Novel pyrrolidines in the venom of the ant Monomorium indicum

New 2,5-dialkylpyrrolidines found in the venom of Monomorium indicum include trans-2-butyl-5-(4-pentenyl)pyrrolidine [1], trans-2-butyl-5-(6-heptenyl)pyrrolidine [4], trans-5-(5-hexenyl)-2-(4-pentenyl)pyrrolidine [6], trans-5-(6-heptenyl)-2-(5-hexenyl)pyrrolidine [8], and trans-5-heptyl-2-hexylpyrrolidine [16], whose structures were confirmed by synthesis. The concomitance of five previously reported trans-2,5-dialkyl-pyrrolidines along with small amounts of the cis isomers and N-methyl analogues makes the venom of M. indicum the most qualitatively diverse blend of alkaloids reported from an ant to date. The toxicities to termites of four of these alkaloids were determined.     

Novel dialkylpiperidines in the venom of the ant Monomorium delagoense

New 2,6-dialkylpiperidines found in the venom of the ant Monomorium delagoense include cis- and trans-2,6-di(4-pentenyl)-piperidine [2], cis- and trans-2-(4-pentenyl)-6-pentylpiperidine [4], and cis- and trans-2-(6-heptenyl)-6-(4-pentenyl)-piperidine [7], whose structures were confirmed by synthesis. These compounds possess insecticidal and repellent properties.     

A novel (5E,9Z)-dialkylindolizidine from the ant Monomorium smithii

The alkaloidal venom of Monomorium smithii was found to contain (5E,9Z)-3-butyl-5-(4-penten-1-yl)indolizidine [1b], a novel indolizidine, its monocyclic analogue trans-2-butyl-5-(8-nonen-1-yl)pyrrolidine [2], (5E,8Z)-3,5-di(5-hexen-1-yl)pyrrolizidine [3], and trans-2-(5-hexen-1-yl)-5-(8-nonen-1-yl)pyrrolidine [4]. The structure of 1b was based on the results of two independent syntheses. Reductive amination of the appropriate triketone confirmed the carbon-nitrogen skeleton of 1b and suggested its stereochemistry, which was verified by the results of a stereoselective synthesis based on pyrrole hydrogenation. The chemotaxonomic implications of this first report of the concomitance of a 3,5-dialkylindolizidine and a 3,5-dialkylpyrrolizidine in an ant venom are discussed.     

Venom chemistry of the ant Myrmicaria melanogaster from Brunei

Analysis of the extracts of the ant Myrmicaria melanogaster from Brunei in the Indonesian archipelago by GC-MS and GC-IR revealed the presence of five new alkaloids, identified as (9Z)-3-propylindolizidine (1), cis- and trans-2-butyl-5-propylpyrrolidine (2 and 3, respectively), (10E)-3-butyllehmizidine (7), and (5Z,8Z,9Z)-3-butyl-5-propyl-8-hydroxyindolizidine (10a), whose structures were established by comparison with synthetic samples. In addition the monoterpene hydrocarbons beta-pinene, myrcene, and limonene were detected along with all four isomers of 3-butyl-5-methylindolizidine (4a-d), cis- and trans-2-butyl-5-(4-pentenyl)pyrrolidine (5a and 5b), trans-2-butyl-5-pentylpyrrolidine (6), (5Z,9Z)-3-butyl-5-propylindolizidine (8), and (5Z,9E)-3-butyl-5-propylindolizidine (9), alkaloids well known from ants and frogs, whose structures were established on the basis of published spectra or comparison with authentic samples. This study utilized vapor-phase infrared analysis for the assignment of stereochemistry using Bohlmann bands for the bicyclic alkaloids and, in the case of 10a, the detection of an intramolecular hydrogen bond. A biogenetic relationship between the mono- and bicyclic ring systems is proposed.     

不同产地壮药土垅大白蚁菌圃指纹图谱的研究

目的:对广西不同产地壮药土垅大白蚁菌圃指纹图谱进行比较研究。方法:采用全自动氨基酸分析仪测定12批不同产地土垅大白蚁菌圃的总氨基酸类成分。分离柱(4.6 mm×40 mm),柱温57℃;缓冲液流速0.4mL.min^-1,茚三酮流速0.3 mL.min^-1。结果:12批样品的指纹图谱中共检出18个共有指纹峰,各样品重叠率为89.4%~100.0%,7批样品中8个主要峰的相对总面积均>52%。结论:广西不同产地土垅大白蚁菌圃药材的氨基酸组分非常相似,大部分样品的品质较优。指纹图谱可为土垅大白蚁菌圃药材的鉴别和质量评价提供有用的信息。     

超临界CO2萃取鼎突多刺蚁蚁油的正交试验和GC-MS分析

目的:研究鼎突多刺蚁蚁油萃取的最佳工艺条件和蚁油的化学成分.方法:超临界CO2萃取蚁油正交试验,GC-MS作成分鉴定与各种成分相对含量测定,等离子发射光谱法测定铅、锌、锰含量.结果:鼎突多刺蚁蚁油的超临界CO2萃取最佳条件为萃取温度50℃、压力30 MPa、时间2 h,蚁油得率11.4%～14.3%.蚁油含[E]-9-十八碳烯酸、9-烯油酸乙脂、胆甾醇、棕榈酸等51种成分,含不饱和脂肪酸64.58%,含铅0.80 μg·g-1,含微量元素锌0.54 μg·g-1、锰0.15 μg.g-1.结论:该法具有收率高,萃取时间短,蚁油品质好,无溶剂残留等优点.     

Venom's antinociceptive property in the primitive ant Dinoponera quadriceps

Ethnopharmacological relevance

In northeastern Brazil, Dinoponera (Ponerinae) ants macerate are used to treat ear ache and its sting, rheumatism, and back pain. Such a popular use is a relevant fact that called for experimental evaluation of the antinociceptive activity of Dinoponera venom.

Materials and methods

Dinoponera quadriceps venom (DqV; 5–500 μg/kg; i.v.) or morphine (3.4 mg/kg; s.c.) were evaluated in mice models of nociception (n=8 animals/group). Negative controls received sterile saline (0.9% NaCl; i.v.).

Results

DqV showed 64% protein content and exhibited antinociceptive activity, without affecting motor function, in the tests: formalin (72%), writhing (52%), von Frey (71%) and hot plate (45%). The antinociceptive activity was abolished under protein denaturant conditions.

Conclusions

This study provided the first demonstration of the antinociceptive property of Dinoponera quadriceps venom in mice models of chemical, mechanical and thermal nociception, corroborating the popular use and suggesting its potential therapeutic utilization in painful conditions.     

不同产地壮药土垅大白蚁菌圃多糖中单糖组分的测定与品质评价

目的 对广西不同产地壮药土垅大白蚁菌圃多糖中单糖组分进行比较研究.方法 采用高效液相色谱法测定土垅大白蚁菌圃多糖的单糖组成.色谱柱为Symmetry shield TM RP18(4.6 mm×250 mm,5μm),室温,检测波长250 nm,流动相为乙腈磷酸二氢钾溶液(0.05 mol·L-1,pH6.8),梯度洗脱.结果 广西12个不同产地的土垅大白蚁菌圃多糖中均含有甘露糖、鼠李糖、半乳糖醛酸、葡萄糖、半乳糖、木糖、阿拉伯糖,10批样品中半乳糖醛酸相近.结论 广西不同产地土垅大白蚁菌圃药材多糖的单糖的摩尔比虽不相同,但总的倾向是一样的,这提示由于具有相似的物质基础,药理活性相似,大部分样品的品质较优.为土垅大白蚁菌圃药材的鉴别和质量评价提供有用的信息.     

超临界CO2萃取鼎突多刺蚁蚁油的正交试验和GC-MS分析

目的 :研究鼎突多刺蚁蚁油萃取的最佳工艺条件和蚁油的化学成分。方法 :超临界CO₂ 萃取蚁油正交试验 ,GC-MS作成分鉴定与各种成分相对含量测定 ,等离子发射光谱法测定铅、锌、锰含量。结果 :鼎突多刺蚁蚁油的超临界CO₂ 萃取最佳条件为萃取温度 5 0℃、压力 30MPa、时间 2h ,蚁油得率 11. 4 %～ 14 . 3%。蚁油含 [E] 9 十八碳烯酸、9 烯油酸乙脂、胆甾醇、棕榈酸等 5 1种成分 ,含不饱和脂肪酸 6 4 . 5 8% ,含铅 0. 80 μg·g^-1,含微量元素锌0 5 4 μg·g^-1、锰 0. 15 μg g^-1。结论 :该法具有收率高 ,萃取时间短 ,蚁油品质好 ,无溶剂残留等优点。     

泽泻颗粒抗家兔动脉粥样硬化形成的实验研究

目的探讨泽泻颗粒抗新西兰兔动脉粥样硬化形成的作用及其机制。方法将新西兰兔36只随机分空白对照组、模型对照组及泽泻颗粒低、高剂量组,各9只。模型对照组及泽泻颗粒低、高剂量组采用高脂饲料和一次性动脉注射牛血清白蛋白的方法复制动脉粥样硬化模型。泽泻颗粒低、高剂量组均予泽泻颗粒灌胃,浓度分别为7.6、15.2 g/kg,灌胃容量2 mL/kg;模型对照组、空白对照组予与泽泻颗粒低剂量组同容量的蒸馏水。从实验第36日开始,每日灌胃1次,共4周。检测实验前后总胆固醇(TC)、甘油三酯(TG)、低密度脂蛋白(LDL)、高密度脂蛋白(HDL)、血清丙二醛(MDA)及超氧化物歧化酶(SOD)的变化情况,并进行主动脉的病理学检查。结果泽泻颗粒高、低剂量组TC、LDL、SOD给药前后差值与模型对照组比较差异均有统计学意义(P<0.05);泽泻颗粒低剂量组TG、HDL、MDA给药前后差值与模型对照组比较差异均有统计学意义(P<0.05)。且泽泻颗粒低剂量组的主动脉内膜增厚程度及结缔组织成分均较模型对照组轻。结论泽泻颗粒调节血脂和抗氧化作用可能是其抗动脉粥样硬化作用的主要机制。     

Briarane diterpenes from the gorgonian octocoral erythropodium caribaeorum from the northern caribbean

An investigation of the gorgonian octocoral Erythropodium caribaeorum collected off the north coast of Jamaica has yielded three new briarane diterpenes. In addition, the six known diterpenes, erythrolides A, B, D, E, F, and I were isolated. The structures of these diterpenes were established by 1H and 13C NMR spectroscopy utilizing DEPT, COSY, and HETCOR experiments.     

Cytotoxic compounds from Mundulea chapelieri from the Madagascar Rainforest

Bioassay-guided fractionation of methanolic extracts of Mundulea chapelieri resulted in the isolation of two new flavonoids, isomundulinol (1) and 3-deoxy-MS-II (2), in addition to the eight known flavonoids 8-(3,3-dimethylallyl)-5,7-dimethoxyflavanone, MS-II, mundulinol, mundulone, munetone, rotenolone, rotenone, and tephrosin, and one known sesquiterpenoid, 8alpha-acetoxyelemol. The structures of the new flavonoids 1 and 2 were determined by 1D and 2D NMR experiments. All the isolated compounds were tested for cytotoxicity against the A2780 human ovarian cancer cell line; rotenolone and rotenone were the most potent compounds isolated, with IC(50) values of 0.5 and 0.7 microg/mL, respectively.     

Bioactive saponins from Swartzia schomburgkii from the suriname rainforest

Bioassay-guided fractionation of the MeOH extract of Swartzia schomburgkii using the engineered yeast strains 1138, 1140, and 1353 as the bioassay tool resulted in the isolation of five active (2, 4-7) and three inactive (1, 3, 8) saponins. Saponins 4 and 6 are previously unreported. The structures of all of the saponins were established based on 1D and 2D NMR spectral analysis, on acid and alkaline hydrolysis followed by TLC and GC-MS, and by comparison with literature data for known compounds. Three of the isolated compounds (4-6) showed weak cytotoxicity against the M-109 cell line.     

Cytotoxic diterpenes from Cassipourea madagascariensis from the Madagascar rainforest

Bioassay-directed fractionation of ethanol extracts of the roots and leaves of the plant Cassipourea madagascariensis resulted in the isolation of the two new terpenoids cassipourol (1) and cassipouryl acetate (2) in addition to the three known compounds, 3beta,30-dihydroxylup-20(29)-ene (3), 30-hydroxylup-20(29)-en-3-one (4), and combretol (5). The structures of the two new compounds were established on the basis of 1D and 2D NMR spectroscopic data and chemical conversion. All the isolated compounds were tested against the A2780 human ovarian cancer cell line; the two diterpenes (1 and 2) showed moderate cytotoxic activity, while the three known compounds (3-5) were weakly active.     

Antibacterial compounds from the mushroom Ganoderma colossum from Nigeria

Three colossolactones (colossolactone E, colossolactone B and 23-hydroxycolossolactone E) were isolated and characterized from an n-hexane:dichloromethane (2:7) extract of Ganoderma colossum using chromatographic techniques. The antimicrobial activity of the three compounds was then tested against Gram-positive and Gram-negative bacteria. The activity was evaluated by the thin-layer chromatography agar overlay method. The results showed that colossolactone E and 23-hydroxycolossolactone E were active against Bacillus subtilis and Pseudomonas syringae. Colossolactone B was not active against the bacteria. Their structures were elucidated by spectroscopic methods. Potency of the compounds against bacteria tested supports the use of this mushroom in therapeutic medicine.     

Bioactive saponins from Acacia tenuifolia from the suriname rainforest

Bioassay-guided fractionation of the MeOH extract of Acacia tenuifolia using the engineered yeast strains 1138, 1140, 1353, and Sc7 as the bioassay tool resulted in the isolation of the three new saponins 3, 5, and 6 and the three known saponins 1, 2, and 4. The structures of the new compounds were established on the basis of HRMS, 1D and 2D NMR spectral data on the intact saponins, and GC-MS analyses of the sugars. Compounds 1,2 and 5,6 showed cytotoxicity against mammalian cell lines.     

Notes from the Editor-in-Chief

<正>The European Congress for Integrative Medicine(ECIM)2015 Global Summit on Integrative Medicine and Healthcare was held on September 26–27,2015 in Greater Copenhagen.Participants from all around the world explored the prominent issues that included global healthcare and integrative medicine models,integrated healthcare     

New cytotoxic terpenoids from the wood of Vepris punctata from the Madagascar Rainforest

Continuation of the chemical examination of the cytotoxic constituents of the wood of Vepris punctata resulted in the isolation of the two new terpenoids 1 and 2 and eight known compounds, glechomanolide (3), isogermafurenolide, (E,E)-germacra-1(10),4,7(11)-triene, alpha-amyrin, lupeol, lupeyl acetate, taraxerol, and 3-epi-taraxerol, in addition to the alkaloids reported reported previously. The structures of the two new compounds were established on the basis of 1D and 2D NMR spectroscopic data interpretation and chemical modifications. All the isolated compounds were tested against the A2780 human ovarian cancer cell line; the four sequiterpenoids showed moderate cytotoxic activity, while the six triterpenoids were inactive.     

New cytotoxic alkaloids from the wood of Vepris punctata from the Madagascar rainforest

Bioassay-guided fractionation of a CH(2)Cl(2)/MeOH extract of the wood of Vepris punctata resulted in the isolation of three new furoquinoline alkaloids, 5-methoxymaculine (1), 5,8-dimethoxymaculine (2), and 4,5,6,7,8-pentamethoxyfuroquinoline (3), in addition to the four known alkaloids flindersiamine (4), kokusaginine (5), maculine (6), and skimmianine (7). The structures of the new alkaloids 1-3 were established on the basis of extensive 1D and 2D NMR spectroscopic data interpretation. All the isolated compounds were tested against the A2780 human ovarian cancer cell line, and all seven alkaloids showed weak cytotoxic activity.     

Cytotoxic xanthones from Psorospermum molluscum from the Madagascar rain forest

Two new cytotoxic xanthones were isolated from extracts of the Madagascar rain forest plant Psorospermum cf. molluscum using bioassay-guided fractionation with the Escherichia coli SOS chromotest. The structures of the new dihydrofuranoxanthones, designated 3',4'-deoxy-4'-chloropsoroxanthin-(3',5'-diol) ( 1) and psoroxanthin ( 4), were determined on the basis of 2D-NMR, MS, and UV spectroscopic data and are structurally related to the psorospermins, a known class of plant antitumor agents. A new hydroxyprenylated xanthone ( 5) is also described. Xanthones 1 and 4 showed selective in vitro cytotoxicity against ABAE cells (bovine endothelial cell line).