title: Ultraviolet irradiation-induced substitution of fluorine with hydroxyl radical for mass spectrometric analysis of perfluorooctane sulfonyl fluoride.
abstract: A rapid and solvent free substitution reaction of a fluorine atom in perfluorooctane sulfonyl fluoride (PFOSF) with a hydroxyl radical is reported. Under irradiation of ultraviolet laser on semiconductor nanoparticles or metal surfaces, hydroxyl radicals can be generated through hole oxidization. Among all fluorine atoms of PFOSF, highly active hydroxyl radicals specifically substitute the fluorine of sulfonyl fluoride functional group. Resultant perfluorooctane sulfonic acid is further ionized through capture of photo-generated electrons that switch the neutral molecules to negatively charged odd electron hypervalent ions. The unpaired electron subsequently initiates α O-H bond cleavage and produces perfluorooctane sulfonate negative ions. Hydroxyl radical substitution and molecular dissociation of PFOSF have been confirmed by masses with high accuracy and resolution. It has been applied to direct mass spectrometric imaging of PFOSF adsorbed on surfaces of plant leaves.
authors.affiliation: Mass Spectrometry Center for Structural Identification of Biological Molecules and Precision Medicine, Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079, PR China.
authors.forename: Peng
authors.initials: P
authors.lastname: Wang
authors.affiliation: Mass Spectrometry Center for Structural Identification of Biological Molecules and Precision Medicine, Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079, PR China.
authors.forename: Xuemei
authors.initials: X
authors.lastname: Tang
authors.affiliation: Mass Spectrometry Center for Structural Identification of Biological Molecules and Precision Medicine, Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079, PR China.
authors.forename: Lulu
authors.initials: L
authors.lastname: Huang
authors.affiliation: Mass Spectrometry Center for Structural Identification of Biological Molecules and Precision Medicine, Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079, PR China.
authors.forename: Jie
authors.initials: J
authors.lastname: Kang
authors.affiliation: Mass Spectrometry Center for Structural Identification of Biological Molecules and Precision Medicine, Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079, PR China. Electronic address: hyzhong@mail.ccnu.edu.cn.
authors.forename: Hongying
authors.initials: H
authors.lastname: Zhong
mesh_terms: D017738:Alkanesulfonic Acids / Q000032:analysis*; D005461:Fluorine / Q000737:chemistry*; D005466:Fluorocarbons / Q000032:analysis*; D017665:Hydroxyl Radical / Q000737:chemistry*; D013058:Mass Spectrometry / Q000379:methods*; D014466:Ultraviolet Rays
chemical_list: D017738:Alkanesulfonic Acids; D005466:Fluorocarbons; D005461:Fluorine; D017665:Hydroxyl Radical; C076994:perfluorooctane sulfonic acid
keywords: Hydroxyl radical; Imaging mass spectrometry; Perfluorooctane sulfonyl fluoride; Plant chemicals; Substitution