title: Simultaneous determination of jasmonic acid epimers as phytohormones by chiral liquid chromatography-quadrupole time-of-flight mass spectrometry and their epimerization study.
abstract: Jasmonic acid (JA) is an essential plant hormone involved in plant development and defense system. There are four stereoisomeric forms of JA and they act quite differently in vivo. In this work, a normal phase liquid chromatography-quadrupole time-of-flight mass spectrometry (NPLC-QTOF-MS) method using cellulose tris (4-methylbenzoate) coated silica gel as the chiral stationary phase was first established for the simultaneous discrimination and direct analysis of all the four JA stereoisomers without need of derivatization. A non-endogenous JA stereoisomer was introduced as the internal standard to ensure the reliability of the developed method. Satisfactory results were obtained in terms of sensitivity (limit of detection, 0.5 ng mL(-1) or 2.4 fmol), linearity (R(2)=0.9996) and repeatability (run-to-run RSD of migration time and peak area, 0.37% and 5.9%, respectively, n=6). Endogenous rise of two natural JA stereoisomers was detected in tobacco leaves and their variations in response to mechanical wounding were monitored. In addition, the configurational stability of JA stereoisomers was investigated using the stereoisomerically pure forms which were not commercially available but easily obtained by our semi-preparative chiral LC method. Experimental evidence indicated that both of the two naturally existing JA stereoisomers were putative signals for wounding response, and the epimerization between them was not a spontaneous process simply promoted by the thermodynamical instability as expected before.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Institute of Analytical Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
authors.forename: Yehua
authors.initials: Y
authors.lastname: Han
authors.forename: Zhigui
authors.initials: Z
authors.lastname: Zhou
authors.forename: Hongliang
authors.initials: H
authors.lastname: Wu
authors.forename: Honggang
authors.initials: H
authors.lastname: Nie
authors.forename: Rong
authors.initials: R
authors.lastname: Lei
authors.forename: Yu
authors.initials: Y
authors.lastname: Bai
authors.forename: Huwei
authors.initials: H
authors.lastname: Liu
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods*; D003517:Cyclopentanes / Q000032:analysis*; D054883:Oxylipins / Q000032:analysis*; D010937:Plant Growth Regulators / Q000032:analysis*; D018515:Plant Leaves / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013237:Stereoisomerism; D053719:Tandem Mass Spectrometry / Q000379:methods*; D014026:Nicotiana / Q000737:chemistry*
chemical_list: D003517:Cyclopentanes; D054883:Oxylipins; D010937:Plant Growth Regulators; C011006:jasmonic acid