based on (25S)-spirost-5-ene-1beta, 3beta-diol [(25S)-ruscogenin] as the aglycon. The structures of 1-4 were determined by spectroscopic analysis, including 2D NMR spectroscopic data, and the results of hydrolytic cleavage. The isolated saponins were evaluated for their cytotoxic activity against HL-60 human promyelocytic leukemia cells.     

人参皂苷20(s)-Rg3对llc-pk1细胞中顺铂所致肾毒性的保护作用

目的:探讨人参皂苷20(s)-Rg3对llc-pk1细胞中顺铂所致肾毒性的保护作用。方法:通过基于细胞的肾脏保护试验,研究了发酵黑参(FBG)及其活性成分人参皂苷20(S)-Rg3对猪肾(LLC-PK1)细胞中顺铂(化疗药物)诱导的损伤的保护作用。结果:由顺铂诱导的细胞活力降低,再使用FBG提取物和人参皂苷20(S)-Rg3依赖剂量后明显恢复。用FBG提取物或人参皂苷20(S)-Rg3处理后会降低顺铂诱导升高与磷酸化c-Jun N-末端激酶(JNK),p53和裂解的半胱天冬酶-3升高的蛋白。通过用FBG和人参皂苷20(S)-Rg3的共同处理,由于顺铂的诱导导致凋亡LLC-PK1细胞升高的百分比显著降低。结论:人参皂苷20(s)-Rg3可改善LLC-PK1的细胞毒性,人参皂苷20(S)-RG3可能是通过阻断JNK-P53-caspase-3信号级联反应来介导这种作用的重要组成部分。     

A new antimalarial quassinoid from Simaba orinocensis

A new antimalarial quassinoid, namely, orinocinolide (1), was isolated from the root bark of Simaba orinocensis, together with the previously reported simalikalactone D (2). The structure of 1 was determined primarily from 1D and 2D NMR analysis, as well as by chemical derivatization. Compound 1 was found to be as equally potent as 2 against Plasmodium falciparum clones D6 and W2 (IC(50) 3.27 and 8.53 ng/mL vs 3.0 and 3.67 ng/mL, respectively), but was 4- and 28-fold less toxic than 2 against VERO cells (IC(50) 10 vs 2.3 microg/mL) and HL-60 (IC(50) 0.7 vs 0.025 microg/mL), respectively. In addition, 2 was >46- and >31-fold more potent than pentamidine and amphotericin B (IC(50) 0.035 vs 1.6 and 1.1 microg/mL) against Leishmania donovani, while 1 was inactive. Orinocinolide (1) inhibited growth of human cancer cells SK-MEL, KB, BT-549, and SK-OV-3, but was less potent than 2 (IC(50) 0.8-1.9 vs 0.3-1.0 microg/mL) against these cells.     

Phenanthrene derivatives from Cymbidium Great Flower Marie Laurencin and their biological activities

A new phenanthrendione, ephemeranthoquinone B (1), two phenanthrenes, marylaurencinols A (2) and B (3), and a phenanthrene glucoside, marylaurencinoside A (4), were isolated from the roots of Cymbidium Great Flower Marie Laurencin, along with six known phenanthrenes, 5-10. The structures of these compounds were established by a combination of extensive NMR spectroscopy and/or X-ray crystallographic analysis and chemical degradation. The compounds were tested for antibacterial activities against Bacillus subtilis and Klebsiella pneumoniae and for cytotoxic activity against the human promyelocytic leukemia (HL-60) cell line. Compounds 1, 3, and 6 showed antibacterial activities with minimum inhibitory concentration (MIC) values in the range of 4.88 to 65.10 μM. Notably, ephemeranthoquinone B (1) had a strong antibacterial effect on B. subtilis. Furthermore, 1 exhibited moderate cytotoxic activity (IC(50) 2.8 μM) against HL-60 cells. Compounds 4-9 also showed weak cytotoxic activity against the HL-60 cell line with IC(50) values of 19.3-52.4 μM.