膳食花色苷衍生物家族的结构及其形成机制

doi:10.3864/j.issn.0578-1752.2013.02.014

摘要/Abstract

摘要： 花色苷是人们熟悉的一类水溶性天然植物色素，具有多种重要的生理功能和生物活性，是广泛存在于水果、蔬菜、豆类、谷薯、花卉和药用植物中的重要呈色物质。花色苷衍生物是近些年发现于富含花色苷果蔬的加工产品及特殊植物器官中，由花色苷在发酵和陈酿过程中形成的或在植物体内经生物代谢合成的一系列花色苷的天然衍生物，构成了不同结构种类、不同色调的花色苷衍生物家族。本文系统介绍了不同类型（花色苷与黄烷醇直接连接、花色苷与酚类通过烷基连接、具有第4个吡喃环和不同连接基团的吡喃花色苷类、具苯并吡喃氧鎓离子的类花色素衍生物、其它特殊类衍生物）的花色苷衍生物家族的发现来源、结构特征及其形成机制，为进一步开展花色苷的结构稳定性与反应活性研究及其在农产品和食品加工中的应用提供有益的参考。

关键词: 膳食花色苷 , 花色苷衍生物 , 反应活性 , 结构 , 形成机制

Abstract: Anthocyanins are one class of natural water-soluble plant pigments which are commonly known to people and possess many important physiological functions and bioactivities. They are important substances responsible for the colours of fruits, vegetables, beans, grains, flowers and medicinal plants. In recent years, anthocyanin derivatives are found in the processed products of fruits and vegetables and some special plants rich in anthocyanins, which are series of natural products derived from anthocyanins and formed during fermentation and ageing or biologically synthesized by metabolization in plants tissues, constituting different families of anthocyanin derivatives with different structures and colours. The present paper summarized the origins of occurrence, structural features and formation mechanism of different types of anthocyanin derivatives (anthocyanin-flavanols, anthocyanin-alkyl-polyphenols, pyranoanthocyanins with the fourth pyran ring linked with different groups, anthocyanidin-like derivatives with flavylium ion and other unique anthocyanin derivatives), which will offer beneficial references for further investigate the structural stability and reactivity of anthocyanins with their applications in processing foods and agricultural products.

Key words: dietary anthocyanins , anthocyanin derivatives , reactivity , structures , formation mechanism

何静仁, 邝敏杰, 邓莉, 刘志伟, 易阳, 杨宁, 段李歌. 膳食花色苷衍生物家族的结构及其形成机制[J]. 中国农业科学, 2013, 46(2): 343-355.

HE Jing-Ren, KUANG Min-Jie, DENG Li, LIU Zhi-Wei, YI Yang, YANG Ning, DUAN Li-Ge. Structures and Formation Mechanism of Diverse Classes of Dietary Anthocyanin Derivatives[J]. Scientia Agricultura Sinica, 2013, 46(2): 343-355.

0
/ / 推荐

导出引用管理器 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

链接本文: https://www.chinaagrisci.com/CN/10.3864/j.issn.0578-1752.2013.02.014

https://www.chinaagrisci.com/CN/Y2013/V46/I2/343

参考文献

[1]Di Majo D, La Guardia M, Giammanco S, La Neve L, Giammanco M. The antioxidant capacity of red wine in relationship with its polyphenolic constituents. Food Chemistry, 2008, 111: 45-49.

[2]于斌, 余小平, 易龙, 朱俊东, 张乾勇, 糜漫天. 黑米花色苷抑制人乳腺癌细胞促血管生成因子表达的机制. 营养学报, 2010, 6: 545-550.

Yu B, Yu X P, Yi L, Zhu J D, Zhang Q Y, Mi M T. Mechanisms of black rice anthocyanins inhibiting expression of angiogenesis- related factors in human breast canter cells. Acta Utrimenta Sinica, 2010, 6: 545-550. (in Chinese)

[3]蔡花真, 王霞. 紫甘薯花色苷组分抑制小鼠肝、肾、心、脾脂质过氧化的研究. 食品工业, 2009(4): 6-8.

Cai H Z. Wang X. The study on APSP components inhibiting lipid peroxidation of rat liver, kidney, heart and spleen. Food Industry, 2009(4): 6-8. (in Chinese)

[4]He J, Giusti M M. Anthocyanins: natural colorants with health-promoting properties. Annual Review of Food Science and Technology, 2010, 1: 163-187.

[5]Taylor C, Wallace. Anthocyanins in cardiovascular disease. Advances in Nutrition, 2011(2): 1-7.

[6]Rein M J, Ollilainen V, Vahermo M, Yli-Kauhaluoma J, Heinonen M. Identi?cation of novel pyranoanthocyanins in berry juices. European Food Research and Technology, 2005, 202: 239-244.

[7]Hillebrand S. Analytik von Polyphenolen in Buntsaäften im Hinblick auf Saftqualität, Farbe und antioxidative Aktivität. Thesis, Göttingen: Cuvillier Verlag, 2004.

[8]García-Puente E R, Alcalde-Eon C, Santos-Buelga C, Rivas-Gonzalo J C, Escribano-Bailón M T. Behaviour and characterization of the colour during red wine making and maturation. Analytica Chimica Acta, 2006, 563: 215-222.

[9]Jurde L, Somers T C. The formation of xanthylium salts from proanthocyanidins. Phytochemistry, 1970, 9(2): 419-427.

[10]Vivar-Quintana A M, Santos-Buelga C, Francia-Aricha E, Rivas- Gonzalo J C. Formation of anthocyanin-derived pigments in experimental red wines. Food Science Technology International, 1999, 5(4): 347-352.

[11]Salas E, Atanasova V, Poncet-Legrand C, Meudec E, Mazauric J P, Cheynier V. Demonstration of the occurrence of flavanol–anthocyanin adducts in wine and in model solutions. Analytica Chimica Acta, 2004, 513(1): 325-332.

[12]Atanasova V. Re´actions des compose´s phe´noliques induites dans les vins rouges par la technique de micro-oxyge´nation. Caracte´risation de nouveaux produits de condensation des anthocyanes avec l’ace´talde´hyde. Montpellier: Thesis ENSAM, 2003.

[13]Gonza´lez-Parama´s A M, Silva F L, Mart?´n-Lo´pez P, Macz-Pop G. Flavanol–anthocyanin condensed pigments in plant extracts. Food Chemistry, 2006, 94: 428-436.

[14]Gonza´lez-Manzano S, Pe´rez-Alonso J J, Salians-moreno Y, Mateus N, Silva M S, Freitas V, Santos-Buelga C. Flavanol–anthocyanin pigments in corn: NMR characterisation and presence in different purple corn varieties. Journal of Food Composition and Analysis, 2008, 21: 521-526.

[15]Salas E, Guerneve C L, Fulcrand H, Poncet-Legrand C, Cheynier V. Structure determination and colour properties of a new directly linked ?avanol–anthocyanin dimmer. Tetrahedron Letters, 2004, 45(9): 8725-8729.

[16]Liao H, Cai Y. Polyphenols interactions. Anthocyanins: copigmentation and colour changes in red wines. Journal of the Science of Food and Agriculture, 1992, 59: 299-305.

[17]Santos-buelga C, Bravo-haro S, Rivas-gonzalo J C. Interactions between catechin and malvidin-3-monglucoside in model solutions. Zeitschrift fur Lebensmittel Untersuchung und Forschung, 1995, 201: 269-274.

[18]Duenas M, Fulcrand H, Chevnier V. Formation of anthocyanin– ?avanol adducts in model solutions. Analytica Chimica Acta, 2006, 563: 15-25.

[19]Salas E, Fulcrand H, Meudec E, Cheynier V. Reactions of anthocyanins and tannins in model solutions. Journal of Agricultural and Food Chemistry, 2003, 51(27): 7951-7961.

[20]He J, Santos-Buelga C, Mateus N, Freitas V. Isolation and quanti?cation of oligomeric pyranoanthocyanin-?avanol pigments from red wines by combination of column chromatographic techniques. Journal of Chromatography A, 2006, 1134: 215-225.

[21]Singleton V L, Berg H W, Guyomon J F. Anthocyanin color level in port-type wine as affected by the use of wine spirits containing aldehydes. American Journal of Enology and Viticulture, 1964, 15(2): 75-81.

[22]Berg H W, Akiyoshi M A. On the nature of reactions responsible for color behavior in red wine: a hypothesis. American Journal of Enology and Viticulture, 1975, 26(3): 134-143.

[23]Timberlake C F, Bridle P. Interactions between anthocyanins, phenolic compounds, and acetaldehyde and their significance in red wines. American Journal of Enology and Viticulture, 1976, 27(3): 97-105.

[24]Bakker J, Pinicelli A, Bridle. Model wine solutions: colour and composition changes during ageing. Vitis, 1993, 32(2): 111-118.

[25]Rivas-Gonzalo J C, Bravo-Haro H, Santos-Buelga V. Detection of compounds formed through the reaction of malvidin-3-monoglucoside in the presence of acetaldehyde. Journal of Agricultural and Food Chemistry, 1995, 43(6): 1444-1449.

[26]Atanasova V, Fulcrand H, Guerneve C L, Cheynier V, Moutounet M. Structure of a new dimeric acetaldehyde malvidin 3-glucoside condensation product. Tetrahedron Letters, 2002, 43: 6151-6153.

[27]Abe Y, Sawada A, Momose T, Sasaki N, Kawahara N, Kamakura H, Goda Y, Ozeki Y. Structure of an anthocyanin–anthocyanin dimer molecule in anthocyanin-producing cells of a carrot suspension culture. Tetrahedron Letters, 2008, 49: 7330-7333.

[28]Pissarra J, Lourenco S, Gonzalez-Paramas A M, Mateus N, Buelga C S, Silva M S, Freitas V. Isolation and structural characterization of new anthocyanin-alkyl-catechin pigments. Food Chemistry, 2005, 90: 81-87.

[29]Mazza G, Miniati E. Anthocyanins in fruits, vegetables and grains. Boca Raton, Florida, USA: CRC Press, 1993.

[30]Schwarz M, Quast P, Von Baer D, Winterhalter P. Vitisin A content in Chilean wines from Vitis vinifera cv. Cabernet Sauvignon and contribution to the color of aged red wines. Journal of Agricultural and Food Chemistry, 2003, 51(21): 6261-6267.

[31]Schwarz M, Hofmann G, Winterhalter P. Investigations on anthocyanins in wines from Vitis vinifera cv. Pinotage: factors in?uencing the formation of pinotin A and its correlation with wine age. Journal of Agricultural and Food Chemistry, 2004, 52: 498-504.

[32]Bakker J, Timberlake C F. Isolation, identi?cation and characterization of new color-stable anthocyanins occurring in some red wines. Journal of Agricultural and Food Chemistry, 1997, 45: 35-43.

[33]Francia-Aricha E M, Guerra M T, Rivas-Gonzalo J C, Santos-Buelga C. New anthocyanin pigments formed after condensation with ?avanols. Journal of Agricultural and Food Chemistry, 1997, 45: 2262-2266.

[34]Morata A, Caldero´n F, Gonza´lez M C, Sua´rez J A. Formation of the highly stable pyranoanthocyanins (vitisins A and B) in red wines by the addition of pyruvic acid and acetaldehyde. Food Chemistry, 2007, 100: 1144-1152.

[35]Atanasova V, Fulcrand H, Cheynier V. E?ect of oxygenation on polyphenol changes occurring in the course of wine making. Analytica Chimica Acta, 2002, 458(1): 15-27.

[36]Morata A, Go´mez-Cordove´s M C, Colomo B, Suarez J A. Pyruvic acid and acetaldehyde production by di?erent strains of Saccharomyces cerevisiae: relationship with vitisin A and B formation in red wines. Journal of Agricultural and Food Chemistry, 2003, 51(25): 7402-7409.

[37]Liu, S Q, Pilone G. J. An overview of formation and roles of acetaldehyde in winemaking with emphasis on microbiological implications. International Journal of Food Science and Technology, 2000, 35: 49-61.

[38]Bakker J, Bridle P, Honda T, Kuwano H, Terahara N, Timberlake C F. Identi?cation of an anthocyanin occurring in some red wines. Phytochemistry, 1997, 44(7): 1375-1382.

[39]Oliveira J, Freitas V, Mateus N. A novel synthetic pathway to vitisin B compounds. Tetrahedron Letters, 2009, 50(27): 3933-3935.

[40]He J, Santos-Buelga C, Silva A M, Mateus N, De Freitas V. Isolation and structural characterization of new anthocyanin derived yellow pigments in aged red wines. Journal of Agricultural and Food Chemistry, 2006, 54: 9598-9603.

[41]Cameira dos Santos P J, Brillouet J M, Cheynier V, Moutounet M. Detection and partial characterisation of new anthocyanin-derived pigments in wine. Journal of the Science of Food and Agriculture, 1996, 70: 204-208.

[42]Fulcrand H, Cameira Dos Santos P J, Sarni-Manchado P, Cheynier V, Favre Bonvin J. Structure of new anthocyanin-derived wine pigments. Journal of the Chemical Society Perkin Transactions, 1996, 1: 735-739.

[43]Lu Y, Foo Y, Sun Y. New pyranoanthocyanins from blackcurrant seeds. Tetrahedron Letters, 2002, 43: 7341-7344.

[44]Hayasaka Y, Asenstorfer R E. Screening for potential pigments derived from anthocyanins in red wine using nanoelectrospray tandem mass spectrometry. Journal of Agricultural and Food Chemistry, 2002, 50: 756-761.

[45]Schwarz M, Jerz G, &Winterhalter P. Isolation and structure of pinotin A, a new anthocyanin derivative from Pinotage wine. Vitis, 2003, 42: 105-106.

[46]Schwarz M, Wabnitz T C, Winterhalter P. Pathway leading to the formation of anthocyanin- vinylphenol adducts and related pigments in red wines. Journal of Agricultural and Food Chemistry, 2003, 51: 3682-3687.

[47]Francia-Aricha E M, Guerra M T, Rivas-Gonzalo J C, Santos-Buelga V. New anthocyanin pigments formed after condensation with ?avanols. Journal of Agricultural and Food Chemistry, 1997, 45, 2262-2266.

[48]Asenstorfer R E, Hayasaka Y, Jones G P. Isolation and structures of oligomeric wine pigments by bisul?te-mediated ion-exchange chromatography. Journal of Agricultural and Food Chemistry, 2001, 49: 5957-5963.

[49]Mateus N, Silva A M, Santos-Buelga C, Rivas-Gonzalo J C, De Freitas V. Identi?cation of anthocyanin-?avanol pigments in red wines by NMR and mass spectrometry. Journal of Agricultural and Food Chemistry, 2002, 50: 2110-2116.

[50]Mateus N, Carvalho E, Carvalho A R , Melo A, Gonza´lez-Parama´s A M, Santos-Buelga C. Isolation and structural characterization of new acylated anthocyanin-vinyl?avanol pigments occurring in aging red wines. Journal of Agricultural and Food Chemistry, 2003, 51: 277-282.

[51]Mateus N, Silva A M, Rivas-Gonzalo J C, Santos-Buelga C, De Freitas V A. A new class of blue anthocyanin-derived pigments isolated from red wines. Journal of Agricultural and Food Chemistry, 2003, 51: 1919-1923.

[52]He J, Carvalho A, Mateus N, Freitas V. Spectral features and stability of oligomeric pyranoanthocyanin-flavanol pigments isolated from red wines. Journal of Agricultural and Food Chemistry, 2010, 58: 9249-9258.

[53]Fulcrand H, Benabdelialil C, Rigaud J, Cheynier V, Moutounet M. A new class of wine pigments generated by reactions between pyruvic acid and grape anthocyanins. Phytochemistry, 1998, 47(7): 1401-1407.

[54]Es-safi N E, Le Guerneve C, Labarbe B, Fulcrand H, Cheynier V, Moutounet M. Structure of a new xanthylium salt derivative. Tetrahedron Letters, 1999, 40(32): 5869-5872.

[55]Es-safi N E, Le Guerneve C, Fulcrand H, Cheynier V, Moutounet M. Xanthylium salts formation involved in wine colour changes. International Journal of Food Science & Technology, 2000, 35(1): 63-74.

[56]Freitas V, Sousa C, Silva A M, Santos-Buelgac C, Mateus N. Synthesis of a new catechin-pyrylium derived pigment. Tetrahedron Letters, 2004, 45: 9349-9352.

[57]Fukui Y, Kusumi T, Masuda K, Iwashita T, Nomoto K. Structure of rosacyanin B, a novel pigment from the petals of Rosa hybrida. Tetrahedron Letters, 2002, 43: 2637-2639.