马铃薯花杀螨活性成分分离、鉴定及其杀螨活性
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摘要
以马铃薯花乙酸乙酯粗提物为分离对象,以朱砂叶螨Tetranychus cinnabarinus等4种叶螨为供试靶标,采用生物活性追踪法,分离得到2种具有杀螨活性的化合物(6a和2′a)。依据质谱、核磁共振氢谱和碳谱,并结合相关文献数据鉴定了其化学结构,分别为江户樱花苷(5,7, 4′-三羟基二氢黄酮-7-O-β-D-吡喃葡萄糖苷)(6a)和α-卡茄碱(2′a),前者系首次从茄科植物马铃薯中分离得到。采用玻片浸渍法测定了2个化合物对朱砂叶螨等4种叶螨的触杀活性。结果表明,化合物6a(江户樱花苷)对朱砂叶螨、二斑叶螨T. urticae和山楂叶螨T. viennensis 24 h LC_(50)值分别为461.98、338.76和732.08 mg/L,其触杀活性强于对照药剂鱼藤酮,相对毒力分别为鱼藤酮的1.17、1.52和3.07倍;化合物2′a(α-卡茄碱)对二斑叶螨和山楂叶螨24 h LC_(50)分别为480.79和834.98 mg/L,相对毒力分别为鱼藤酮的1.07和2.69倍。可见,江户樱花苷和α-卡茄碱具有一定的杀螨活性和潜在的应用价值。
Two compounds, 6a and 2′a, with acaricidal activities against four species of mites using bioassay-guided methods were isolated from the ethyl acetate extract of potato flowers. These two compounds were identified as prunin(5, 7, 4′-trihydroxyflavanone-7-O-β-D-glucopyranoside)(6a) andα-chaconine(2′a) by mass spectrometry, ~(13)C and ~1H nuclear magnetic resonance(NMR) and comparison with data from literatures. The former was first isolated from the Solanaceae plant potato.We determined the contact acaricidal activities of prunin and α-chaconine against four species of mites by slide-dip method and the results demonstrated that these compounds were more effective compared to pesticide rotenone, which was the positive control. The 24 h LC_(50) for prunin against Tetranychus cinnabarinus, T. urticae and T. viennensis were 461.98, 338.76 and 732.08 mg/L, respectively, which were 1.17, 1.52 and 3.07 times more active than rotenone, respectively. The 24 h LC_(50)for α-chaconine against T. urticae and T. viennensis were 480.79 and 834.98 mg/L, respectively, the relative toxicity are1.07 and 2.69 times higher compared to rotenone, respectively. Obviously, prunin and α-chaconine have acaricidal activities and potential application value.
Two compounds, 6a and 2′a, with acaricidal activities against four species of mites using bioassay-guided methods were isolated from the ethyl acetate extract of potato flowers. These two compounds were identified as prunin(5, 7, 4′-trihydroxyflavanone-7-O-β-D-glucopyranoside)(6a) andα-chaconine(2′a) by mass spectrometry, ~(13)C and ~1H nuclear magnetic resonance(NMR) and comparison with data from literatures. The former was first isolated from the Solanaceae plant potato.We determined the contact acaricidal activities of prunin and α-chaconine against four species of mites by slide-dip method and the results demonstrated that these compounds were more effective compared to pesticide rotenone, which was the positive control. The 24 h LC_(50) for prunin against Tetranychus cinnabarinus, T. urticae and T. viennensis were 461.98, 338.76 and 732.08 mg/L, respectively, which were 1.17, 1.52 and 3.07 times more active than rotenone, respectively. The 24 h LC_(50)for α-chaconine against T. urticae and T. viennensis were 480.79 and 834.98 mg/L, respectively, the relative toxicity are1.07 and 2.69 times higher compared to rotenone, respectively. Obviously, prunin and α-chaconine have acaricidal activities and potential application value.
引文
[1]木泰华,李鹏高.马铃薯中生物活性成分及其功能[J].食品科学,2016,37(19):269-276.MU T H,LI P G.Bioactive components of potato and their functions[J].Food Sci,2016,37(19):269-276.
[2]BLADES D,MITCHELL B K.Effect of alkaloids on feeding by Phormia regina[J].Entomol Exp Appl,1986,41(3):299-304.
[3]SINDEN S L,SANFORD L L,OSMAN S F.Glycoalkaloids and resistance to the Colorado potato beetle in Solanum chacoense bitter[J].Am Potato J,1980,57(7):331-343.
[4]SMITH D B,RODDICK J G,JONES J L.Synergism between the potato glycoalkaloidsα-chaconine andα-solanine in inhibition of snail feeding[J].Phytochemistry,2001,57(2):229-234.
[5]ALLEN E H,KUC J.α-solanine andα-chaconine as fungitoxic compounds in extracts of Irish potato tubers[J].Phytopathology,1968,58(6):776-781.
[6]FEWELL A M,RODDICK J G.Interactive antifungal activity of the glycoalkaloidsα-solanine andα-chaconine[J].Phytochemistry,1993,33(2):323-328.
[7]FRIEDMAN M,HENIKA P R.Absence of genotoxicity of potato alkaloidsα-chaconine,α-solanine and solanidine in the ames salmonella and adault and foetal erythrocyte micronucleus assays[J].Food Chem Toxic,1992,30(8):689-694.
[8]FEWELL A M,RODDICK J G,WEISSENBERG M.Interactions between the glycoalkaloids solasonine and solamargine in relation to inhibition of fungal growth[J].Phytochemistry,1994,37(4):1007-1011.
[9]MORRISSEY J P,OSBOURN A E.Fungal resistance to plant antibiotics as a mechanism of pathogenesis[J].Microbiol Mol BiolRev,1999,63(3):708-724.
[10]KEUKENS E A J,DE VRIJE T,FABRIE C H J P,et al.Dual specificity of sterol-mediated glycoalkaloid induced membrane disruption[J].Biochimica et Biophysica Acta(BBA)-Biomembranes,1992,1110(2):127-136.
[11]胡冠芳.马铃薯芽与花杀虫活性的研究及活性成分的分离鉴定[D].兰州:甘肃农业大学,2012.HU G F.Insecticidal activities,separation and identification of active compositions on buds and flowers of Solanum tuberosum L.[D].Lanzhou:Gansu Agricultural University,2012.
[12]郭致杰,胡冠芳,刘敏艳,等.马铃薯无光干芽和花乙酸乙酯粗提物杀虫活性的研究[J].草业学报,2013,22(6):173-181.GUO Z J,HU G F,LIU M Y,et al.Insecticidal activity of ethyl acetate extract from dry buds on dark condition and flowers of Solanum tuberosum[J].Acta Prataculturae Sinica,2013,22(6):173-181.
[13]王玉灵,刘敏艳,胡冠芳,等.马铃薯花杀虫活性成分提取方法的研究[J].西南农业学报,2014,27(4):1499-1504.WANG Y L,LIU M Y,HU G F,et al.Extraction method of insecticidal active composition from flowers of Solanum tuberosum[J].Southwest China J Agric Sci,2014,27(4):1499-1504.
[14]陈晓青,蒋新宇,刘佳佳.中草药成分分离分析技术与方法[M].北京:化学工业出版社,2006:56-60.CHEN X Q,JIANG X Y,LIU J J.Technology and method for analysis and separation of Chinese traditional herbal medicine components[M].Beijing:Chemical Industry Press,2006:56-60.
[15]陈年春.农药生物测定技术[M].北京:北京农业大学出版社,1991:68-71.CHEN N C.Pesticide bioassay technology[M].Beijing:China Agricultural University Press,1991:68-71.
[16]龚运淮,丁立生.天然产物核磁共振碳谱分析[M].昆明:云南科技出版社,2006:569-574.GONG Y H,DING L S.13C NMR analysis of natural products[M].Kunming:Yunnan Science and Technology Press,2006:569-574.
[17]高颖.骨碎补抗骨质疏松活性部位的化学成分研究[D].沈阳:沈阳药科大学,2008.GAO Y.Studies on the chemical constituents of anti-osteoporosis active site of Rhizoma Drynariae[D].Shenyang:Shenyang Pharmaceutical University,2008.
[18]COWAN M M.Plant products as antimicrobial agent[J].Clin Microbiol Rev,1999,12(4):564-582.
[19]柯樱,蒋毅,罗思齐.风轮菜的化学成分研究[J].中草药,1999,30(1):10-12.KE Y,JIANG Y,LUO S Q.Studies on the chemical consitiuents of Clinopodium chinense[J].Chin Tradit Herbal Drugs,1999,30(1):10-12.
[20]邹海艳,屠鹏飞.珍珠菜黄酮类化合物的研究[J].中国天然药物,2004,2(1):59-61.ZOU H Y,TU P F.Study on flavonoids from Lysimachia clethroides[J].Chin J Nat Med,2004,2(1):59-61.
[21]刘海洋,何红平,杨献文,等.蜡菊花的化学成分研究[J].天然产物研究与开发,2007,19(3):423-426.LIU H Y,HE H P,YANG X W,et al.Chemical constituents of the flowers of Helichrysum bracteatum[J].Nat Prod Res Dev,2007,19(3):423-426.
[22]唐丽华,徐向毅,游本刚,等.珍珠菜总黄酮苷的抗肿瘤作用及机制研究[J].上海中医药杂志,2007,41(5):74-76.TANG L H,XU X Y,YOU B G,et al.Anti-tumor effect and its mechanism of total flavones of Lysimachia clethroides Duby[J].Shanghai J Tradit Chin Med,2007,41(5):74-76.
[2]BLADES D,MITCHELL B K.Effect of alkaloids on feeding by Phormia regina[J].Entomol Exp Appl,1986,41(3):299-304.
[3]SINDEN S L,SANFORD L L,OSMAN S F.Glycoalkaloids and resistance to the Colorado potato beetle in Solanum chacoense bitter[J].Am Potato J,1980,57(7):331-343.
[4]SMITH D B,RODDICK J G,JONES J L.Synergism between the potato glycoalkaloidsα-chaconine andα-solanine in inhibition of snail feeding[J].Phytochemistry,2001,57(2):229-234.
[5]ALLEN E H,KUC J.α-solanine andα-chaconine as fungitoxic compounds in extracts of Irish potato tubers[J].Phytopathology,1968,58(6):776-781.
[6]FEWELL A M,RODDICK J G.Interactive antifungal activity of the glycoalkaloidsα-solanine andα-chaconine[J].Phytochemistry,1993,33(2):323-328.
[7]FRIEDMAN M,HENIKA P R.Absence of genotoxicity of potato alkaloidsα-chaconine,α-solanine and solanidine in the ames salmonella and adault and foetal erythrocyte micronucleus assays[J].Food Chem Toxic,1992,30(8):689-694.
[8]FEWELL A M,RODDICK J G,WEISSENBERG M.Interactions between the glycoalkaloids solasonine and solamargine in relation to inhibition of fungal growth[J].Phytochemistry,1994,37(4):1007-1011.
[9]MORRISSEY J P,OSBOURN A E.Fungal resistance to plant antibiotics as a mechanism of pathogenesis[J].Microbiol Mol BiolRev,1999,63(3):708-724.
[10]KEUKENS E A J,DE VRIJE T,FABRIE C H J P,et al.Dual specificity of sterol-mediated glycoalkaloid induced membrane disruption[J].Biochimica et Biophysica Acta(BBA)-Biomembranes,1992,1110(2):127-136.
[11]胡冠芳.马铃薯芽与花杀虫活性的研究及活性成分的分离鉴定[D].兰州:甘肃农业大学,2012.HU G F.Insecticidal activities,separation and identification of active compositions on buds and flowers of Solanum tuberosum L.[D].Lanzhou:Gansu Agricultural University,2012.
[12]郭致杰,胡冠芳,刘敏艳,等.马铃薯无光干芽和花乙酸乙酯粗提物杀虫活性的研究[J].草业学报,2013,22(6):173-181.GUO Z J,HU G F,LIU M Y,et al.Insecticidal activity of ethyl acetate extract from dry buds on dark condition and flowers of Solanum tuberosum[J].Acta Prataculturae Sinica,2013,22(6):173-181.
[13]王玉灵,刘敏艳,胡冠芳,等.马铃薯花杀虫活性成分提取方法的研究[J].西南农业学报,2014,27(4):1499-1504.WANG Y L,LIU M Y,HU G F,et al.Extraction method of insecticidal active composition from flowers of Solanum tuberosum[J].Southwest China J Agric Sci,2014,27(4):1499-1504.
[14]陈晓青,蒋新宇,刘佳佳.中草药成分分离分析技术与方法[M].北京:化学工业出版社,2006:56-60.CHEN X Q,JIANG X Y,LIU J J.Technology and method for analysis and separation of Chinese traditional herbal medicine components[M].Beijing:Chemical Industry Press,2006:56-60.
[15]陈年春.农药生物测定技术[M].北京:北京农业大学出版社,1991:68-71.CHEN N C.Pesticide bioassay technology[M].Beijing:China Agricultural University Press,1991:68-71.
[16]龚运淮,丁立生.天然产物核磁共振碳谱分析[M].昆明:云南科技出版社,2006:569-574.GONG Y H,DING L S.13C NMR analysis of natural products[M].Kunming:Yunnan Science and Technology Press,2006:569-574.
[17]高颖.骨碎补抗骨质疏松活性部位的化学成分研究[D].沈阳:沈阳药科大学,2008.GAO Y.Studies on the chemical constituents of anti-osteoporosis active site of Rhizoma Drynariae[D].Shenyang:Shenyang Pharmaceutical University,2008.
[18]COWAN M M.Plant products as antimicrobial agent[J].Clin Microbiol Rev,1999,12(4):564-582.
[19]柯樱,蒋毅,罗思齐.风轮菜的化学成分研究[J].中草药,1999,30(1):10-12.KE Y,JIANG Y,LUO S Q.Studies on the chemical consitiuents of Clinopodium chinense[J].Chin Tradit Herbal Drugs,1999,30(1):10-12.
[20]邹海艳,屠鹏飞.珍珠菜黄酮类化合物的研究[J].中国天然药物,2004,2(1):59-61.ZOU H Y,TU P F.Study on flavonoids from Lysimachia clethroides[J].Chin J Nat Med,2004,2(1):59-61.
[21]刘海洋,何红平,杨献文,等.蜡菊花的化学成分研究[J].天然产物研究与开发,2007,19(3):423-426.LIU H Y,HE H P,YANG X W,et al.Chemical constituents of the flowers of Helichrysum bracteatum[J].Nat Prod Res Dev,2007,19(3):423-426.
[22]唐丽华,徐向毅,游本刚,等.珍珠菜总黄酮苷的抗肿瘤作用及机制研究[J].上海中医药杂志,2007,41(5):74-76.TANG L H,XU X Y,YOU B G,et al.Anti-tumor effect and its mechanism of total flavones of Lysimachia clethroides Duby[J].Shanghai J Tradit Chin Med,2007,41(5):74-76.