‘紫枝’玫瑰(Rosa rugosa ‘Zi zhi’)开花过程花青素相关化合物及代谢途径分析
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摘要
【目的】分析‘紫枝’玫瑰5个开花时期花瓣中的花青苷、类黄酮苷和类胡萝卜素的种类和含量,推定‘紫枝’玫瑰花的花青苷代谢途径,为探讨玫瑰花色的呈色机理和花色育种提供参考。【方法】以‘紫枝’玫瑰不同开花时期的花瓣为试材,用高效液相色谱(HPLC)和超高效液相色质联用分析法(UPLC-DAD-Q-TOF-MS)对其花青苷、类黄酮苷和类萝卜素进行结构推定和定量分析,结合化学反应过程推测‘紫枝’玫瑰花青苷代谢途径。【结果】在‘紫枝’玫瑰中鉴定出8种花青苷、16种类黄酮苷和β-胡萝卜素,没有检测到叶黄素;花青苷主要以芍药素、飞燕草素、矢车菊素和天竺葵素的双糖苷为主,四类花青苷都在花蕾期和初开期相对含量最高;检测到芍药苷的两种甲基化衍生物,没有发现飞燕草苷的甲基化衍生物;类黄酮苷以槲皮素和山萘酚的糖苷化、酰基化和甲基化的衍生物为主。定量分析显示,芍药苷和飞燕草苷占‘紫枝’玫瑰总花青苷含量的90%以上;芍药苷含量在‘紫枝’玫瑰开花过程中随花色变浅而降低,飞燕草苷在开花过程含量变化不大;芍药苷和飞燕草苷的比例(Pn/Dp)随花色变浅而降低。【结论】‘紫枝’玫瑰花中含有芍药素、飞燕草素、矢车菊素和天竺葵素,这四类花青素在半开期之前完成全部积累,盛开期后只降解不合成。芍药素是形成‘紫枝’玫瑰花色的主要成分。‘紫枝’玫瑰的花青苷代谢途径中,甲基酶(Rr AOMT)的催化作用有底物特异性。
【Objective】The composition content and structure of pigments in Rosa rugosa ‘Zi zhi' and their biosynthetic pathways were studied in order to lay a foundation for further investigation of the floral pigment mechanism and molecular breeding of R. rugosa. 【Method】 Anthocyanins, flavonoids and carotenes in the petals of flowers at different blooming stages were determined using HPLC and ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry(UPLC-DAD-Q-TOF-MS). The biosynthetic pathways of anthocyanins in R. rugosa ‘Zi zhi' were proposed according to the results of HPLC, UPLC-DAD-QTOF-MS and chemical reactions. 【Result】 In all, 8 kinds of anthocyanins, 16 kinds of flavones and flavonol glycosides and β-carotene were detected from the petals of R. rugosa ‘Zi zhi', but xanthin was not detected. The main structures of the anthocyanins were bioside of peonidin, delphinidin, cyanindin and pelargondin. The highest relative contents of the four anthocyanins were detected at budding-flower and initial flowering stages. Two types of methylation of paeonidin were detected while no methylation was detected in delphindin. The main compounds of flavonoid were glycosylations, acylations, methylated quercetin and kaempferol. The results of quantitative analysis showed that the contents of paeonidin and delphindin accounted for more than 90% of the total anthocyanins. The content of paeonidin was reduced with the color fading while the content of delphindin was stable at all stages and the ratio of paeonidin to delphindin was reduced with the flower blooming.【Conclusion】There are peonidin, delphinidin, cyanindin and pelargondin in the petals of R. rugosa‘Zi Zhi'. The four anthocyanins are synthesized at the budding-flower and initial flowering stages, and the contents of them are reduced during the flower blooming. Peonidin is the main composition that determines the flower color of R. rugosa‘Zi zhi'. The catalytic reactions of Rr AOMT exhibit substrate specific patterns.
【Objective】The composition content and structure of pigments in Rosa rugosa ‘Zi zhi' and their biosynthetic pathways were studied in order to lay a foundation for further investigation of the floral pigment mechanism and molecular breeding of R. rugosa. 【Method】 Anthocyanins, flavonoids and carotenes in the petals of flowers at different blooming stages were determined using HPLC and ultra performance liquid chromatography-quadrupole-time of flight-mass spectrometry(UPLC-DAD-Q-TOF-MS). The biosynthetic pathways of anthocyanins in R. rugosa ‘Zi zhi' were proposed according to the results of HPLC, UPLC-DAD-QTOF-MS and chemical reactions. 【Result】 In all, 8 kinds of anthocyanins, 16 kinds of flavones and flavonol glycosides and β-carotene were detected from the petals of R. rugosa ‘Zi zhi', but xanthin was not detected. The main structures of the anthocyanins were bioside of peonidin, delphinidin, cyanindin and pelargondin. The highest relative contents of the four anthocyanins were detected at budding-flower and initial flowering stages. Two types of methylation of paeonidin were detected while no methylation was detected in delphindin. The main compounds of flavonoid were glycosylations, acylations, methylated quercetin and kaempferol. The results of quantitative analysis showed that the contents of paeonidin and delphindin accounted for more than 90% of the total anthocyanins. The content of paeonidin was reduced with the color fading while the content of delphindin was stable at all stages and the ratio of paeonidin to delphindin was reduced with the flower blooming.【Conclusion】There are peonidin, delphinidin, cyanindin and pelargondin in the petals of R. rugosa‘Zi Zhi'. The four anthocyanins are synthesized at the budding-flower and initial flowering stages, and the contents of them are reduced during the flower blooming. Peonidin is the main composition that determines the flower color of R. rugosa‘Zi zhi'. The catalytic reactions of Rr AOMT exhibit substrate specific patterns.
引文
[1]张洁,王亮生,高锦明,李圣波,徐彦军,李崇晖,杨瑞珍.贴梗海棠花青苷组成及其与花色的关系.园艺学报,2011,38(3):527-534.Zhang J,Wang L S,Gao J M,Li S B,Xu Y J,Li C H,Yang R Z.Identification of anthocyanins involving in petal coloration in Chaenomeles speciosa cultivars.Acta Horticulturae Sinica,2011,38(3):527-534.(in Chinese)
[2]Weiss M R.Floral color changes as cues for pollinators.Nature,1991,354(6350):227-229.
[3]Grotewold E.The genetics and biochemistry of floral pigments.Annual Review of Plant Biology,2006(57):761-780.
[4]Nicholls E,Ibarra N H.Bees associate colour cues with differences in pollen rewards.Journal of Experimentas Biology,2014,217(15):2783-2788.
[5]葛翠莲,黄春辉,徐小彪.果实花青素生物合成研究进展.园艺学报,2012,39(9):1655-1664.Ge C L,Huang C H,Xu X B.Research on anthocyanins biosynthesis in fruit.Acta Horticulturae Sinica,2012,39(9):1655-1664.(in Chinese)
[6]Welch C R,Wu Q,Simon J E.Recent advances in anthocyanin analysis and characterization.Current Analytical Chemistry,2008,4(2):75-101.
[7]Mikanagi Y,Saito N,Yokoi M,Tatsuzawa F.Anthocyanins in flowers of genus Rosa,sections Cinnamomeae(=Rosa),Chineses,Gallicanaw and some modern garden roses.Biochemical Systematics and Ecology,2000,28(9):887-902.
[8]徐宗大,张玲,杨志莹,赵兰勇.玫瑰SRAP遗传多样性分析与品种指纹图谱构建.中国农业科学,2011,44(8):1662-1669.Xu Z D,Zhang L,Yang Z Y,Zhao L Y.Analysis of genetic diversity and construction of fingerprint of Rosa rugosa by SRAP.Scientia Agricultura Sinica,2011,44(8):1662-1669.(in Chinese)
[9]于晓艳,邢树堂,赵兰勇.玫瑰与月季中间杂交障碍原因分析.中国农业科学,2014,47(15):3112-3120.Yu X Y,Xing S T,Zhao L Y.Analysis on the barriers of interspecific hybridization between Rosa rugosa and Rosa hybrid.Scientia Agricultura Sinica,2014,47(15):3112-3120.(in Chinese)
[10]李玉舒.中国玫瑰种质资源调查及品种分类研究[D].北京:北京林业大学,2006.Li Y S.Studies on germplasm resources and cultivars classification of Rosa Rugosa in China[D].Beijing:Beijing Forestry University,2006.(in Chinese)
[11]Feng L,Chen,C,Li T,Wang M,Tao J,Zhao D,Sheng L X.Flowery odor formation revealed by differential expression of monoterpene biosynthetic genes and monoterpene accumulation in rose(Rosa rugosa Thunb.).Plant Physiology and Biochemistry,2014,75:80-88.
[12]钟培星,王亮生,李珊珊,徐彦军,朱满兰.芍药开花过程中花色和色素的变化.园艺学报,2012,39(11):2271-2282.Zhong P X,Wang L S,Li S S,Xu Y J,Zhu M L.The changes of floral color and pigments composition during the flowering period in Paeonia lactiflora Pallas.Acta Horticulturae Sinica,2012,39(11):2271-2282.(in Chinese)
[13]Mikanagi Y,Yokoi M,Ueda Y,Saito N.Flower flavonol and anthocyanin distribution in subgenus Rosa.Biochemical Systematics and Ecology,1995,23:183-200.
[14]张洁,李崇辉,王亮生,陈峰.植物花青苷液质联用方法的分析鉴定.食品安全质量检测学报,2013,4(3):760-768.Zhang J,Li C H,Wang L S,Chen F.Golden rules of separation and characterization of plant anthocyanins by high pressure liquid chromatography-tandem mass spectrometry.Journal of Food Safety and Quality,2013,4(3):760-768.(in Chinese)
[15]Veberic R S A,Brzjak J,Stampar F,Maja M.Anthocyanin composition of different wild and cultivated berry species.LWT-Food Science and Technology,2015,60(2015):509-517.
[16]孙卫,李崇晖,王亮生,戴思兰.菊花不同花色品种中花青素苷代谢分析.植物学报,2010,45(3):327-336.Sun W,Li C H,Wang L S,Dai S L.Metabolism analysis of anthocyanin in different color cultivars of chrysanthemum.Chinese Bulletin of Botany,2010,45(3):327-336.(in Chinese)
[17]Harborne J B,Williams C A.Advances in flavonoid research since1992.Phytochemistry,2000,481-504.
[18]孙卫,李崇晖,王亮生,戴思兰.蓝色瓜叶菊花青苷在花发育过程中的积累和变化规律.北京林业大学学报,2010,32(3):128-134.Sun W,Li C H,Wang L S,Dai S L.Accumulation and variation of anthocyanins in blue flowers of Senecio cruentus at different flowering stages.Journal of Beijing Forestry University,2010,32(3):128-134.(in Chinese)
[19]Sood S,Vas D,Nagar P K.Physiological and biochemical studies during flower development in two rose species.Scientia Horticulturae,2006,108(4):390-396.
[20]Yoshida K,Mori M,Kondo T.Blue flower color development by anthocyanins:from chemical structure to cell physiology.Natural Product Reports,2009,26(7):884-915.
[21]Asen S,Stewart R N,Norris K H.Co-pigmentation of anthocyanins in plant tissues and its effect on color.Phytochemistry,1972,1139-1144.
[22]Baranac J M,Petranovie N A,Dimitri-Markovic J M.Spectrophotometic study of anthocyan copigmentation reactions.Journal of Agricultural and Food Chemistry,1996,44:1333-1336.
[23]Malien-Aubert C,Dangles Q,Amiot M J.Color stability of commercial anthocuanin-based extracts in relation to the phenolic composition.Protective effects by intra-and intermolecular copigmentation.Journal of Agriculural and Food Chemistry,2001(49):170-176.
[24]Tanaka Y,Ohmiya A.Seeing is believing:engineering anthocyanin and carotenoid biosynthetic pathway.Current Opinion in Biotechnology,2008,19(2):190-197.
[25]Tanaka Y,Sasaki N,Ohmiya A.Biosynthesis of plant pigments:anthocyanins,betalains and carotenoids.Plant Journal,2008,54(4):733-749.
[26]Sumner L W,Lei Z,Nikolau B J,Saito K.Modern plant metabolomics:advanced natural product gene discoveries,improved technologies and future prospects.Natural Product Reports,2015,32(2):212-229.
[2]Weiss M R.Floral color changes as cues for pollinators.Nature,1991,354(6350):227-229.
[3]Grotewold E.The genetics and biochemistry of floral pigments.Annual Review of Plant Biology,2006(57):761-780.
[4]Nicholls E,Ibarra N H.Bees associate colour cues with differences in pollen rewards.Journal of Experimentas Biology,2014,217(15):2783-2788.
[5]葛翠莲,黄春辉,徐小彪.果实花青素生物合成研究进展.园艺学报,2012,39(9):1655-1664.Ge C L,Huang C H,Xu X B.Research on anthocyanins biosynthesis in fruit.Acta Horticulturae Sinica,2012,39(9):1655-1664.(in Chinese)
[6]Welch C R,Wu Q,Simon J E.Recent advances in anthocyanin analysis and characterization.Current Analytical Chemistry,2008,4(2):75-101.
[7]Mikanagi Y,Saito N,Yokoi M,Tatsuzawa F.Anthocyanins in flowers of genus Rosa,sections Cinnamomeae(=Rosa),Chineses,Gallicanaw and some modern garden roses.Biochemical Systematics and Ecology,2000,28(9):887-902.
[8]徐宗大,张玲,杨志莹,赵兰勇.玫瑰SRAP遗传多样性分析与品种指纹图谱构建.中国农业科学,2011,44(8):1662-1669.Xu Z D,Zhang L,Yang Z Y,Zhao L Y.Analysis of genetic diversity and construction of fingerprint of Rosa rugosa by SRAP.Scientia Agricultura Sinica,2011,44(8):1662-1669.(in Chinese)
[9]于晓艳,邢树堂,赵兰勇.玫瑰与月季中间杂交障碍原因分析.中国农业科学,2014,47(15):3112-3120.Yu X Y,Xing S T,Zhao L Y.Analysis on the barriers of interspecific hybridization between Rosa rugosa and Rosa hybrid.Scientia Agricultura Sinica,2014,47(15):3112-3120.(in Chinese)
[10]李玉舒.中国玫瑰种质资源调查及品种分类研究[D].北京:北京林业大学,2006.Li Y S.Studies on germplasm resources and cultivars classification of Rosa Rugosa in China[D].Beijing:Beijing Forestry University,2006.(in Chinese)
[11]Feng L,Chen,C,Li T,Wang M,Tao J,Zhao D,Sheng L X.Flowery odor formation revealed by differential expression of monoterpene biosynthetic genes and monoterpene accumulation in rose(Rosa rugosa Thunb.).Plant Physiology and Biochemistry,2014,75:80-88.
[12]钟培星,王亮生,李珊珊,徐彦军,朱满兰.芍药开花过程中花色和色素的变化.园艺学报,2012,39(11):2271-2282.Zhong P X,Wang L S,Li S S,Xu Y J,Zhu M L.The changes of floral color and pigments composition during the flowering period in Paeonia lactiflora Pallas.Acta Horticulturae Sinica,2012,39(11):2271-2282.(in Chinese)
[13]Mikanagi Y,Yokoi M,Ueda Y,Saito N.Flower flavonol and anthocyanin distribution in subgenus Rosa.Biochemical Systematics and Ecology,1995,23:183-200.
[14]张洁,李崇辉,王亮生,陈峰.植物花青苷液质联用方法的分析鉴定.食品安全质量检测学报,2013,4(3):760-768.Zhang J,Li C H,Wang L S,Chen F.Golden rules of separation and characterization of plant anthocyanins by high pressure liquid chromatography-tandem mass spectrometry.Journal of Food Safety and Quality,2013,4(3):760-768.(in Chinese)
[15]Veberic R S A,Brzjak J,Stampar F,Maja M.Anthocyanin composition of different wild and cultivated berry species.LWT-Food Science and Technology,2015,60(2015):509-517.
[16]孙卫,李崇晖,王亮生,戴思兰.菊花不同花色品种中花青素苷代谢分析.植物学报,2010,45(3):327-336.Sun W,Li C H,Wang L S,Dai S L.Metabolism analysis of anthocyanin in different color cultivars of chrysanthemum.Chinese Bulletin of Botany,2010,45(3):327-336.(in Chinese)
[17]Harborne J B,Williams C A.Advances in flavonoid research since1992.Phytochemistry,2000,481-504.
[18]孙卫,李崇晖,王亮生,戴思兰.蓝色瓜叶菊花青苷在花发育过程中的积累和变化规律.北京林业大学学报,2010,32(3):128-134.Sun W,Li C H,Wang L S,Dai S L.Accumulation and variation of anthocyanins in blue flowers of Senecio cruentus at different flowering stages.Journal of Beijing Forestry University,2010,32(3):128-134.(in Chinese)
[19]Sood S,Vas D,Nagar P K.Physiological and biochemical studies during flower development in two rose species.Scientia Horticulturae,2006,108(4):390-396.
[20]Yoshida K,Mori M,Kondo T.Blue flower color development by anthocyanins:from chemical structure to cell physiology.Natural Product Reports,2009,26(7):884-915.
[21]Asen S,Stewart R N,Norris K H.Co-pigmentation of anthocyanins in plant tissues and its effect on color.Phytochemistry,1972,1139-1144.
[22]Baranac J M,Petranovie N A,Dimitri-Markovic J M.Spectrophotometic study of anthocyan copigmentation reactions.Journal of Agricultural and Food Chemistry,1996,44:1333-1336.
[23]Malien-Aubert C,Dangles Q,Amiot M J.Color stability of commercial anthocuanin-based extracts in relation to the phenolic composition.Protective effects by intra-and intermolecular copigmentation.Journal of Agriculural and Food Chemistry,2001(49):170-176.
[24]Tanaka Y,Ohmiya A.Seeing is believing:engineering anthocyanin and carotenoid biosynthetic pathway.Current Opinion in Biotechnology,2008,19(2):190-197.
[25]Tanaka Y,Sasaki N,Ohmiya A.Biosynthesis of plant pigments:anthocyanins,betalains and carotenoids.Plant Journal,2008,54(4):733-749.
[26]Sumner L W,Lei Z,Nikolau B J,Saito K.Modern plant metabolomics:advanced natural product gene discoveries,improved technologies and future prospects.Natural Product Reports,2015,32(2):212-229.
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