title: The Distribution of Coumarins and Furanocoumarins in Citrus Species Closely Matches Citrus Phylogeny and Reflects the Organization of Biosynthetic Pathways.
abstract: Citrus plants are able to produce defense compounds such as coumarins and furanocoumarins to cope with herbivorous insects and pathogens. In humans, these chemical compounds are strong photosensitizers and can interact with medications, leading to the "grapefruit juice effect". Removing coumarins and furanocoumarins from food and cosmetics imply additional costs and might alter product quality. Thus, the selection of Citrus cultivars displaying low coumarin and furanocoumarin contents constitutes a valuable alternative. In this study, we performed ultra-performance liquid chromatography coupled with mass spectrometry analyses to determine the contents of these compounds within the peel and the pulp of 61 Citrus species representative of the genetic diversity all Citrus. Generally, Citrus peel contains larger diversity and higher concentrations of coumarin/furanocoumarin than the pulp of the same fruits. According to the chemotypes found in the peel, Citrus species can be separated into 4 groups that correspond to the 4 ancestral taxa (pummelos, mandarins, citrons and papedas) and extended with their respective secondary species descendants. Three of the 4 ancestral taxa (pummelos, citrons and papedas) synthesize high amounts of these compounds, whereas mandarins appear practically devoid of them. Additionally, all ancestral taxa and their hybrids are logically organized according to the coumarin and furanocoumarin pathways described in the literature. This organization allows hypotheses to be drawn regarding the biosynthetic origin of compounds for which the biogenesis remains unresolved. Determining coumarin and furanocoumarin contents is also helpful for hypothesizing the origin of Citrus species for which the phylogeny is presently not firmly established. Finally, this work also notes favorable hybridization schemes that will lead to low coumarin and furanocoumarin contents, and we propose to select mandarins and Ichang papeda as Citrus varieties for use in creating species devoid of these toxic compounds in future breeding programs.
authors.affiliation: Université de Lorraine, UMR 1121 Laboratoire Agronomie et Environnement Nancy-Colmar, 2 avenue de la forêt de Haye, TSA 40602, 54518, Vandœuvre-lès-Nancy, France.|INRA, UMR 1121 Université de Lorraine, UMR 1121 Laboratoire Agronomie et Environnement Nancy-Colmar, 2 avenue de la forêt de Haye, TSA 40602, 54518, Vandœuvre-lès-Nancy, France.
authors.forename: Audray
authors.initials: A
authors.lastname: Dugrand-Judek
authors.affiliation: Université de Lorraine, UMR 1121 Laboratoire Agronomie et Environnement Nancy-Colmar, 2 avenue de la forêt de Haye, TSA 40602, 54518, Vandœuvre-lès-Nancy, France.|INRA, UMR 1121 Université de Lorraine, UMR 1121 Laboratoire Agronomie et Environnement Nancy-Colmar, 2 avenue de la forêt de Haye, TSA 40602, 54518, Vandœuvre-lès-Nancy, France.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Olry
authors.affiliation: Université de Lorraine, UMR 1121 Laboratoire Agronomie et Environnement Nancy-Colmar, 2 avenue de la forêt de Haye, TSA 40602, 54518, Vandœuvre-lès-Nancy, France.|INRA, UMR 1121 Université de Lorraine, UMR 1121 Laboratoire Agronomie et Environnement Nancy-Colmar, 2 avenue de la forêt de Haye, TSA 40602, 54518, Vandœuvre-lès-Nancy, France.
authors.forename: Alain
authors.initials: A
authors.lastname: Hehn
authors.affiliation: INRA, UMR AGAP, Station INRA, F-20230, San Giuliano, France.
authors.forename: Gilles
authors.initials: G
authors.lastname: Costantino
authors.affiliation: Centro de Protección Vegetal y Biotecnología, Instituto Valenciano de Investigaciones Agrarias (Ivia), 46113 Moncada, Valencia, Spain.|CIRAD, UMR AGAP, Station de Roujol, 97170 Petit-Bourg, Guadeloupe, France.
authors.forename: Patrick
authors.initials: P
authors.lastname: Ollitrault
authors.affiliation: CIRAD, UMR AGAP, Station INRA, F-20230, San Giuliano, France.
authors.forename: Yann
authors.initials: Y
authors.lastname: Froelicher
authors.affiliation: Université de Lorraine, UMR 1121 Laboratoire Agronomie et Environnement Nancy-Colmar, 2 avenue de la forêt de Haye, TSA 40602, 54518, Vandœuvre-lès-Nancy, France.|INRA, UMR 1121 Université de Lorraine, UMR 1121 Laboratoire Agronomie et Environnement Nancy-Colmar, 2 avenue de la forêt de Haye, TSA 40602, 54518, Vandœuvre-lès-Nancy, France.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Bourgaud
mesh_terms: D002851:Chromatography, High Pressure Liquid; D002957:Citrus / Q000737:chemistry* / Q000145:classification / Q000378:metabolism; D003374:Coumarins / Q000737:chemistry / Q000378:metabolism*; D005638:Fruit / Q000737:chemistry / Q000378:metabolism; D011564:Furocoumarins / Q000096:biosynthesis* / Q000737:chemistry; D013058:Mass Spectrometry; D010802:Phylogeny; D025341:Principal Component Analysis
chemical_list: D003374:Coumarins; D011564:Furocoumarins; C030123:coumarin