长药隔重楼中甾体皂苷成分的分离与结构鉴定

目的 研究长药隔重楼Paris polyphylla Smith varh.pseudothibetica的化学成分.方法 采用硅胶柱层析、大孔吸附树脂、葡聚糖凝胶Sephadex LH-20、预装硅胶中压柱层析及半制备RP-HPLC等技术分离纯化单体化合物,根据理化性质及波谱数据鉴定其结构.结果 从长药隔重楼乙醇提取物中分离并鉴定了8个甾体皂苷类单体化合物,分别是偏诺皂苷元-3-O-β-D-葡萄吡喃糖苷(Ⅰ)、薯蓣皂苷元-3-O-а-L-阿拉伯呋喃糖基(1→4)-[а-L-鼠李吡喃糖基(1→2)]-B-D-葡萄吡喃糖苷(Ⅱ)、薯蓣皂苷元-3-O-а-D-葡萄吡喃糖基(1→)-[а-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖苷(Ⅲ)、偏诺皂苷元-3-а-L-鼠李吡喃糖基(1→2)-B-D-葡萄吡喃糖苷(Ⅳ)、偏诺皂苷元-3-O-а-L-阿拉伯呋喃糖基(1→4)-[а-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖苷(Ⅴ)、偏诺皂苷元-3-O-а-L-鼠李吡喃糖基(1→4)-a-L一鼠李吡喃糖基(1→4)-[а-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖苷(Ⅵ)、偏诺皂苷元-3-D-β-L-鼠李吡喃糖基(1→4)-[a-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖苷(Ⅶ)、偏诺皂苷元-3-O-β-D-木呋喃糖基(1→5)-а-L-阿拉伯呋喃糖基(1→4)-[а-L-鼠李吡喃糖基(1→2)]-β-D-葡萄吡喃糖苷(Ⅷ).结论 首次从长药隔重楼中分离并鉴定出化合物Ⅰ～Ⅷ.     

藏药独一味根化学成分的研究

继前报从藏药独一味(Lamiophlomisrotatakudo)根的正丁醇提取物中分离得到两个甙类成分。经化学和光谱分析,两个化合物的结构分别鉴定为3-羟基-4-甲氧基苯乙基-O-[α-L-吡喃鼠李糖(1→3)]-O-[β-D-呋喃芹菜糖(1→6)]-4-O-阿魏酰基-β-D-吡喃葡萄糖甙(1)和3-甲氧基-4-羟基苯乙基-O-[α-L-吡喃鼠李糖(1→3)]-O-[β-D-呋喃芹菜糖(1→6)]-4-O-阿魏酰基-β-D-吡喃葡萄糖甙(2),后者为一新化合物,命名为独一味甙A(lamiophlomiosideA)。     

维药斯亚旦化学成分研究

目的研究维药斯亚旦的化学成分。方法采用正相硅胶、ODS、Sephadex LH-20等柱色谱以及高效制备液相等手段进行分离纯化,并用化学方法和光谱方法鉴定了化合物的结构。结果从斯亚旦中分离鉴定了10个化合物,分别为:五加苷K(1)、常春藤皂苷元-3-O-α-L-鼠李糖基(1→2)-α-L-吡喃阿拉伯糖苷(2)、常春藤皂苷元-3-O-β-D-吡喃木糖基(1→3)-α-L-鼠李糖基(1→2)-α-L-吡喃阿拉伯糖苷(3)、quercetin-3-[6-ferulyl-β-D-glucopyranosyl(1→2)-β-D-glucopyranosyl(1→2)-β-D-glucopyrano-side](4)、quercetin-3-sophorotriosides(5)、quercetin-3-glucosyl(1→2)-galactosyl(1→2)-glucoside(6)、quercetin-3-(6-feruloylglu-cosyl)(1→2)-galactosyl(1→2)-glucoside(7)、3-O-α-L-吡喃鼠李糖-(1→2)-α-L-吡喃阿拉伯糖常春藤皂苷元-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖(8)、3-O-β-D-吡喃葡萄糖基(1→6)-吡喃鼠李糖基-(1→2)-α-L-吡喃阿拉伯糖常春藤皂苷元-28-O-α-L-吡喃鼠李糖基(1→4)-β-D-吡喃葡萄糖基(1→6)-β-D-吡喃葡萄糖苷(9)和芦丁(10)。结论化合物1,4,5为首次从黑种草属中分离得到,化合物6为首次从该种中分离得到。     

瘤果黑种草子的化学成分

目的研究中药瘤果黑种草子的化学成分。方法运用多种色谱方法分离化学成分;依据这些化学成分的理化性质和波谱(NMR、EI-MS)数据分析鉴定化合物的结构。结果从瘤果黑种草子中初步分离得到5个化合物,分别鉴定为胡萝卜苷(1)、常春藤皂苷元-3-O-α-L-吡喃鼠李糖基-(1→2)-α-L-吡喃阿拉伯糖苷(2)、常春藤皂苷元-3-O-β-D-吡喃木糖基-(1→3)-α-L-吡喃鼠李糖基-(1→2)-α-L-吡喃阿拉伯糖苷(3)、3-O-β-D-吡喃木糖基-(1→3)-α-L-吡喃鼠李糖基-(1→2)-α-L-吡喃阿拉伯糖常春藤皂苷元-28-O-β-D-吡喃葡萄糖酯苷(4)、山奈酚-3-O-β-D-吡喃葡萄糖基-(1→2)-β-D-吡喃半乳糖基-(1→2)-β-D-吡喃葡萄糖苷(5)。结论化合物4为首次从黑种草属植物中分离得到,化合物5为首次从该种植物中分离得到。     

延龄草化学成分的分离与鉴定

目的研究延龄草(Trillium tschonoskii Maxim.)根及根茎的化学成分。方法利用硅胶柱色谱、凝胶柱色谱、ODS(反相C18键合硅胶)柱色谱、高效液相色谱等色谱技术对延龄草的化学成分进行分离和纯化,通过理化性质和NMR等波谱数据分析确定化合物的结构。结果从延龄草根及根茎70%(φ)乙醇提取物中分离得到11个已知成分,分别确定为重楼皂苷Ⅵ(chonglouosideⅥ,1)、偏诺皂苷元-3β-O-α-L-吡喃鼠李糖基-(1→4)-[O-α-L-吡喃鼠李糖基-(1→2)]-O-β-D-吡喃葡萄糖苷(penogenin-3β-O-α-L-rhamnopyranosyl-(1→4)-[O-α-L-rhamnopyranosyl-(1→2)]-O-β-D-glu-copyranoside,2)、重楼皂苷Ⅶ(chonglouosideⅦ,3)、偏诺皂苷元-3β-O-β-D-吡喃葡萄糖基-(1→6)-[O-α-L-吡喃鼠李糖基-(1→2)]-O-β-D-吡喃葡萄糖苷(trikamsteroside B,4)、(25S)-27-羟基偏诺皂苷元-3β-O-α-L-吡喃鼠李糖基-(1→2)-O-β-D-吡喃葡萄糖苷((25S)-27-hydroxypenogenin-3β-O-α-L-rhamnopyranosyl-(1→2)-O-β-D-glucopyranoside,5)、(25S)-27-羟基偏诺皂苷元-3β-O-α-L-吡喃鼠李糖基-(1→4)-[O-α-L-吡喃鼠李糖基-(1→2)]-O-β-D-吡喃葡萄糖苷((25S)-27-hydroxypenogenin-3β-O-α-L-rhamnopyranosyl-(1→4)-[O-α-L-rhamnopyranosyl-(1→2)]-O-β-D-glucopyranoside,6)、(25S)-27-羟基偏诺皂苷元-3β-O-α-L-吡喃鼠李糖基-(1→4)-O-α-L-吡喃鼠李糖基-(1→4)-[O-α-L-吡喃鼠李糖基-(1→2)]-O-β-D-吡喃葡萄糖苷(polyphyllosideⅢ,7)、(23S,24S,25S)-螺甾-5-烯-1β,3β,21,23,24-五羟基-1β-O-β-D-呋喃芹糖基-(1→3)-O-α-L-吡喃鼠李糖基-(1→2)-[O-β-D-吡喃木糖基-(1→3)]-O-α-L-吡喃阿拉伯糖苷(trikamsteroside E,8)、3β-O-α-L-rhamnopyranosyl-(1→2)-O-β-D-glucopyranosylhomo-aro-cholest-5-ene-26-O-β-D-glucopyranoside(parispseudoside B,9)、3β-O-α-L-rhamnopyranosyl-(1→4)-[O-α-L-rhamnopyranosyl-(1→2)]-O-β-D-glucopyranosylhomo-aro-cholest-5-ene-26-O-β-D-glucopyranoside(aethioside A,10)、3β-O-α-L-rhamnopyranosyl-(1→4)-O-α-L-rham-nopyranosyl-(1→4)-[O-α-L-rhamnopyranosyl-(1→2)]-O-β-D-glucopyranosylhomo-aro-cholest-5-ene-26-O-β-D-glucopyranoside(parispseudoside A,11)。结论化合物9-11为首次从百合科植物中分离得到,7为首次从延龄草属植物中分离得到,4-6、8为首次从延龄草中分离得到。     

丫蕊花的化学成分

从百合科丫蕊花属植物丫蕊花(Ypsilandra thibetica Franch)全草中分离鉴定了8个化合物,分别为:偏诺皂苷元(1),偏诺皂苷元-3-O-α-L-呋喃阿拉伯糖基(1→4)-[α-L-吡喃鼠李糖基(1→2)]-β-D-吡喃葡萄糖苷(2),偏诺皂苷元-3-O-α-L-吡喃鼠李糖基(1→4)-[α-L-吡喃鼠李糖基(1→2)]-β-D-吡喃葡萄糖苷(3),偏诺皂苷元-3-O-α-L-吡喃葡萄糖(1→4)-α-L-吡喃鼠李糖(1→4)-[α-L-吡喃鼠李糖(1→2)]-β-D-吡喃葡萄糖苷(4),薯蓣皂苷元(5),薯蓣皂苷元-3-O-α-L-吡喃鼠李糖基(1→4)-[α-L-吡喃鼠李糖基(1→2)]-β-D-吡喃葡萄糖苷(6),木犀草素(7),木犀草苷(8)。其中化合物1,2,5,7,8均首次在丫蕊花植物中分到。     

长药隔重楼的化学成分研究

目的 研究长药隔重楼的化学成分.方法 采用柱色谱方法单分离纯化单体化合物,通过波谱学方法鉴定其结构.结果 分离并鉴定了5个化合物,分别是△5,22-豆甾醇3-O-β-D-葡萄吡喃糖苷(I),20β-羟基蜕皮激素(Ⅱ),B-L-脱氧胸腺嘧啶苷(Ⅲ),偏诺皂苷元3-O-α-L-鼠李吡喃糖基-(1→2)-p-D-葡萄吡喃糖苷(Ⅳ)和偏诺皂苷元3-O-α-L-鼠李吡喃糖基-(1→4)-α-L-鼠李吡喃糖基-(1→4)-[α-L-鼠李吡喃糖基-(1→2)-]-β-D-葡萄吡喃糖苷(Ⅴ).结论 所有化合物均为首次从该植物中得到;其中化合物Ⅲ为首次从该属植物中分离得到.     

娑罗子提取物酶解产物的化学成分研究

目的制备新的七叶皂苷衍生物。方法采用β-葡萄糖苷酶对娑罗子提取物进行生物转化,采用大孔吸附树脂、反相硅胶柱色谱等分离方法对酶解产物进行分离纯化,根据MS、NMR数据,对得到的单体化合物进行了结构鉴定。结果 4个化合物分别鉴定为21β-O-巴豆酰基-22α-O-乙酰基原七叶皂苷元-3β-O-[β-D-葡萄糖基(1→2)]-β-D-葡萄糖醛酸苷(1)、21β-O-当归酰基-22α-O-乙酰基原七叶皂苷元-3β-O-[β-D-葡萄糖基(1→2)]-β-D-葡萄糖醛酸苷(2)、21β-O-巴豆酰基-28-O-乙酰基原七叶皂苷元-3β-O-[β-D-葡萄糖基(1→2)]-β-D-葡萄糖醛酸苷(3)、21β-O-当归酰基-28-O-乙酰基原七叶皂苷元-3β-O-[β-D-葡萄糖基(1→2)]-β-D-葡萄糖醛酸苷(4)。分别命名为七叶皂苷Ie、七叶皂苷If、异七叶皂苷Ie和异七叶皂苷If。结论 4个化合物均为新化合物。     

合欢皮中一个新的三萜皂甙

从合欢皮的乙醇提取物中用色谱法分离得到1个三糖链三萜皂甙（1）,其21位侧链含有较为少见的木糖。经化学和波谱分析,将皂甙1的结构鉴定为3－O－[β-D-吡喃木糖基-(1→2)-β-D-吡喃呋糖基－（1→6)-β-D-吡喃葡萄糖基]-21-O-{(6S)-2-反式－2－羟甲基－6－甲基－6－O－[4-O-(6R)-2-反式－2,6－二甲基－6－O－β-D-吡喃木糖基）－2,7－辛二烯酰基]－β-D-吡喃鸡纳糖基]-2,7-辛二烯酰基}-金合欢酸－28－O－β－D－吡喃葡萄糖基－（1→3)-[α-L-呋喃阿拉伯糖基－（1→4)]-α-L-吡喃鼠李糖基－（1→2)-β-D-吡喃葡萄糖基酯,为一新化合物,命名为合欢皂甙J23（1）。     

灯台七化学成分及抗癌活性研究

目的研究灯台七化学成分及抗癌活性。方法采用硅胶柱色谱、Sephadex LH-20凝胶柱色谱、半制备高效液相色谱等方法分离纯化,理化性质及现代波谱技术鉴定其结构。通过MTT法评价化合物4~8的抗癌活性。结果共分离鉴定了8个化合物,分别为β-蜕皮激素(1)、pinnatasterone(2)、豆甾醇(3)、豆甾醇-3-O-β-D-吡喃葡萄糖苷(4)、偏诺皂苷元3-O-α-L-鼠李吡喃糖(l→2)[α-L-阿拉伯呋喃糖(1→4)]-β-D-葡萄吡喃糖苷(5)、偏诺皂苷元-3-O-α-L-鼠李吡喃糖(l→4)α-L-鼠李吡喃糖(1→4)-[α-L-鼠李吡喃糖(l→2)]-β-D葡萄吡喃糖苷(6)、偏诺皂苷元-3-O-α-L-鼠李吡喃糖(l→4)-[α-L-鼠李吡喃糖基(1→2)]-β-D-葡萄糖苷(7)、偏诺皂苷元-3-O-α-L-鼠李吡喃糖基(l→4)-[α-L-鼠李吡喃糖基(1→4)]-β-D-葡萄糖苷(8)。化合物5~8对结肠癌SW620和HT-29细胞有显著的抑制作用。结论化合物5~8均表现出很强的细胞毒活性。     

Efficacy of gut lavage,hemodialysis, and hemoperfusion in the therapy of paraquat or diquat intoxication

Clinical and in vitro investigations were carried out to test the efficacy of gut lavage, hemodialysis, and hemoperfusion in the treatment of poisoning with paraquat or diquat. In a patient suffering from diquat intoxication 130 times more diquat was removed by gut lavage 30 h after ingestion than was removed by complete aspiration of the gastric contents.Determination of in vitro clearances for paraquat and diquat by hemodialysis showed that, at serum concentrations of 1–2 ppm, such as are frequently encountered in poisoning in man, toxicologically relevant quantities of herbicide cannot be removed from the body. At a concentration of 20 ppm, on the other hand, hemodialysis proved to be effective, the clearance being 70 ml/min at a blood flow rate of 100 ml/min. The efficacy of hemoperfusion with coated activated charcoal was on the whole better. Especially at concentrations around 1–2 ppm, the clearance values for hemoperfusion were some 5–7 times higher than those for hemodialysis.In a patient suffering from paraquat poisoning, both hemodialysis as well as hemoperfusion were carried out. The in vitro results could be confirmed: At serum concentrations of paraquat less than 1 ppm no clearance could be obtained by hemodialysis while by hemoperfusion with activated charcoal quite high clearance values were measured and the serum level dropped down to zero.

---

Zusammenfassung Klinische Untersuchungen und Laboratoriumsversuche wurden durchgeführt, um die Wirksamkeit von Darmspülung, Hämodialyse und Hämoperfusion bei Paraquat- und Deiquat-Vergiftungen zu prüfen.Bei einem Patienten wurde 30 Std nach Deiquat-Aufnahme durch Darmspülung 130mal mehr Deiquat entfernt als durch vollständige Aspiration des Mageninhaltes. In vitro-Versuche ergaben, daß bei Blutserumkonzentrationen von 1–2 ppm, die bei Vergiftungen oft gemessen werden, durch Hämodialyse keine toxikologisch relevanten Paraquat- oder Deiquat-Mengen entfernt werden können. Dagegen erwies sich die Hämodialyse bei 20 ppm und einer Blutumlaufgeschwindigkeit von 100 ml/min mit einer Clearance von 70 ml/min als wirksam. Die Hämoperfusion mit beschicheter Aktivkohle war in diesen Versuchen aber eindeutig überlegen, denn insbesondere bei Konzentrationen um 1–2 ppm waren die Clearance-Werte 5–7mal höher als bei der Hämodialyse.Die in vitro-Ergebnisse wurden bei einem Patienten mit einer Paraquat-Vergiftung bestätigt: Bei Konzentrationen unter 1 ppm war die Hämodialyse wirkungslos, während durch Hämoperfusion relativ hohe Clearance-Werte erreicht wurden, so daß der Serumspiegel rasch unter die Nachweisgrenze abfiel.

     

In vitro studies on sterically stabilized liposomes (SL) as enzyme carriers in organophosphorus (OP) antagonism

This study describes a new approach for organophosphorous (OP) antidotal treatment by encapsulating an OP hydrolyzing enzyme, OPA anhydrolase (OPAA), within sterically stabilized liposomes. The recombinant OPAA enzyme was derived from Alteromonas strain JD6. It has broad substrate specificity to a wide range of OP compounds: DFP and the nerve agents, soman and sarin. Liposomes encapsulating OPAA (SL)* were made by mechanical dispersion method. Hydrolysis of DFP by (SL)* was measured by following an increase of fluoride ion concentration using a fluoride ion selective electrode. OPAA entrapped in the carrier liposomes rapidly hydrolyze DFP, with the rate of DFP hydrolysis directly proportional to the amount of (SL)* added to the solution. Liposomal carriers containing no enzyme did not hydrolyze DFP. The reaction was linear and the rate of hydrolysis was first order in the substrate. This enzyme carrier system serves as a biodegradable protective environment for the recombinant OP-metabolizing enzyme, OPAA, resulting in prolongation of enzymatic concentration in the body. These studies suggest that the protection of OP intoxication can be strikingly enhanced by adding OPAA encapsulated within (SL)* to pralidoxime and atropine.     

Steroidal sapogenin contents in some domestic plants

In order to find out the values of the steroid resources for the future use. the compositions and contents of steroidal sapogenins from 13 domestic plants have been investigated. As a result,Dioscorea nipponica, D. quinqueloba andSmilax china were found to have large amount of diosgenin. And pennogenin inTrillium kamtschaticum andParis verticillata, yuccagenin inAllium fistulosum, hecogenin inAgave americana and neochlorogenin inSolanum nigum were appeared to be major steroidal sapogenins.     

Synthesis,Cytotoxicity and Antileishmanial Activity of Some N-(2-(indol-3-yl)ethyl)-7-chloroquinolin-4-amines

We report herein the condensation of 4,7-dichloroquinoline (1) with tryptamine (2) and D-tryptophan methyl ester (3) . Hydrolysis of the methyl ester adduct (5) yielded the free acid (6) . The compounds were evaluated in vitro for activity against four different species of Leishmania promastigote forms and for cytotoxic activity against Kb and Vero cells. Compound (5) showed good activity against the Leishmania species tested, while all three compounds displayed moderate activity in both Kb and Vero cells.     

Aquatic Insects and Trace Metals: Bioavailability,Bioaccumulation, and Toxicity

Abstract

The uptake of metals from food and water sources by insects is thought to be additive. For a given metal, the proportions taken up from water and food will depend both on the bioavailable concentration of the metal associated with each source and the mechanism and rate by which the metal enters the insect. Attempts to correlate insect trace metal concentrations with the trophic level of insects should be made with a knowledge of the feeding relationships of the individual taxa concerned. Pathways for the uptake of essential metals, such as copper and zinc, exist at the cellular level, and other nonessential metals, such as cadmium, also appear to enter via these routes. Within cells, trace metals can be bound to proteins or stored in granules. The internal distribution of metals among body tissues is very heterogeneous, and distribution patterns tend to be both metal and taxon specific. Trace metals associated with insects can be both bound on the surface of their chitinous exoskeleton and incorporated into body tissues. The quantities of trace meals accumulated by an individual reflect the net balance between the rate of metal influx from both dissolved and particulate sources and the rate of metal efflux from the organism. The toxicity of metals has been demonstrated at all levels of biological organization: cell, tissue, individual, population, and community. Much of the literature pertaining to the toxic effects of metals on aquatic insects is based on laboratory observations and, as such, it is difficult to extrapolate the data to insects in nature. The few experimental studies in nature suggest that trace metal contaminants can affect both the distribution and the abundance of aquatic insects. Insects have a largely unexploited potential as biomonitors of metal contamination in nature. A better understanding of the physico-chemical and biological mechanisms mediating trace metal bioavailability and exchange will facilitate the development of general predictive models relating trace metal concentrations in insects to those in their environment. Such models will facilitate the use of insects as contaminant biomonitors.