花椒茎的化学成分
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摘要
目的:对95%乙醇提取花椒茎的化学成分进行分离和鉴定。方法:取花椒茎(25 kg),95%乙醇加热回流提取3次,过滤后合并滤液,浓缩得总浸膏,加水混悬后依次用石油醚、二氯甲烷、乙酸乙酯、正丁醇萃取,得到相应的5个流分。石油醚部分、二氯甲烷部分、乙酸乙酯部分分离方法相似,依次先用硅胶柱色谱分离,后经过LH-20型羟丙基葡聚糖凝胶(Sephadex LH-20),中压制备液相、高压制备液相等分离、纯化。正丁醇部位先用D101型大孔树脂分段,后经过凝胶Sephadex LH-20,中压制备液相,高压制备液相等分离、纯化。得到的化合物用红外、核磁氢谱、核磁碳谱、质谱等波谱技术进行鉴定。结果:花椒茎中分离得到10个化合物,(+)-木兰花碱(1),(-)-异紫花前胡内酯(2),(-)-二氢欧山芹醇(3),(-)-紫花前胡醇(4),羽扇豆醇(5),α-香树脂醇(6),β-香树脂醇(7),δ-香树脂醇(8),槲皮素(9),芦丁(10),其中1为生物碱,2,3,4为香豆素,5,6,7,8为三萜,9,10为黄酮。结论:其中化合物1～8为首次从花椒发现。
Objective:To isolate and identify the chemical constituents from 95%ethanol extracts from stems of Zanthoxylum bungeanum.Method:The stems(25 kg)were extracted with 95%ethanol under reflux for three times and then filtrated,and the combined filtrates were concentrated under vacuum to get the extracts.After suspension with water,the extracts were extracted with petroleum ether,dichloromethane,ethyl acetate and nbutanol successively,and five corresponding parts were obtained.The parts of petroleum ether,dichloromethane,ethyl acetate were separated in a similar way to get pure compounds.By the method the subjects were first chromatographed on silica gel column respectively,then the selected sub-fractions were further separated by Sephadex LH-20,and finally purified on preparation HPLC to get the monomer compound.The n-butanol part was first treated with macroporous resin D101,and then the sub-fractions were further purified by almost the same method as mentioned above.The structures of these compounds were determined by spectrum technology as IR,MS,~1H-NMR,~(13)C-NMR.Result:Ten compounds were isolated from Z.bungeanum stems and identified as follows:(+)-magnoflorine(1),(-)-marmesin(2),(-)-columbianetin(3),(-)-decursinol(4),lupeol(5),α-amyrin(6),β-amyrin(7),δ-amyrin(8),quercetin(9),rutin(10).Among them,1 was alkaloid,2,3,4 were coumarin,5,6,7,8 were triterpenoid,9,10 were flavonoids.Conclusion:Compounds 1-8 were isolated from this plant for the first time.
Objective:To isolate and identify the chemical constituents from 95%ethanol extracts from stems of Zanthoxylum bungeanum.Method:The stems(25 kg)were extracted with 95%ethanol under reflux for three times and then filtrated,and the combined filtrates were concentrated under vacuum to get the extracts.After suspension with water,the extracts were extracted with petroleum ether,dichloromethane,ethyl acetate and nbutanol successively,and five corresponding parts were obtained.The parts of petroleum ether,dichloromethane,ethyl acetate were separated in a similar way to get pure compounds.By the method the subjects were first chromatographed on silica gel column respectively,then the selected sub-fractions were further separated by Sephadex LH-20,and finally purified on preparation HPLC to get the monomer compound.The n-butanol part was first treated with macroporous resin D101,and then the sub-fractions were further purified by almost the same method as mentioned above.The structures of these compounds were determined by spectrum technology as IR,MS,~1H-NMR,~(13)C-NMR.Result:Ten compounds were isolated from Z.bungeanum stems and identified as follows:(+)-magnoflorine(1),(-)-marmesin(2),(-)-columbianetin(3),(-)-decursinol(4),lupeol(5),α-amyrin(6),β-amyrin(7),δ-amyrin(8),quercetin(9),rutin(10).Among them,1 was alkaloid,2,3,4 were coumarin,5,6,7,8 were triterpenoid,9,10 were flavonoids.Conclusion:Compounds 1-8 were isolated from this plant for the first time.
引文
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[2]刘飞,梅国荣,卢俊宇,等. GC-MS-AMDIS结合保留指数分析比较花椒与青椒挥发油的组成[J].中国实验方剂学杂志,2017,23(5):84-89.
[3]孟佳敏,邸江雪,江汉美,等.花椒及花椒叶挥发性成分对比研究[J].中国调味品,2018,43(4). 49-52,58.
[4]韦敏,臧林泉,陶亮.花椒挥发油对离体豚鼠气管平滑肌作用的实验研究[J].蛇志,2007,19(3):184-187.
[5]袁娟丽.花椒挥发油的抗炎、镇痛作用[J].中药材,2010,33(5):794-797.
[6]马建旸,石应康,方定志.花椒挥发油对实验性动脉粥样硬化的影响[J].四川大学学报:医学版,2005,36(5):696-699.
[7]袁太宁,王艳林,汪鋆植.花椒挥发油抗宫颈癌Hela细胞作用研究[J].湖北民族学院学报:医学版,2008,25(3):26-27.
[8]黄海潮,王如意,周伟民.花椒挥发油对嗜铬细胞瘤细胞的杀伤作用[J].黑龙江医药,2010,23(4):514-515.
[9]王锐清,郭盛,段金廒,等.花椒果实不同部位及其种子油资源性化学成分分析与评价[J].中国中药杂志,2016,41(15):2781-2789.
[10]石雪萍,张卫明,张鸣镝,等.花椒总生物碱镇痛、抗炎、止痒作用研究[J].中国野生植物资源,2011,30(1):46-49.
[11]CHEN J,ZHANG T,ZHANG Q. Isobutylhydroxyamides from Sichuan pepper and their protective activity on PC12 cells damaged by corticosterone[J]. J Agric Food Chem,2018,66:3408-3416.
[12]游玉明,周敏,王倩倩,等.花椒麻素的抗氧化活性[J].食品科学,2015,36(13):27-31.
[13]李焱,黄筑艳.微波萃取花椒叶挥发油的工艺研究[J].贵州化工,2005,30(3):17-18.
[14]刘军海.微波辅助提取花椒叶黄酮及其抗氧化活性研究[J].中国调味品,2015,40(7):16-20.
[15]范菁华,徐怀德,李钰金,等.超声波辅助提取花椒叶总黄酮及其体外抗氧化性研究[J].中国食品学报,2010,10(6):22-28.
[16]徐怀德,范菁华.大孔吸附树脂分离纯化花椒叶总黄酮及其产品抗氧化功能研究[J].食品科学,2010,31(14):111-115.
[17]杨立琛.花椒叶黄酮的微波提取及其成分分析[D].天津:天津商业大学,2013.
[18]张玉娟.花椒叶抗氧化活性成分的分离、结构鉴定及其构效关系[D].杨凌:西北农林科技大学,2014.
[19]郭换,刘飞,梅国荣,等.色度分析花椒黄酮类成分含量与颜色值的相关性[J].中国实验方剂学杂志,2017,23(6):91-97.
[20]齐素芬,张华峰,姚美,等.苯酚-硫酸法测定花椒叶多糖含量[J].食品科学技术学报,2015,33(4):40-46.
[21]方一丁,刘绥鹏,樊泽楠.花椒挥发性化合物的固相微萃取GC-MS分析[J].陕西林业科技,2017(3):9-14.
[22]陈槐萱,谢王俊,李霄洁,等.汉源产红花椒叶中麻味物质特征的研究[J].中国调味品,2014,39(6):43-47.
[23]李霄洁,陈槐萱,谢王俊,等.汉源产红花椒叶中麻味物质的研究[J].中国调味品,2014,39(12):124-128.
[24]王娅娅.花椒籽油的提取、分析检测及降血脂功能研究[D].西安:陕西师范大学,2007.
[25]马传国,毕艳兰,林敏刚,等.花椒籽皮油和仁油化学成分分析[J].郑州工程学院学报,2002,23(1):39-42.
[26]刘春叶,张剑,苗延青,等.花椒籽油的提取及GC-MS分析[J].安徽农业科学,2012,40(6):3594-3596,3599.
[27]韦邱梦,陈椿,谭艳红,等.花椒籽油对大鼠动脉粥样硬化的作用研究[J].实用药物与临床,2017,20(1):9-11.
[28]王娅娅,张有林.花椒籽中脂肪酸及挥发性成分的GC/MS分析研究[J].中成药,2007,29(12):1838-1840.
[29]吴红洋.花椒籽蛋白降血压肽的制备及性质研究[D].雅安:四川农业大学,2015.
[30]董小华.花椒籽活性物质的提取、抗氧化和抑菌活性的研究[D].雅安:四川农业大学,2016.
[31]姜太玲,吴红洋,申光辉,等.酸性蛋白酶制备花椒籽蛋白抗菌肽的研究[J].食品科学,2015,36(13):148-153.
[32]姜太玲,吴红洋,申光辉,等.花椒籽蛋白抗菌肽的抑菌作用及其稳定性研究[J].现代食品科技,2015,31(8):129-135.
[33]董小华,课敬璇,申光辉,等.花椒籽黑色素体外抗氧化能力研究[J].中国油脂,2016,41(8):66-69.
[34]任丽娟,谢凤指.花椒根的生物碱研究[J].药学学报,1981(9):672-677.
[35]吕子明,张庆建,陈若芸,等.陵水暗罗枝、叶中的化学成分[J].中国中药杂志,2011,36(8):1024-1027.
[36]汪灿,伍城颖,汪文涛,等. HPLC测定刺壳花椒中木兰花碱含量的研究[J].中国中药杂志,2009,34(7):922-923.
[37]Ross S A,Sultana G N N,Burandt C L,et al.Syncarpamide, a new antiplasmodial(+)-norepinephrine derivative from Zanthoxylum syncarpum[J]. J Nat Prod,2004,67(1):88-90.
[38]蒋运斌,卢晓琳,杨枝中,等.与熏硫加工相关的白芷化学成分研究[J].中国实验方剂学杂志,2013,19(22):74-78.
[39]赵爱红,杨秀伟.兴安白芷脂溶性部位中新的天然产物[J].中草药,2014,45(13):1820-1828.
[40]Yao-Kouassi P A,Caron C,Ramiarantsoa H,et al. New nitro-benzo[c]phenanthridine and indolopyridoquinazoline alkaloids from Zanthoxylum atchoum[J]. CR Chim,2015,18(8):891-897.
[41]Lee J H,Bang H B,Han S Y,et al. A convenient total synthesis of(+)‐decursinol from Resorcinol[J].Cheminform,2007,38(19):2104-2106.
[42]GUO T,TANG X F,ZHANG J B,et al. Chemical constituents from the root and stem of Zanthoxylum avicennae[J]. Appl Mech Mater,2014,3379(618):426-430.
[43]李慧娟,杜成林,李娜,等.垂盆草的化学成分分离鉴定[J].中国实验方剂学杂志,2017,23(4):76-80.
[44]Toriumi Y,Kakuda R,Kikuchi M,et al. New triterpenoids from Gentiana lutea[J]. Chem Pharm Bull,2003,51(1):89-91.
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