title: Environmentally persistent free radicals (EPFRs). 3. Free versus bound hydroxyl radicals in EPFR aqueous solutions.
abstract: Additional experimental evidence is presented for in vitro generation of hydroxyl radicals because of redox cycling of environmentally persistent free radicals (EPFRs) produced after adsorption of 2-monochlorophenol at 230 °C (2-MCP-230) on copper oxide supported by silica, 5% Cu(II)O/silica (3.9% Cu). A chemical spin trapping agent, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed. Experiments in spiked O(17) water have shown that ∼15% of hydroxyl radicals formed as a result of redox cycling. This amount of hydroxyl radicals arises from an exogenous Fenton reaction and may stay either partially trapped on the surface of particulate matter (physisorbed or chemisorbed) or transferred into solution as free OH. Computational work confirms the highly stable nature of the DMPO-OH adduct, as an intermediate produced by interaction of DMPO with physisorbed/chemisorbed OH (at the interface of solid catalyst/solution). All reaction pathways have been supported by ab initio calculations.
authors.affiliation: Department of Chemistry, Louisiana State University , Baton Rouge, Louisiana 70803, United States.
authors.forename: Lavrent
authors.initials: L
authors.lastname: Khachatryan
authors.forename: Cheri A
authors.initials: CA
authors.lastname: McFerrin
authors.forename: Randall W
authors.initials: RW
authors.lastname: Hall
authors.forename: Barry
authors.initials: B
authors.lastname: Dellinger
mesh_terms: D000327:Adsorption; D002733:Chlorophenols / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D003497:Cyclic N-Oxides / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D017665:Hydroxyl Radical / Q000737:chemistry*; D052638:Particulate Matter / Q000737:chemistry; D012822:Silicon Dioxide / Q000737:chemistry; D012996:Solutions
chemical_list: D002733:Chlorophenols; D003497:Cyclic N-Oxides; D052638:Particulate Matter; D012996:Solutions; D017665:Hydroxyl Radical; C069977:2,2-dimethyl-5-hydroxy-1-pyrrolidinyloxy; D012822:Silicon Dioxide; D003300:Copper; C030683:2-chlorophenol; C000520:cuprous oxide