title: Mass spectrometry-based fragmentation as an identification tool in lignomics.
abstract: The ensemble of all phenolics for which the biosynthesis is coregulated with lignin biosynthesis, i.e., metabolites from the general phenylpropanoid, monolignol, and (neo)lignan biosynthetic pathways and their derivatives, as well as the lignin oligomers, is coined the lignome. In lignifying tissues, the lignome comprises a significant portion of the metabolome. However, as is true for metabolomics in general, the structural elucidation of unknowns represents the biggest challenge in characterizing the lignome. To minimize the necessity to purify unknowns for NMR analysis, it would be desirable to be able to extract structural information from liquid chromatography-mass spectrometry data directly. However, mass spectral libraries for metabolomics are scarce, and no libraries exist for the lignome. Therefore, elucidating the gas-phase fragmentation behavior of the major bonding types encountered in lignome-associated molecules would considerably advance the systematic characterization of the lignome. By comparative MS(n) analysis of a series of molecules belonging to the β-aryl ether, benzodioxane, phenylcoumaran, and resinol groups, we succeeded in annotating typical fragmentations for each of these bonding structures as well as fragmentations that enabled the identification of the aromatic units involved in each bonding structure. Consequently, this work lays the foundation for a detailed characterization of the lignome in different plant species, mutants, and transgenics and for the MS-based sequencing of lignin oligomers and (neo)lignans.
authors.affiliation: Department of Plant Systems Biology, VIB, B-9052 Ghent, Belgium. kris.morreel@psb.vib-ugent.be
authors.forename: Kris
authors.initials: K
authors.lastname: Morreel
authors.forename: Hoon
authors.initials: H
authors.lastname: Kim
authors.forename: Fachuang
authors.initials: F
authors.lastname: Lu
authors.forename: Oana
authors.initials: O
authors.lastname: Dima
authors.forename: Takuya
authors.initials: T
authors.lastname: Akiyama
authors.forename: Ruben
authors.initials: R
authors.lastname: Vanholme
authors.forename: Claudiu
authors.initials: C
authors.lastname: Niculaes
authors.forename: Geert
authors.initials: G
authors.lastname: Goeminne
authors.forename: Dirk
authors.initials: D
authors.lastname: Inzé
authors.forename: Eric
authors.initials: E
authors.lastname: Messens
authors.forename: John
authors.initials: J
authors.lastname: Ralph
authors.forename: Wout
authors.initials: W
authors.lastname: Boerjan
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D005740:Gases / Q000737:chemistry; D008031:Lignin / Q000737:chemistry* / Q000378:metabolism; D013058:Mass Spectrometry / Q000379:methods*; D055442:Metabolome
chemical_list: D005740:Gases; D008031:Lignin