title: A Fundamental Tandem Mass Spectrometry Study of the Collision-Activated Dissociation of Small Deprotonated Molecules Related to Lignin.
abstract: The collision-activated fragmentation pathways and reaction mechanisms of 34 deprotonated model compounds representative of lignin degradation products were explored experimentally and computationally. The compounds were evaporated and ionized by using negative-ion mode electrospray ionization doped with NaOH to produce abundant deprotonated molecules. The ions were isolated and subjected to collision-activated dissociation (CAD). Their fragment ions were then isolated and also subjected to CAD. This was repeated until no further fragmentation was observed (up to MS6). This approach enabled the identification of characteristic reaction pathways and delineation of reasonable fragmentation mechanisms for deprotonated molecules containing various functional groups. The varying fragmentation patterns observed for different types of compounds allow for the identification of the functionalities in these compounds. This information was utilized to identify the presence of specific functionalities and their combinations in molecules in an organosolv lignin sample.
authors.affiliation: Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 47907, USA.
authors.forename: Christopher L
authors.identifier: http://orcid.org/0000-0001-5157-8337
authors.initials: CL
authors.lastname: Marcum
authors.affiliation: Merck & Co., 126 E Lincoln Ave, Rahway, NJ, 07065, USA.
authors.forename: Tiffany M
authors.initials: TM
authors.lastname: Jarrell
authors.affiliation: Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 47907, USA.
authors.forename: Hanyu
authors.identifier: http://orcid.org/0000-0002-3873-7417
authors.initials: H
authors.lastname: Zhu
authors.affiliation: Agilent Technologies, Inc., 201 Hansen Ct #108, Wood Dale, IL, 60191, USA.
authors.forename: Benjamin C
authors.identifier: http://orcid.org/0000-0003-3919-0780
authors.initials: BC
authors.lastname: Owen
authors.affiliation: 1300 Barbour Way, Rising Sun, IN, 47040, USA.
authors.forename: Laura J
authors.initials: LJ
authors.lastname: Haupert
authors.affiliation: School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN, 47907, USA.
authors.forename: Mckay
authors.initials: M
authors.lastname: Easton
authors.affiliation: Center for Renewable Carbon, University of Tennessee, 2506 Jacob Drive, Knoxville, TN, 37996, USA.
authors.forename: Omid
authors.initials: O
authors.lastname: Hosseinaei
authors.affiliation: Center for Renewable Carbon, University of Tennessee, 2506 Jacob Drive, Knoxville, TN, 37996, USA.
authors.forename: Joseph
authors.initials: J
authors.lastname: Bozell
authors.affiliation: Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 47907, USA.
authors.forename: John J
authors.identifier: http://orcid.org/0000-0003-2925-8710
authors.initials: JJ
authors.lastname: Nash
authors.affiliation: Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN, 47907, USA.
authors.forename: Hilkka I
authors.identifier: http://orcid.org/0000-0001-8988-6984
authors.initials: HI
authors.lastname: Kenttämaa
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D004952:Esters / Q000737:chemistry; D008031:Lignin / Q000737:chemistry*; D010636:Phenols / Q000737:chemistry; D011522:Protons; D053719:Tandem Mass Spectrometry
chemical_list: D000447:Aldehydes; D002264:Carboxylic Acids; D004952:Esters; D010636:Phenols; D011522:Protons; D008031:Lignin
keywords: collision-activated dissociation; lignin; liquid chromatography; mass spectrometry; reaction mechanisms