title: An ab initio molecular dynamics analysis of lignin as a potential antioxidant for hydrocarbons.
abstract: Lignins are complex phenolic polymers with limited industrial uses. To identify new applications of lignins, this study aims to evaluate the conifer alcohol lignin as a potential antioxidant for hydrocarbons, using the petroleum asphalt as an example. Using the ab initio molecular dynamics (AIMD) method, the evaluation is accomplished by tracking the generation of critical species in a lignin-asphalt mixture under a simulated oxidative condition. The generation of new species was detected using nuclear magnetic resonance and four analytical methods including density of states analysis, highest occupied molecular orbital and lowest unoccupied molecular orbital analyses, bonding and energy level analysis, and electrostatic potential energy analysis. Results of the analyses show that the chemical radicals of carbon, nitrogen and sulfur generated in the oxidation process could enhance the agglomeration and/or decomposition tendency of asphalt. The effectiveness of lignins as an antioxidant depends on their chemical compositions. Lignins with a HOMO-LUMO gap larger than the HOMO-LUMO gap of the hydrocarbon system to be protected, such as the conifer alcohol lignin to protect petroleum asphalt as was studied in this work, do not demonstrate beneficial anti-oxidation capacity. Lignins, however, may be effective oxidants for hydrocarbon systems with a larger HOMO-LUMO gap. In addition, lignins may contain more polar sites than the hydrocarbons to be protected; thus the lignins' hydrophobicity and compatibility with the host hydrocarbons need to be well evaluated. The developed AIMD model provides a useful tool for developing antioxidants for generic hydrocarbons.
authors.affiliation: Department of Civil, Architectural and Environmental Engineering, Illinois Institute of Technology, 3201 S. Dearborn St. Alumni Memorial Hall 215, Chicago, IL 60616, United States. Electronic address: tpan@iit.edu.
authors.forename: Tongyan
authors.initials: T
authors.lastname: Pan
authors.affiliation: Department of Civil, Architectural and Environmental Engineering, Illinois Institute of Technology, 3201 S. Dearborn St. Alumni Memorial Hall 215, Chicago, IL 60616, United States. Electronic address: ccheng20@hawk.iit.edu.
authors.forename: Cheng
authors.initials: C
authors.lastname: Cheng
mesh_terms: D000975:Antioxidants; D008031:Lignin / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D056004:Molecular Dynamics Simulation; D010084:Oxidation-Reduction; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D000975:Antioxidants; D008031:Lignin
keywords: Ab initio molecular dynamics; Hydrocarbon oxidation; Lignin