中文名 | 绿原酸 |
英文名 | Chlorogenic acid |
别名 | 绿原酸 金银花提取物 (1S,3R,4R,5R)-3-[[3-(3,4-二羟基苯基)-1-氧代-2-丙烯基]氧]-1,4,5-三羟基环己烷甲酸 |
英文别名 | Chlorogenic acid 3-O-Caffeoylquinic acid Honeysuckle Flower Extract 5-O-(3,4-dihydroxycinnamoyl)-L-quinic acid 3-[[3-(3,4-Dihydroxyphenyl)-1-oxo-2-propenyl]oxy]-1,4,5-trihydroxycyclohexanecarboxylic acid (1S,3R,4R,5R)-3-[[3-(3,4-Dihydroxyphenyl)-1-oxo-2-propenyl]oxy]-1,4,5-trihydroxycyclohexanecarboxylic acid |
CAS | 327-97-9 |
EINECS | 206-325-6 |
化学式 | C16H18O9 |
分子量 | 354.31 |
InChI | InChI=1/C16H18O9/c17-9-3-1-8(5-10(9)18)2-4-13(20)25-12-7-16(24,15(22)23)6-11(19)14(12)21/h1-5,11-12,14,17-19,21,24H,6-7H2,(H,22,23)/b4-2+/t11-,12-,14-,16+/m1/s1 |
密度 | 1.65g/cm3 |
熔点 | 205-209℃ |
沸点 | 665°C at 760 mmHg |
比旋光度 | -35.0°~ -38.0°(C=1, H2O) |
闪点 | 245.5°C |
水溶性 | SOLUBLE IN HOT WATER |
蒸汽压 | 1.38E-18mmHg at 25°C |
溶解度 | 易溶于乙醇及丙酮,极微溶于醋酸乙酯,难溶于三氯甲烷、乙醚、苯等亲脂性有机溶剂。 |
折射率 | 1.69 |
存储条件 | 2-8℃ |
外观 | 白色至浅黄褐色粉末 |
MDL号 | MFCD00003862 |
安全术语 | S24/25 - 避免与皮肤和眼睛接触。 |
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绿原酸是金银花的主要抗菌、抗病毒有效药理成分之一。
绿原酸具有较广泛的抗菌作用,但在体内能被蛋白质灭活。与咖啡酸相似,口服或腹腔注射时,可提高大鼠的中枢兴奋性。可增加大鼠及小鼠的小肠蠕动和大鼠子宫的张力。有利胆作用,能增进大鼠的胆汁分泌 。对人有致敏作用,吸入含有本品的植物尘埃后,可发生气喘、皮炎等。
金银花所含的绿原酸有利胆作用,能增进大鼠胆汁分泌。黄褐毛忍冬总皂苷皮下注射200mg/kg能显著对抗CCl4、扑热息痛及半乳糖胺所致小鼠肝中血清GPT的升高及肝脏甘油三酯含量,并明显减轻肝脏病理损伤的严重程度,使肝脏点状坏死数总和及坏死出现率明显降低。
绿原酸是由咖啡酸与奎尼酸形成的酯,其分子结构中有酯键、不饱和双键及多元酚三个不稳定部分。在从植物提取过程中,往往通过水解和分子内酯基迁移而发生异构化。由于绿原酸的特殊结构,决定了其可以利用乙醇、丙酮、甲醇等极性溶剂从植物中提取出来,但是由于绿原酸本身的不稳定性,提取时不能高温、强光及长时间加热。绿原酸的供试液放置于棕色瓶、冰箱(2℃)保存时最为稳定。
由(1S)-1-乙氧甲酰氧基-3-顺-[3,4-二羟基-反-肉桂酰氧基]-4′-反-5′-反-二羟基环己烷-γ-甲酸甲酯在甲醇中用氢氧化钡催化水解,或由绿咖啡豆中离析而得绿原酸。
绿原酸是一种常见的天然有机酸,也被称为咖啡酸。其化学式为C9H8O4。以下是绿原酸的一些性质:
1. 外观:绿原酸是无色结晶状固体。常见的形式为无水和单水合物。
2. 溶解性:绿原酸在水中可溶解,溶解度较高。它也可溶解于许多有机溶剂,如乙醇和醚类。
3. 酸性:绿原酸是一种较弱的有机酸,可以与碱反应生成盐。它在水溶液中表现出酸性,可以与金属离子或碱性物质发生反应。
4. 稳定性:绿原酸在常温下稳定,并且不易被光、热和氧化剂分解。
5. 生物活性:绿原酸具有许多生物活性,如抗氧化、抗炎、抗菌和抗肿瘤等。它也被广泛应用于食品、医药和化学领域。
绿原酸对人有致敏作用,可引起气喘、皮炎等变态反应,但口服无此反应,因绿原酸可被小肠分泌物转化成无致敏活性的物质。绿原酸毒性很小,对幼大鼠灌服的LD50大于1g/kg,腹腔注射大于0.25g/kg。
半水合物为针状结晶(水)。110℃变为无水化合物,熔点: 208℃,[α]20D-35.2。(C=2.8)。25℃水中溶解度为4%,热水中溶解度更大。易溶于乙醇及丙酮,极微溶于醋酸乙酯。
危险品标志 Xi
危险类别码 68
安全说明 24/25
WGK Germany 3
RTECS号 GU8480000
Hazard Note Irritant
类别 有毒物质
毒性分级 中毒
急性毒性 腹腔-大鼠 LDL0: 4000 毫克/公斤
可燃性危险特性 可燃; 火场释放辛辣刺激烟雾
储运特性 库房低温, 通风, 干燥
灭火剂 水, 二氧化碳, 干粉, 砂土
杜仲科植物杜仲Eucommia ulmoides Oliv. 的叶,忍冬科植物忍冬Lonicera japonica Thumb.、红腺忍冬Lonicera hypoglauca Miq.、山银花Lonicera confusa DC.或毛花柱忍冬Lonicera dasytyla Rehd.的干燥花蕾或带初开的花,蔷薇科植物英国山楂Crataegus oxyacantha Linn.的果实,千屈菜科植物千屈菜Lythrum salicaria L.花,无患子科植物坡柳Dodonaea viscose (L.)Jacp.,水龙骨科植物欧亚水龙骨Polypodium vulgare L.根茎,马鞭草科植物假败酱Stachytarpheta jamaicensis(L.)Vahl根,十字花科植物卷心菜Brassica oleracea L.var.capitata L.茎、叶,蓼科植物扁蓄Polygonum aviculare L.全草,茜草科植物篷子菜Galium verum L.全草,忍冬科植物蒴翟Sambucus javanica Reinw.全草。旋花科植物红薯 ( Ipomoea batatas )的叶。茜草科植物小果咖啡(Coffeaarabical.)、中果咖啡(CoffeacanephoraPierreexFroehn.)及大果咖啡(CoffealibericaBul1.exH1en.)的种子。菊科植物牛蒡(Arctium lappa L.)
半水合物为针状结晶(水)。110 ℃变为无水化合物,熔点 208 ℃, [ α ]24D-35.2 ℃( c=2.8)。
25 ℃水中溶解度为 4%,热水中溶解度更大;易溶于乙醇及丙酮,极微溶于醋酸乙酯,难溶于三氯甲烷、乙醚、苯等亲脂性有机溶剂。 13CNMR(H2O)A:126.6(C-1), 114.1(C-2), 144.2(C-3), 147.0(C-4), 116.0(C-5), 122.6(C-6), 145.9(C-7), 115.2(C-8), 168.9(C-9); B: 76.6(C-1), 38.3(C-2), 70.6(C-3), 72.8(C-4), 71.0(C-5), 37.3(C-6), 180.1(C-7)[1] 。 绿原酸是由咖啡酸与奎尼酸形成的酯,其分子结构中有酯键、不饱和双键及多元酚三个不稳定部分。Microherb研究表明,在从植物提取过程中,往往通过水解和分子内酯基迁移而发生异构化。由于绿原酸的特殊结构,决定了其可以利用乙醇、丙酮、甲醇等极性溶剂从植物中提取出来,但是由于绿原酸本身的不稳定性,提取时不能高温、强光及长时间加热。建议保存时避光密封低温保存。
本品加热水溶解,摇匀,滤过,续滤液进入高效液相色谱仪进行色谱分离,用紫外吸收检测器,于波长324nm处检测绿原酸的吸收值,计算出其含量。
试剂: 1. 甲醇,2. 冰醋酸;
仪器;
色谱条件:
取重量差异项下的本品,剪碎,混匀,取约0.5g,精密称定,为供试品。
精密称取绿原酸对照品适量,置棕色量瓶中,加水制成每1mL含10mg的溶液。
取重量差异项下的本品,剪碎,混匀,取约0.5g,精密称定,置锥形瓶中,加热水40mL使溶解,放冷,滤过,滤液置100mL量瓶中,容器与滤器用热水洗涤2次(30mL,20mL),洗液并入同一量瓶中.加水至刻度,摇匀,滤过,取续滤液作为供试品溶液。
分别精密吸取对照品溶液和供试品溶液各20µL,注入高效液相色谱仪,用紫外吸收检测器于波长324nm处测定绿原酸(C16H18O9)的峰面积,计算出其含量。[7]
绿原酸具有广泛的生物活性,现代科学对绿原酸生物活性的研究已深入到食品、保健、医药和日用化工等多个领域。绿原酸是一种重要的生物活性物质,具有抗菌、抗病毒、增高白血球、保肝利胆、抗肿瘤、降血压、降血脂、清除自由基和兴奋中枢神经系统等作用。
杜仲绿原酸有较强的抗菌消炎作用,桃叶珊瑚苷及其多聚体有明显的抑菌作用,桃叶珊瑚苷元对革兰氏阴性、阳性菌都有抑制作用。桃叶珊瑚苷有抑菌、利尿作用,并能促进伤口愈合;桃叶珊瑚苷与葡萄糖苷一起预培养后还会产生明显的抗病毒作用,但其本身开不具有抗病毒功能。日本爱知医科大学加龄医科学研究所经研究确认,从杜仲中提取的碱性物质有抗破坏人体免疫系统病毒的功能,这种物质有可能用于预防和治疗艾滋病。
绿原酸是一种有效的酚型抗氧化剂,其抗氧化能力要强于咖啡酸、对羟苯酸、阿魏酸、丁香酸、丁基羟基茴香醚(BHA)和生育酚。绿原酸之所以有抗氧化作用,是因为它含有一定量的R-OH基,能形成具有抗氧化作用的氢自由基,以消除羟基自由基和超氧阴离子等自由基的活性,从而保护组织免受氧化作用的损害。
绿原酸及其衍生物具有比抗坏血酸、咖啡酸和生育酚 (维生素E) 更强的自由基清除效果,可有效清除DPPH自由基、羟基自由基和超氧阴离子自由基,还可抑制低密度脂蛋白的氧化。绿原酸对有效地清除体内自由基、维持机体细胞正常的结构和功能、防止和延缓肿瘤突变和衰老等现象的发生具有重要作用。杜仲绿原酸含有一种可促进人体的皮肤、骨骼、肌肉中胶蛋白的合成与分解的特殊成分,具有促进代谢、防止衰退的功能,可用来预防宇航员因太空失重而引起的骨骼和肌肉衰退,同时发现杜仲绿原酸无论在体内还是体外,均有明显抗自由基作用。
绿原酸作为一种自由基清除剂及抗氧化剂已被大量的试验证明,绿原酸的这种生物活性,对心血管系统能产生保护作用。异绿原酸B对大鼠具有较强促进前异绿原酸B对大鼠具有较强促进前列腺环素(PGI2)的释放和抗血小板凝集作用;对豚鼠肺碎片感应的抗体诱导SRS-A释放抑制率达62.3%。异绿原酸C也有促进PGI2释放作用。另外,异绿原酸B对血小板学栓素的生物合成和氢过氧化无诱发的内皮素损伤有极强的抑制作用。
经多年临床试验证实的,杜仲绿原酸有明显的降压作用,而且疗效平稳,无毒、无副作用。美国威斯康星大学研究发现杜仲绿降血压的有效成分是松酯醇二葡萄糖苷,桃叶珊瑚甙,绿原酸,和杜仲绿原酸多糖类。
由于绿原酸对透明质酸(HAase)及葡萄糖-6-磷酸酶(Gl-6-Pase)有特殊的抑制作用,所以绿原酸对于创伤的治愈、皮肤健康湿润、润滑关节、防止炎症以及体内血糖的平衡调控等都有一定得疗效。绿原酸对多种疾病和病毒还有较强的抑制和杀灭作用。绿原酸有降血压、抗菌、抗病毒、消炎、增高白血球、预防糖尿病、显著增加胃肠蠕动和促进胃液分泌等药理作用,对急性咽喉炎症有明显的疗效。研究表明,口服绿原酸能够显著的刺激胆汁的分泌,具有利胆保肝的功效;它还可有效抑制H2O2引起的大鼠红细胞溶血作用。
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