title: Mechanistic analysis of ultrasound assisted enzymatic desulfurization of liquid fuels using horseradish peroxidase.
abstract: This study has attempted to gain physical insight into ultrasound-assisted enzymatic desulfurization using system comprising horseradish peroxidase enzyme and dibenzothiophene (DBT). Desulfurization pathway (comprising DBT-sulfoxide and DBT-sulfone as intermediates and 4-methoxy benzoic acid as final product) has been established with GC-MS analysis. Intrinsic fluorescence and circular dichroism spectra of ultrasound-treated enzyme reveal conformational changes in secondary structure (reduction in α-helix and β-conformations and increase in random coil content) leading to enhancement in activity. Concurrent analysis of desulfurization profiles, Arrhenius and thermodynamic parameters, and simulations of cavitation bubble dynamics reveal that strong micro-convection generated by sonication enhances enzyme activity and desulfurization kinetics. Parallel oxidation of DBT by radicals generated from transient cavitation gives further boost to desulfurization kinetics. However, random motion of enzyme molecules induced by shock waves reduces frequency factor and limits the ultrasonic enhancement of enzymatic desulfurization.
authors.affiliation: Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam, India.
authors.forename: Jaykumar
authors.initials: J
authors.lastname: Bhasarkar
authors.affiliation: Center for Energy, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam, India.
authors.forename: Arup Jyoti
authors.initials: AJ
authors.lastname: Borah
authors.affiliation: Center for Energy, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam, India; Department of Biosciences and Bioengineering, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam, India.
authors.forename: Pranab
authors.initials: P
authors.lastname: Goswami
authors.affiliation: Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam, India; Center for Energy, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam, India. Electronic address: vmoholkar@iitg.ernet.in.
authors.forename: Vijayanand S
authors.initials: VS
authors.lastname: Moholkar
mesh_terms: D001272:Atmosphere; D002942:Circular Dichroism; D003198:Computer Simulation; D019220:High-Energy Shock Waves; D006735:Horseradish Peroxidase / Q000378:metabolism*; D007700:Kinetics; D013058:Mass Spectrometry; D010084:Oxidation-Reduction; D017433:Protein Structure, Secondary; D013010:Sonication; D013050:Spectrometry, Fluorescence; D013455:Sulfur / Q000378:metabolism*; D013816:Thermodynamics; D013876:Thiophenes / Q000378:metabolism; D014465:Ultrasonics / Q000379:methods*
chemical_list: D013876:Thiophenes; D013455:Sulfur; D006735:Horseradish Peroxidase; C016366:dibenzothiophene
keywords: Cavitation; Desulfurization; Horseradish peroxidase; Secondary structure; Ultrasound