Glucosinolate turnover in Brassicales species to an oxazolidin-2-one, formed via the 2-thione and without formation of thioamide

被引:18
作者
Agerbirk, Niels [1 ,2 ]
Matthes, Annemarie [1 ,2 ]
Erthmann, Pernille O. [1 ,2 ]
Ugolini, Luisa [3 ]
Cinti, Susanna [3 ]
Lazaridi, Eleni [1 ,2 ]
Nuzillard, Jean-Marc [5 ,6 ]
Mueller, Caroline [4 ]
Bak, Soren [1 ,2 ]
Rollin, Patrick [7 ,8 ]
Lazzeri, Luca [3 ]
机构
[1] Univ Copenhagen, Copenhagen Plant Sci Ctr, Thorvaldsensvej 40, DK-1871 Frederiksberg C, Denmark
[2] Univ Copenhagen, Dept Plant & Environm Sci, Thorvaldsensvej 40, DK-1871 Frederiksberg C, Denmark
[3] Council Agr Res & Econ, Res Ctr Cereal & Ind Crops, Via Corticella 133, I-40128 Bologna, Italy
[4] Bielefeld Univ, Dept Chem Ecol, Univ Str 25, D-33615 Bielefeld, Germany
[5] Univ Reims, F-51687 Reims, France
[6] CNRS, Inst Chim Mol Reims, UMR 7312, SFR CAP SANTE, F-51687 Reims, France
[7] Univ Orleans, BP 6759, F-45067 Orleans, France
[8] CNRS, ICOA, UMR 7311, BP 6759, F-45067 Orleans, France
关键词
Barbarea vulgaris R.Br. (Brassicaceae); Glucosinolate hydrolysis; Turnover; 1,3-Oxazolidine-2-thione; 1,3-Oxazolidin-2-one; Nitrile; Thioamide; Reseda luteola; Nasturtium officinale; ISOTHIOCYANATE GLUCOSIDE GLUCOBARBARIN; BARBAREA-VULGARIS; PIERIS-RAPAE; PRODUCTS; HYDROLYSIS; METABOLITES; BIOSYNTHESIS; POLYMORPHISM; RESISTANCE; MYROSINASE;
D O I
10.1016/j.phytochem.2018.05.006
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Glucosinolates are found in plants of the order Brassicales and hydrolyzed to different breakdown products, particularly after tissue damage. In Barbarea vulgaris R.Br. (Brassicaceae), the dominant glucosinolate in the investigated "G-type" is glucobarbarin, (S)-2-hydroxy-2-phenylethylglucosinolate. Formation of the nitrile from glucobarbarin was observed in vitro, while a previously suggested thioamide (synonym thionamide) was not confirmed. Resedine (5-phenyl-1,3-oxazolidin-2-one) was detected after glucobarbarin hydrolysis in crushed B. vulgaris leaves and siliques, but not in intact parts. The abundance increased for several hours after completion of hydrolysis. The corresponding 1,3-oxazolidine-2-thione (OAT), with the common name barbarin, was also formed, and appeared to be the precursor of resedine. Addition of each of two non-endogenous OATs, (S)-5-ethyl-5-methylOAT and (R)-5-vinylOAT (R-goitrin), to a leaf homogenate resulted in formation of the corresponding 1,3-oxazolidin-2-ones (OAOs), confirming the metabolic connection of OAT to OAO. Formation of OAOs was inhibited by prior brief heating of the homogenate, suggesting enzyme involvement. We suggest the conversion of OATs to OAOs to be catalyzed by an enzyme ("oxazolidinethionase") responsible for turnover of OAT formed in intact plants. Resedine had been reported as an alkaloid from another species - Reseda luteola L. (Resedaceae) - naturally containing the glucosinolate glucobarbarin. However, resedine was not detected in intact R. luteola plants, but formed after tissue damage. The formation of resedine in two families suggests a broad distribution of putative OATases in the Brassicales; potentially involved in glucosinolate turnover that needs myrosinase activity as the committed step. In agreement with the proposed function of OATase, several candidate genes for myrosinases in glucosinolate turnover in intact plants were discovered in the B. vulgaris genome. We also suggest that biotechnological conversion of OATs to OAOs might improve the nutritional value of Brassicales protein. HPLC-MS/MS methods for detection of these glucobarbarin products are described. (C) 2018 Elsevier Ltd. All rights reserved.
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页码:79 / 93
页数:15
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