Formation of a complex pattern of sinapate esters in Brassica napus seeds, catalyzed by enzymes of a serine carboxypeptidase-like acyltransferase family?
Members of the Brassicaceae accumulate complex patterns of sinapate esters, as shown in this communication with seeds of oilseed rape (Brassica napus). Fifteen seed constituents were isolated and identified by a combination of high-field NMR spectroscopy and high resolution electrospray ionisation mass spectrometry. These include glucose, gentiobiose and kaempferol glycoside esters as well as sinapine (sinapoylcholine), sinapoylmalate and an unusual cyclic spermidine amide. One of the glucose esters (1,6-di-O-sinapoylglucose), two gentiobiose esters (1-O-caffeoylgentiobiose and 1,2,6'-tri-O-sinapoylgentiobiose) and two kaempferol conjugates [4'-(6-O-sinapoylglucoside)-3,7-di-O-glucoside and 3-O-sophoroside-7-O-(2-O-sinapoylglucoside)] seem to be new plant products. Serine carboxypeptidase-like (SCPL) acyltransferases catalyze the formation of sinapine and sinapoylmalate accepting 1-O-beta-acetal esters (1-O-beta-glucose esters) as acyl donors. To address the question whether the formation of other components of the complex pattern of the sinapate esters in B. napus seeds is catalyzed via 1-O-sinapoyl-beta-glucose, we performed a seed-specific dsRNAi-based suppression of the sinapate glucosyltransferase gene (BnSGT1) expression. In seeds of BnSGT1-suppressing plants the amount of sinapoylglucose decreased below the HPLC detection limit resulting in turn in the disappearance or marked decrease of all the other sinapate esters, indicating that formation of the complex pattern of these esters in B. napus seeds is dependent on sinapoylglucose. This gives rise to the assumption that enzymes of an SCPL acyltransferase family catalyze the appropriate transfer reactions to synthesize the accumulating esters.
Baumert
Alfred
A
Leibniz-Institut für Pflanzenbiochemie (IPB), Weinberg 3, D-06120 Halle (Saale), Germany.
Milkowski
Carsten
C
Schmidt
Jürgen
J
Nimtz
Manfred
M
Wray
Victor
V
Strack
Dieter
D
D000217:Acyltransferases / Q000378:metabolism*; D029688:Brassica napus / Q000201:enzymology*; D002268:Carboxypeptidases / Q000378:metabolism*; D003373:Coumaric Acids / Q000737:chemistry / Q000378:metabolism*; D004952:Esters / Q000737:chemistry / Q000378:metabolism*; D015394:Molecular Structure; D012639:Seeds / Q000201:enzymology*
D003373:Coumaric Acids; D004952:Esters; C073734:sinapinic acid; D000217:Acyltransferases; D002268:Carboxypeptidases