Skip to Main Content
Density functional theory study of spirodienone stereoisomers in ligninAuthor(s): Thomas Elder; Laura Berstis; Gregg T. Beckham; Michael F. Crowley
Source: ACS Sustainable Chemistry & Engineering
Publication Series: Scientific Journal (JRNL)
Station: Southern Research Station
Download Publication (2.0 MB)
DescriptionThe spirodienone structure in lignin is a relatively recent discovery, and it has been found to occur in lignin of various plant species at concentrations of ∼3%, which is sufficiently high to be important for better understanding of its properties and reactivity. The cyclic structure, with a β-1 bond, has been proposed to be a precursor for acyclic β-1 linkages in lignin. Previous analytical work has revealed the presence, but not the absolute configuration, of two stereoisomeric forms of spirodienone. The objective of the current work was to determine if there are thermodynamic differences that could help identify the experimentally observed stereoisomers. Results from density functional theory calculations reveal the presence of clusters of stereoisomers with varying stability that may be of use in narrowing the list of possible structures. Furthermore, the bond dissociation enthalpy of the cyclic ring exhibited a particularly high value for the C−O cleavage reaction relative to more conventional ether bonds in lignin, perhaps due to limited electron delocalization possibilities.
- You may send email to email@example.com to request a hard copy of this publication.
- (Please specify exactly which publication you are requesting and your mailing address.)
- We recommend that you also print this page and attach it to the printout of the article, to retain the full citation information.
- This article was written and prepared by U.S. Government employees on official time, and is therefore in the public domain.
CitationElder, Thomas; Berstis, Laura; Beckham, Gregg T.; Crowley, Michael F. 2017. Density functional theory study of spirodienone stereoisomers in lignin. ACS Sustainable Chemistry & Engineering. 5(8): 7188-7194. 7 p. https://doi.org/10.1021/acssuschemeng.7b01373.
KeywordsLignin, Spirodienone, Density functional theory, Stereoisomerism, Bond dissociation energy
- Radical nature of C- lignin
- Model lignin oligomer pyrolysis: Coupled conformational and thermodynamic analysis of β-O-4′ bond cleavage
- The application of computational chemistry to lignin
XML: View XML