Evaluation of potential reaction mechanisms leading to the formation of coniferyl alcohol a-linkages in lignin: a density functional theory study
- Earth & Environmental Systems Inst. (EESI), Penn State Univ., State College, PA (United States)
- Center for NanoCellulosics (CNC), Penn State Univ., State College, PA (United States)
- Center for Lignocellulose Structure and Formation (CLSF), Penn State Univ., State College, PA (United States)
Five potential reaction mechanisms, each leading to the formation of an α-O-4-linked coniferyl alcohol dimer, and one scheme leading to the formation of a recently proposed free-radical coniferyl alcohol trimer were assessed using density functional theory (DFT) calculations. These potential reaction mechanisms were evaluated using both the calculated Gibbs free energies, to predict the spontaneity of the constituent reactions, and the electron-density mapped Fukui function, to determine the most reactive sites of each intermediate species. The results indicate that each reaction in one of the six mechanisms is thermodynamically favorable to those in the other mechanisms; what is more, the Fukui function for each free radical intermediate corroborates with the thermochemical results for this mechanism. This mechanism proceeds via the formation of two distinct free-radical intermediates, which then react to produce the four α-O-4 stereoisomers.
- Research Organization:
- Energy Frontier Research Centers (EFRC) (United States). Center for Lignocellulose Structure and Formation (CLSF)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- SC0001090
- OSTI ID:
- 1065685
- Journal Information:
- Physical Chemistry Chemical Physics. PCCP (Print), Vol. 13, Issue 47; Related Information: CLSF partners with Pennsylvania State University (lead); North Carolina State University; University of Rhode Island; Virginia Tech University; ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
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