Profiling of structurally labile oxylipins in plants by in situ derivatization with pentafluorobenzyl hydroxylamine

被引:42
作者
Schulze, B [1 ]
Lauchli, R [1 ]
Sonwa, MM [1 ]
Schmidt, A [1 ]
Boland, W [1 ]
机构
[1] Max Planck Inst Chem Ecol, D-07745 Jena, Germany
关键词
plant defense; oxylipin profiling; pentafluorobenzyl hydroxylamine; PFB oximes; NCl-GC-MS; jasmonic acid; 12-oxophytodienoic acid; alpha-Ketol; Phaseolus lunatus; herbivory;
D O I
10.1016/j.ab.2005.10.021
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
A GC-MS-based method for the simultaneous quantification of common oxylipins along with labile and highly reactive Compounds based on in situ derivatization with pentafluorobenzyl hydroxylamine to the corresponding O-2,3,4,5,6-pentafluorobenzyI oximes (PFB oximes) is presented. The approach covers oxo derivatives Such as jasmonic acid (JA), 12-oxophytodienoic acid (OPDA), certain phytoprostanes, unsaturated oxo-acids, oxo-hydroxy acids, and aldehyde fragments front the polar head of fatty acids. In the positive electron impact-MS mode, the PFB oximes display characteristic fragment ions that greatly facilitate the identification of oxylipins in complex matrices. In addition, the fluorinated derivatives allow a highly selective and low-background analysis by negative chemical ionization. Besides showing the general value of the method for the identification of a broad range of oxylipins (IS examples), we also demonstrate sensitivity, linearity, and reproducibility for the quantification of JA, OPDA, 11-oxo-9-undecenoic acid, and 13-oxo-9,11-tridecadienoic acid. The efficiency of the method is demonstrated by differential profiling of these four oxylipins in lima bean leaves after mechanical wounding and feeding by the herbivore Spodoptera littoralis. Caterpillar feeding induced several oxylipins, whereas after wounding only the level of JA increased. The rapid in situ derivatization prevents the isomerization of cis-JA to trans-M. The resting level of JA in lima beans showed an isomer ratio of 80:20 for trans/cis-M. After wounding, de novo synthesis of JA alters the ratio to 20:80 in favor of the cis isomer. (C) 2005 Elsevier Inc. All rights reserved.
引用
收藏
页码:269 / 283
页数:15
相关论文
共 53 条
[1]   Synthesis and biological activity of α,β,γ,δ-unsaturated aldehydes from diatoms [J].
Adolph, S ;
Poulet, SA ;
Pohnert, G .
TETRAHEDRON, 2003, 59 (17) :3003-3008
[2]   Identification of abscisic acid, indole-3-acetic acid, jasmonic acid, indole-3-acetonitrile, methyl jasmonate and gibberellins in developing, dormant and stratified seeds of ash (Fraxinus excelsior) [J].
Blake, PS ;
Taylor, JM ;
Finch-Savage, WE .
PLANT GROWTH REGULATION, 2002, 37 (02) :119-125
[3]   Oxoammonium salts. 6. 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium perchlorate: A stable and convenient reagent for the oxidation of alcohols. Silica gel catalysis [J].
Bobbitt, JM .
JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (25) :9367-9374
[4]   P-2-NICKEL CATALYST WITH ETHYLENEDIAMINE, A NOVEL SYSTEM FOR HIGHLY STEREOSPECIFIC REDUCTION OF ALKYNES TO CIS-OLEFINS [J].
BROWN, CA ;
AHUJA, VK .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1973, (15) :553-554
[5]   Biosynthesis and action of jasmonates in plants [J].
Creelman, RA ;
Mullet, JE .
ANNUAL REVIEW OF PLANT PHYSIOLOGY AND PLANT MOLECULAR BIOLOGY, 1997, 48 :355-381
[6]   Ion channel-forming alamethicin is a potent elicitor of volatile biosynthesis and tendril coiling.: Cross talk between jasmonate and salicylate signaling in lima bean [J].
Engelberth, J ;
Koch, T ;
Schüler, G ;
Bachmann, N ;
Rechtenbach, J ;
Boland, W .
PLANT PHYSIOLOGY, 2001, 125 (01) :369-377
[7]   Synthesis of 9,12-dioxo-10(Z)-dodecenoic acid, a new fatty acid metabolite derived from 9-hydroperoxy-10,12-octadecadienoic acid in lentil seed (Lens culinaris medik.) [J].
Gallasch, BAW ;
Spiteller, G .
LIPIDS, 2000, 35 (09) :953-960
[8]  
Gilabert MP, 2002, ANAL CHIM ACTA, V465, P319
[9]   The lipoxygenase pathway in tulip (Tulipa gesneriana):: detection of the ketol route [J].
Grechkin, AN ;
Mukhtarova, LS ;
Hamberg, M .
BIOCHEMICAL JOURNAL, 2000, 352 :501-509
[10]   Silencing of hydroperoxide lyase and allene oxide synthase reveals substrate and defense signaling crosstalk in Nicotiana attenuata [J].
Halitschke, R ;
Ziegler, J ;
Keinänen, M ;
Baldwin, IT .
PLANT JOURNAL, 2004, 40 (01) :35-46