温郁金的化学成分及其研究近况

笔者收集相关文献对温郁金的化学成分及研究方法进行了汇总分析,结果表明,温郁金含有多种化学成分,活性成分主要为挥发油、姜黄素、微量元素等。挥发油类目前已分离得到40多个倍半萜类化合物,并在其地上部分茎叶中发现了与其块根中相近的部分活性成分,说明其茎叶具有一定的应用价值。姜黄素类已分离鉴定出20种化合物。温郁金化学成分的研究方法也在迅速发展,为其有效成分的研究开发提供了良好的技术基础。     

大黄橐吾的化学成分

大黄橐吾(Ligularia duciformis)为菊科橐吾属植物，据报道有治疗支气管炎、咳嗽等功效。为寻找其生物活性成分，对其根和根茎的85%乙醇提取物进行了溶剂萃取和硅胶、Sephadex LH-20柱色谱分离。从乙酸乙酯部位得到6个化合物，经理化性质和波谱数据分析，鉴定为咖啡酸-(3-甲氧基-4-羟基)苯丙酯(I)，6β,8β-双羟基雅槛蓝-7(11)-烯-12,8α-内酯(II)，6β,8α-双羟基雅槛蓝-7(11)-烯-12,8β-内酯(III)，6β-羟基雅槛蓝-7(11)-烯-12,8α内酯(IV)，豆甾醇(V)，胡萝卜苷(VI)。化合物I为新化合物，化合物II～V为首次从该植物中分得。化合物的止咳作用正在评价中。     

我国姜黄属植物的研究——Ⅱ.五种姜黄属药用植物根茎挥发油化学成分的比较

用GC,GC-MS和TLC分析了国产5种姜黄属植物(姜黄,温郁金,莪术,桂莪术和川郁金)根茎挥发油的化学成分。在OV-17柱上分离出30多个色谱峰,鉴定了24种成分,其中4种(柠檬烯,α-松油烯,芳樟醇和丁香烯)以前未见报道。不同姜黄属植物有许多相同成分,但也有很高含量的不同成分,例如川郁金中的桉叶素,莪术中的莪术酮,姜黄中的姜黄酮和芳姜黄酮。因此根据5种挥发油中主要成分的差别,列出了区分姜黄属品种的表。     

连钱草的化学成分研究

目的对连钱草地上全草进一步进行化学成分的研究。方法应用多种色谱法分离连钱草中的化学成分，采用多种光谱分析法鉴定它们的结构。结果从连钱草全草中又得到9个化合物，即连钱草酮(1)、6R,9R-3-氧代-α-紫罗兰醇(2)、S(+)-去氢催吐萝芙叶醇(3)、催吐萝芙叶醇(4)、可乐苏酸(5)、槲皮素(6)、豆甾烯醇(7)、肉豆蔻酸(8)和正三十烷醇(9)。结论化合物1为未见报道的新化合物，化合物2～9均为首次从该植物中分离得到。     

真菌Chaetomium sp.的次级代谢产物研究

目的 对海洋毛壳属真菌Chaetomium sp.的次级代谢产物进行研究。方法 运用硅胶柱色谱、Sephadex LH-20凝胶柱色谱、HPLC等现代色谱方法对Chaetomium sp.的发酵产物进行分离纯化,利用现代波谱技术结合文献报道进行结构鉴定。结果 共分离得到4个十元环内酯化合物,botryolides A、botryolides B、botryolides D和decarestrictine I,1个倍半萜类化合物trichothecolone。结论 本研究是对海洋真菌Chaetomium sp.次级代谢产物的首次报道,5种化合物均为首次从该种真菌中分离得到。     

北沙参中一个新香豆素苷

为了研究北沙参的化学成分，本文通过大孔树脂吸附柱色谱、Sephadex LH-20及开放反相ODS柱色谱进行化合物的分离，利用多种波谱技术鉴定化合物结构。分离得到9个化合物，鉴定为：bergaptol 5-O-β-D-gentiobioside (1)、(7R，8S)-dehydrodiconiferylalcohol-4，9-di-O-β-D-glucoside (2)、橙皮素A(3)、(-)-seco-isolariciresinol 4-O-β-D-glucopyranoside (4)、白花前胡苷(5)、花椒毒酚8-O-β-D-吡喃葡糖苷(6)、5′-硫甲基腺苷(7)、腺苷(8)、色氨酸(9)。化合物1为新化合物；化合物2和7为首次从该属植物中分离得到。     

前胡香豆素A的分离和结构鉴定

从中药白花前胡(Peucedanum praeruptorum Dunn)根中分离得到7个化合物,经理化常数和波谱数据的测定以及化学反应,鉴定为补骨脂素(Ⅱ)、5-甲氧基补骨脂素(Ⅲ)、8-甲氧基补骨脂素(Ⅳ)、北美芹素(Ⅴ)、peucedanocoumarin Ⅱ(Ⅵ)、β-谷甾醇(Ⅶ)和前胡香豆素A(Ⅷ)。Ⅷ为一新化合物,通过和凯林内酯的化学沟通确定了其绝对构型,化学结构为3′(R)-羟基-4′(E)-惕各酰氧基-3′,4′-二氢邪蒿内酯。Ⅱ～Ⅳ和Ⅶ为首次从白花前胡中分离得到。     

荚果蕨贯众化学成分研究

目的对荚果蕨贯众的化学成分进行研究。方法用色谱法分离化合物，根据理化性质和光谱数据鉴定结构。结果分离鉴定了4个化合物：1-O-β-D-葡糖基-(2S,3R,4E，8Z)-2-N-(2′-羟基二十二碳酰)-二十碳鞘氨醇-4,8-二烯(1)，1-O-β-D-半乳糖-(6→1)-α-D-半乳糖-2,3-O-十六烷酸甘油二酯(2)，丁二酸(3)，D-甘露糖醇(4)。结论 化合物1和2为新化合物，3和4为首次从该植物中分离得到。     

浅裂鳞毛蕨根茎中的二氢黄酮苷类化学成分

为研究浅裂鳞毛蕨根茎中的化学成分，用Sephadex LH-20，silica gel等柱色谱方法从其水提物中分离得到化合物，并根据理化性质和波谱数据鉴定其结构。分离得到9个化合物，分别为浅裂鳞毛蕨素A(1)，浅裂鳞毛蕨素B(2)，浅裂鳞毛蕨素C(3)，浅裂鳞毛蕨素D(4)，东方荚果蕨酯A(5)，东方荚果蕨酯C(6)，熊果苷(7)，3-甲氧基-4-羟基苯基-1-O-β-D-葡糖苷(8)和3,4-二甲基苯基-1-O-β-D-葡糖苷(9)。其中化合物1～4为新化合物，其余均为首次从本植物中分得。     

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。     

知母中的两种新呋甾皂苷

目的研究知母根茎的化学成分。方法采用水煎提取、大孔吸附树脂SP825柱色谱、反相C₁₈柱色谱等进行分离，并通过化学手段和光谱分析(FAB-MS，¹H NMR，13C NMR，¹H-¹H COSY)鉴定其化学结构。结果从知母根茎中分离得到6种甾体皂苷，分别鉴定为：(25S)-26-O-β-D-吡喃葡糖基-22-羟基-5β-呋甾-2β，3β，26-三醇-3-O-β-D-吡喃葡糖基-(1→2)-β-D-吡喃半乳糖苷(知母皂苷N，1)，知母皂苷E_l(2)，(25S)-26-O-β-D-吡喃葡糖基-22-甲氧基-5β-呋甾-2β，3β，26-三醇-3-O-β-D-吡喃葡糖基-(1→2)-β-D-吡喃半乳糖苷(知母皂苷O，3)，知母皂苷E₂(4)，(25R)-26-O-β-D-吡喃葡糖基-22-羟基-5α-呋甾-2α，3β，26-三醇-3-O-β-D-吡喃葡糖基-(1→2)-［β-D-吡喃木糖基-(1→3)］-β-D-吡喃葡糖基-(1→4)-β-D-吡喃半乳糖苷(purpureagitosid，5)，marcogenin-3-O-β-D-glucopyranosyl-(1→2)-β-D-galactopyranoside (6)。结论化合物1和3为新化合物，命名为知母皂苷N和知母皂苷O，化合物5为首次从知母中分离得到。     

黄山药中甾体皂苷的分离与鉴定

目的　研究黄山药的化学成分,寻找新的活性物质。方法　用硅胶柱色谱及高效液相色谱等进行分离,通过理化方法及光谱分析(IR,ESI-MS,¹HNMR,¹³CNMR,DEPT,¹H-¹HCOSY,HMQC,HMBC,NOESY)鉴定化学结构。结果　从黄山药根茎的乙醇提取物中分离得到3种甾体皂苷,其化学结构分别鉴定为26-O-β-D-吡喃葡糖基-3β,26-二醇-23(S)-甲氧基-25(R)-Δ^5,20(22)-二烯-呋甾-3-O-［α-L-吡喃鼠李糖基-(1→2)-O-α-L-吡喃鼠李糖基-(1→4)］-β-D-吡喃葡糖苷(I),伪原薯蓣皂苷(pseudoprotodioscin,II),26-O-β-D-葡吡喃糖基25(R)-呋甾-Δ^5,20(22)-二烯-3β,26-二羟基-3-O-［α-L-鼠李吡喃糖基(1→2)］-β-D-葡吡喃糖苷(III)。结论　I为新化合物,命名为黄山药皂苷C,II,III为首次从本属植物中分得。     

人参芦头抗心律失常活性成分研究

从人参(Panax ginseng C.A.Meyer)芦头中分离得到10个化合物。经理化性质、波谱分析和薄层析分别鉴定为:20(R)-人参皂甙-Rh_1(Ⅰ),人参皂甙-Rg_3(Ⅱ),20(S)-人参皂甙-Rg_2(Ⅲ),-Rg_1(Ⅳ),-B(Ⅴ),-Rd(Ⅵ),-Rc(Ⅶ),-Rb_2(Ⅷ),-Rb_1(Ⅸ),-Ro(Ⅹ).其中化合物Ⅰ,Ⅱ为首次从人参芦头中分离得到的已知成分,并对其中9种主要人参皂甙进行了抗氯化钡诱发大白鼠心律失常作用的研究。     

Chemical constituents of the rhizomes of Coeloglossum viride var. bracteatum

Seven new compounds, named coelovirins A-G (1-7), along with fourteen known constituents were isolated from the rhizomes of Coeloglossom viride var. bracteatum (Orchidaceae). On the basis of chemical and spectroscopic methods, including 2D-NMR techniques, the structures of new compounds were elucidated as 1-(4-beta-D-glucopyranosyloxybenzyl)-(2R,3S)-2-isobutyltartrate (1), 4-(4-beta-glucopyranosyloxybenzyl)-(2R,3S)-2-isobutyltartrate (2), 1-(4-beta-D-glucopyranosyloxybenzyl)-(2R,3S)-2-beta-D-glucopyranosyl-2-isobutyltartrate (3), 4-(4-beta-D-glucopyranosyloxybenzyl)-(2R,3S)-2-beta-D-glucopyranosyl-2-isobutyltartrate (4), (2R,3S)-2-beta-D-glucopyranosyl-2-isobutyltartaric acid (5), bis(4-beta-D-glucopyranosyloxybenzyl)-(2R,3S)-2-[beta-D-glucopyranosyl-(1 --> 4)-beta-D-glucopyranosyl]-2-isobutyltartrate (6) and bis(4-beta-D-glucopyranosyloxybenzyl)-(2R)-2-[beta-D-glucopyranosyl-(1 --> 4)-beta-D-glucopyranosyl]-2-isobutylmalate (7). The known compounds are 4-hydroxybenzaldehyde, 4-hydroxybenzyl alcohol, 4,4'-dihydroxydibenzyl ether, 4,4'-dihydroxydiphenylmethane, 4-(4-hydroxybenzyloxy)benzyl alcohol, gastrodin, quercetin-3,7-diglucoside, thymidine, loroglossin, militarine, dactylorhin A, dactylorhin B, beta-sitosterol and daucosterol.     

A new picrotoxane-type sesquiterpene from Dendrobium findlayanum

A new picrotoxane-type sesquiterpene, findlayanin (1), was isolated from Dendrobium findlayanum with crystallinin (2). The structure of compound 1 was established to be (1R,2S,3R,4S,5R,6S,9R)-2,3,11,12-tetrahydroxypicrotoxan-12(15)-lactone by spectroscopic methods.     

Anti-allergic activity of sesquiterpenes from the rhizomes of <Emphasis Type="Italic">Cyperus rotundus</Emphasis>

From the 70% ethanol extract of the rhizomes of Cyperus rotundus (CRE), several major constituents including the sesquiterpene derivatives (valencene, nootkatone, and caryophyllene α-oxide), monoterpenes (β-pinene, 1,8-cineole, and limonene) and 4-cymene were isolated and examined for their anti-allergic activity in vitro and in vivo. In rat basophilic leukemia (RBL)-1 cells, the sesquiterpenes strongly inhibited 5-lipoxygenase-catalyzed leukotrienes production. In addition, they inhibited β-hexosaminidase release by antigen-stimulated RBL-2H3 cells, with valencene having the highest inhibitory effect. CRE inhibited leukotrienes production and β-hexosaminidase release at 300 μg/mL. It was also found that the most active sesquiterpene (valencene) and CRE inhibited β-hexosaminidase degranulation by inhibiting the initial activation reaction, Lyn phosphorylation, in IgE-stimulated RBL-2H3 cells. Moreover, CRE, valencene and nootkatone significantly inhibited the delayed-type hypersensitivity reaction in mice when administered orally at 50–300 mg/kg. In conclusion, C. rotundus and its constituents, valencene, nootkatone, and caryophyllene α-oxide, exert anti-allergic activity in vitro and in vivo. These sesquiterpenes, but not monoterpenes, certainly contribute to the anti-allergic activity of the rhizomes of C. rotundus.     

Three new guaiane sesquiterpene lactones from rhizomes of Curcuma wenyujin

Three new guaiane sesquiterpene lactones (4S)-4-hydroxy-gweicurculactone (1), zedoalactone G (2), and (1R, 4R, 5S, 10S)-zedoalactone B (3), and three known guaiane sesquiterpene lactones, including zedoarolide B (4), zedoalactone B (5), and a new natural product (+)-zedoalactone A (6), were isolated from the rhizomes of Curcuma wenyujin Y.H. Chen et C. Ling. The structures were elucidated by spectroscopic methods including 1D and 2D NMR and HR-ESI-MS. The absolute configuration of 2 was determined via the calculated electronic circular dichroism (ECD), whereas the absolute configurations of 1 and 3 were determined via the ECD data of the [Rh₂(OCOCF₃)₄] complex and [Mo₂(OAc)₄] complex, respectively. The inhibitory effects of compounds 1–6 on nitric oxide production in lipopolysaccharide-activated macrophages were evaluated. All of them exhibited weak anti-inflammatory activity.     

小升麻中的环菠萝蜜烷型三萜及其糖苷成分

目的研究小升麻［Cimicifuga acerina(Sieb.etZucc.)Tanaka.］根茎的化学成分。方法小升麻根茎的乙醇提取物经硅胶柱和ODS柱色谱分离得到5个化合物,通过波谱和化学方法进行结构鉴定。结果5个化合物分别被鉴定为(22R)-22-羟基升麻醇(I),(22R)-22-hydroxy-24-O-acetylhydroshengmanol3-O-β-D-xylopyranoside(II),dahurinol(III),24-epi-24-O-acetyl-7,8-didehydroshengmanol-3-O-β-D-xylopyranoside(IV)和25-O-乙酰基-7,8-去氢升麻醇3-O-β-D-吡喃木糖苷(V)。结论I为新天然产物,II为新化合物,IV和V为首次从小升麻中分离得到。     

Analytic investigations of sesquiterpenes of Petasites albus (L.) GAERTN

A simple and rapid HPLC method is presented which allows an efficient and easily reproducible gradient separation of the 6 main sesquiterpene constituents of P. albus and which can therefore be used for routine determinations of the sesquiterpene content of different plant parts, even of single plants. Sesquiterpenes 1–6 are separated on a HPLC-system with photodiode array detector (DAD) in combination with a normal-phase RoSil CN column by use of a hexane-MeO-t-Bu/acetonitrile gradient. Five of the six compounds (albopetasin 2, bakkenolide-A 3, petasalbin 4, 6-angeloyl-albopetasol 5 and 6-senecioyl-albopetasol 6) have been quantitatively determined with the help of calibration plots of isolated main sesquiterpenes. These compounds are abundant in similar ratios and total amounts in rhizomes and buds (but rhizomes are better suited for extraction, containing less non-sesquiterpenoic compounds) while extracts from leaves contain large amounts of polar compounds. Due to the sensitivity of the method, parts of rhizomes of single plants may be investigated and show a considerable variation of the total amount of the main sesquiterpenes 2 + 4 + 5 within the same population. Seasonal influences on sesquiterpene contents show the same trends as for P. hybridus but are much more pronounced for P. albus: based on the weight of powdered rhizomes, the total amounts of main compounds 2 + 4 + 5 are surprisingly small from July till October, relatively high in winter and peaking in May.