酸枣仁芽的化学成分分离鉴定
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摘要
目的:研究酸枣仁芽的化学成分,从物质基础的角度探寻萌发对酸枣仁活性的影响。方法:将干燥的酸枣仁芽粉碎后石油醚浸泡提取,除去油脂类成分,残渣干燥后再用甲醇加热回流提取,减压浓缩后得酸枣仁芽甲醇浸膏,将浸膏溶解,采用硅胶,C_(18)反相硅胶,LH-20型羟丙基葡聚糖凝胶等多种柱色谱方法进行分离纯化,并利用NMR和MS等现代波谱技术,结合参考文献确定化合物的化学结构。结果:从酸枣仁芽中分离鉴定13个化合物,分别为酸枣仁皂苷B (1),酸枣仁皂苷D (2),酸枣仁皂苷A (3),白桦脂酸(4),白桦脂醇(5),羽扇豆醇(6),麦珠子酸(7),美洲茶酸(8),齐墩果酸(9),熊果酸(10),木兰花碱(11),荷叶碱(12),当药黄素(13)。结论:以上化合物均首次从酸枣仁芽中分离得到。经对比,发现酸枣仁芽的化学成分与传统药用部位种子相似,主要为三萜及皂苷类、黄酮类、生物碱类化合物等,为酸枣仁芽药用资源的开发利用提供了一定的化学依据。
Objective: To investigate the chemical constituents from sprout of Ziziphi jujuba var. spinosa,and explore the effect of germination on the activity of Z. jujuba var. spinosa seed from the perspective of material basis. Method: The dry sprout of Z. jujuba var. spinosa was crushed and extracted with petroleum ether to remove oils and fats, then the residues were dried and received reflux extraction with methanol. The solvent was decompressed and recovered to obtain methanol fractions. The fractions were dissolved,isolated and purified by column chromatography technologies such as silica gel,RP C_(18) and Sephadex LH-20,and the structures of the compounds were identified by nuclear magnetic resonance( NMR), mass spectrometry( MS) and reference liteature. Result: The 13 compounds were isolated from the sprout of Z. jujuba var. spinosa and identified as jujuboside B( 1), jujuboside D( 2), jujuboside A( 3), betulinic acid( 4), betulin( 5), lupeol( 6),alphitolic acid( 7),ceanothic acid( 8),oleanolic acid( 9),ursolic acid( 10),magnoflorine( 11),nuciferine( 12) and swertisin( 13). Conclusion: All the above compounds were isolated from the sprout of of Z. jujuba var.spinosa for the first time. The study showed that the chemical constituents from the sprout were quite similar with those from the seeds of Z. jujuba var. spinosa,mainly including triterpenoids and saponins,flavonoids,alkaloid,etc. Overall,the results described in this study could provide certain chemical basis for further resources exploitation and utilization of the sprout of Z. jujuba var. spinosa.
Objective: To investigate the chemical constituents from sprout of Ziziphi jujuba var. spinosa,and explore the effect of germination on the activity of Z. jujuba var. spinosa seed from the perspective of material basis. Method: The dry sprout of Z. jujuba var. spinosa was crushed and extracted with petroleum ether to remove oils and fats, then the residues were dried and received reflux extraction with methanol. The solvent was decompressed and recovered to obtain methanol fractions. The fractions were dissolved,isolated and purified by column chromatography technologies such as silica gel,RP C_(18) and Sephadex LH-20,and the structures of the compounds were identified by nuclear magnetic resonance( NMR), mass spectrometry( MS) and reference liteature. Result: The 13 compounds were isolated from the sprout of Z. jujuba var. spinosa and identified as jujuboside B( 1), jujuboside D( 2), jujuboside A( 3), betulinic acid( 4), betulin( 5), lupeol( 6),alphitolic acid( 7),ceanothic acid( 8),oleanolic acid( 9),ursolic acid( 10),magnoflorine( 11),nuciferine( 12) and swertisin( 13). Conclusion: All the above compounds were isolated from the sprout of of Z. jujuba var.spinosa for the first time. The study showed that the chemical constituents from the sprout were quite similar with those from the seeds of Z. jujuba var. spinosa,mainly including triterpenoids and saponins,flavonoids,alkaloid,etc. Overall,the results described in this study could provide certain chemical basis for further resources exploitation and utilization of the sprout of Z. jujuba var. spinosa.
引文
[1]国家药典委员会.中华人民共和国药典.一部[M].北京:中国医药科技出版社,2015:22.
[2]周翔,姚鑫,孙丽红,等.基于HILIC-UPLC-MS/MS测定酸枣仁核苷及碱基类成分[J].中国实验方剂学杂志,2017,23(7):86-90.
[3]陈科先,赵丽梅,嵇长久,等.酸枣仁中的黄酮碳苷类成分研究[J].中国中药杂志,2015,40(8):1503-1507.
[4]黄之镨,马伟光.酸枣仁及活性物质的药理研究进展[J].中国民族民间医药,2018,27(3):57-60.
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[6]袁玉鲜.酸枣仁、理枣仁发芽前后有效成分含量及药效学变化的研究[D].昆明:云南中医学院,2012.
[7] Yoshikawa M,Murakami T,Ikebata A,et al. Structures and histamine release-inhibitory effects of jujubosides A1and C and acetyljujuboside B[J]. Chem Pharm Bull,1997,45(7):1186-1192.
[8]刘沁舡,王邠,梁鸿,等.酸枣仁皂苷D的分离及结构鉴定[J].药学学报,2004,39(8):601-604.
[9] Yoshidawa K,Shimono N,Arihara S,et al. Antisweet natural products VI. jujubasaponinsⅣ. V and VI from Zizyphus jujuba Mill.[J]. Chem Pharm Bull,1992,40(9):2275-2278.
[10] Reynolds W F,Mclean S,Poplawski J,et al. Total assignment of13C and1H spectra of three isomeric triterpenol derivatives by 2D NMR[J]. Tetrahedron,1986,42(13):3419-3428.
[11]林大都,刘嘉炜,李武国,等.蒲桃茎化学成分及其体外细胞毒活性研究[J].中草药,2014,45(14):1993-1997.
[12] Mondal D N,Kundu A B. A nor-triterpenoid from Zizyphus jujuba[J]. J Indian Chem Soc,1998,75(6):384-385.
[13]黄艳萍,宋家玲,吴继平,等.凉粉草化学成分分离鉴定[J].中国实验方剂学杂志,2018,24(6):77-81.
[14] GUO S,DUAN J A,TANG Y P,et al. Triterpenoids from the fruits of Ziziphus jujuba var. spinosa[J]. Biochem Syst Ecol,2011,39(4-6):880-882.
[15]高建华,李斌鑫,白凤,等.蒙药复方协日嘎四味化学成分的研究[J].北京中医药大学学报,2016,39(9):755-758.
[16]李萍,杨光明,张玉玲,等.莲子心脂溶性生物碱的分离鉴定[J].食品与生物技术学报,2016,35(1):19-27.
[17] WU Y,HE F,PAN Q,et al. C-glucosyl flavones from the seeds of Ziziphus jujuba var. spinosa[J]. Chem Nat Compd,2011,47(3):369-372.
[18]张舜波,王平,田代志,等.酸枣仁总皂苷对失眠老年大鼠脑氨基酸类神经递质及受体表达的影响[J].中国实验方剂学杂志,2014,20(4):124-127.
[19]王慧,罗坤,武静.酸枣仁汤对失眠大鼠中脑中缝背核神经胶质细胞的影响[J].中国实验方剂学杂志,2012,18(21):235-239.
[20]李佳虹,唐旗羚,郭纪全,等.基于受体配体结合技术研究酸枣仁镇静催眠活性成分[J].中国药理学通报,2016,32(4):508-513.
[21]邓伟,唐其柱,李欣,等.酸枣仁皂苷A对大鼠心室肌细胞L-型钙通道的影响[J].武汉大学学报:医学版,2009,30(3):299-302.
[22]杨莉军,常冠楠,徐新,等.氧化低密度脂蛋白、荷叶生物碱对THP-1巨噬细胞源性泡沫细胞ABCA1表达的影响[J].心血管康复医学杂志,2012,21(1):21-25,105.
[23] Shibano M,Kakutani K,Taniguchi M,et al. Antioxidant constituents in the dayflower(Commelina communis L.)and theirα-glucosidase-inhibitory activity[J]. J Nat Med,2008,62(3):349-353.
[24]沈国平,龙启福.木兰花碱对HERG钾通道蛋白表达的影响[J].山东医药,2011,51(31):36-37.
[2]周翔,姚鑫,孙丽红,等.基于HILIC-UPLC-MS/MS测定酸枣仁核苷及碱基类成分[J].中国实验方剂学杂志,2017,23(7):86-90.
[3]陈科先,赵丽梅,嵇长久,等.酸枣仁中的黄酮碳苷类成分研究[J].中国中药杂志,2015,40(8):1503-1507.
[4]黄之镨,马伟光.酸枣仁及活性物质的药理研究进展[J].中国民族民间医药,2018,27(3):57-60.
[5] Brown I L. Application and uses of resistant starch[J]. J Assoc Off Anal Chem Int,2004,87(3):727-732.
[6]袁玉鲜.酸枣仁、理枣仁发芽前后有效成分含量及药效学变化的研究[D].昆明:云南中医学院,2012.
[7] Yoshikawa M,Murakami T,Ikebata A,et al. Structures and histamine release-inhibitory effects of jujubosides A1and C and acetyljujuboside B[J]. Chem Pharm Bull,1997,45(7):1186-1192.
[8]刘沁舡,王邠,梁鸿,等.酸枣仁皂苷D的分离及结构鉴定[J].药学学报,2004,39(8):601-604.
[9] Yoshidawa K,Shimono N,Arihara S,et al. Antisweet natural products VI. jujubasaponinsⅣ. V and VI from Zizyphus jujuba Mill.[J]. Chem Pharm Bull,1992,40(9):2275-2278.
[10] Reynolds W F,Mclean S,Poplawski J,et al. Total assignment of13C and1H spectra of three isomeric triterpenol derivatives by 2D NMR[J]. Tetrahedron,1986,42(13):3419-3428.
[11]林大都,刘嘉炜,李武国,等.蒲桃茎化学成分及其体外细胞毒活性研究[J].中草药,2014,45(14):1993-1997.
[12] Mondal D N,Kundu A B. A nor-triterpenoid from Zizyphus jujuba[J]. J Indian Chem Soc,1998,75(6):384-385.
[13]黄艳萍,宋家玲,吴继平,等.凉粉草化学成分分离鉴定[J].中国实验方剂学杂志,2018,24(6):77-81.
[14] GUO S,DUAN J A,TANG Y P,et al. Triterpenoids from the fruits of Ziziphus jujuba var. spinosa[J]. Biochem Syst Ecol,2011,39(4-6):880-882.
[15]高建华,李斌鑫,白凤,等.蒙药复方协日嘎四味化学成分的研究[J].北京中医药大学学报,2016,39(9):755-758.
[16]李萍,杨光明,张玉玲,等.莲子心脂溶性生物碱的分离鉴定[J].食品与生物技术学报,2016,35(1):19-27.
[17] WU Y,HE F,PAN Q,et al. C-glucosyl flavones from the seeds of Ziziphus jujuba var. spinosa[J]. Chem Nat Compd,2011,47(3):369-372.
[18]张舜波,王平,田代志,等.酸枣仁总皂苷对失眠老年大鼠脑氨基酸类神经递质及受体表达的影响[J].中国实验方剂学杂志,2014,20(4):124-127.
[19]王慧,罗坤,武静.酸枣仁汤对失眠大鼠中脑中缝背核神经胶质细胞的影响[J].中国实验方剂学杂志,2012,18(21):235-239.
[20]李佳虹,唐旗羚,郭纪全,等.基于受体配体结合技术研究酸枣仁镇静催眠活性成分[J].中国药理学通报,2016,32(4):508-513.
[21]邓伟,唐其柱,李欣,等.酸枣仁皂苷A对大鼠心室肌细胞L-型钙通道的影响[J].武汉大学学报:医学版,2009,30(3):299-302.
[22]杨莉军,常冠楠,徐新,等.氧化低密度脂蛋白、荷叶生物碱对THP-1巨噬细胞源性泡沫细胞ABCA1表达的影响[J].心血管康复医学杂志,2012,21(1):21-25,105.
[23] Shibano M,Kakutani K,Taniguchi M,et al. Antioxidant constituents in the dayflower(Commelina communis L.)and theirα-glucosidase-inhibitory activity[J]. J Nat Med,2008,62(3):349-353.
[24]沈国平,龙启福.木兰花碱对HERG钾通道蛋白表达的影响[J].山东医药,2011,51(31):36-37.