The Nature and Kinetic Analysis of Carbon-Carbon Bond Fragmentation Reactions of Cation Radicals Derived from SET-Oxidation of Lignin Model Compounds

Author

Adam Pimentel

Publication Date

2-8-2011

Abstract

The lignin peroxidase promoted α-carbon β-carbon bond cleavage of two diastereomeric pairs of dimeric lignin model compounds were investigated to determine which structural units are more readily cleaved. These model compounds, β-1 (1,2-diaryl-1,3-propanediol) and β-O-4 (1-diaryl-2-aryloxy-1,3-propanediol), represent the most common structural units present in the plant cell wall polymer lignin. The lignin peroxidase catalyzed reaction mechanism was shown to parallel two mechanistically well understood systems, the cerric (IV) ammonium nitrate promoted chemical reacton, and the dicyannoanthracene promoted photochemical reaction, both of which proceed by a SET mechanism. Product profiles and kinetic rate constants were determined and compared for all four model compounds by HPLC and Stopped Flow kinetic techniques.

Language

English

Keywords

Lignocellulosic, Biomass

Document Type

Thesis

Degree Name

Chemistry and Chemical Biology

Level of Degree

Masters

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Mariano, Patrick

Second Committee Member

Wang, Wei

Recommended Citation

Pimentel, Adam. "The Nature and Kinetic Analysis of Carbon-Carbon Bond Fragmentation Reactions of Cation Radicals Derived from SET-Oxidation of Lignin Model Compounds." (2011). https://digitalrepository.unm.edu/chem_etds/47