title: Substituent Effects on the Photodeprotection Reactions of Selected Ketoprofen Derivatives in Phosphate Buffered Aqueous Solutions.
abstract: Photodeprotection is an important reaction that has been attracting broad interest for use in a variety of applications. Recent advances in ultrafast and vibrational time-resolved spectroscopies can facilitate obtaining data to help unravel the reaction mechanisms involving in the photochemical reactions of interest. The kinetics and reaction mechanisms for the photodeprotection reactions of ketoprofen derivatives containing three different substituents (ibuprofen, Br and I) were investigated by femtosecond transient absorption (fs-TA) and nanosecond time-resolved resonance Raman (ns-TR(3)) spectroscopy methods in phosphate buffered solutions (PBS). Fs-TA allows us to detect the decay kinetics of the triplet species as the key precursor for formation of a carbanion species for three different substituents attached to ketoprofen. To characterize the structural and electronic properties of the corresponding carbanion and triplet intermediates, TR(3) spectroscopic experiments were conducted. The transient spectroscopy work reveals that the different substituents affect the photodecarboxylation reaction to produce carbon dioxide which in turn influences the generation of the carbanion species which determines the rate of the photorelease of the functional groups attached on the ketoprofen parent molecule. The fingerprint TR(3) spectroscopy results suggest that ketoprofen derivatives may be deactivated to produce a triplet carbanion when increasing the atom mass of the halogen atoms.
authors.affiliation: Department of Chemistry, the University of Hong Kong, Pokfulam Road, Hong Kong.
authors.forename: Mingyue
authors.initials: M
authors.lastname: Liu
authors.affiliation: Department of Chemistry, the University of Hong Kong, Pokfulam Road, Hong Kong.
authors.forename: Ming-De
authors.initials: MD
authors.lastname: Li
authors.affiliation: Department of Chemistry, the University of Hong Kong, Pokfulam Road, Hong Kong.
authors.forename: Jinqing
authors.initials: J
authors.lastname: Huang
authors.affiliation: Department of Chemistry, the University of Hong Kong, Pokfulam Road, Hong Kong.
authors.forename: Tianlu
authors.initials: T
authors.lastname: Li
authors.affiliation: Department of Chemistry, the University of Hong Kong, Pokfulam Road, Hong Kong.
authors.forename: Han
authors.initials: H
authors.lastname: Liu
authors.affiliation: Department of Chemistry, the University of Hong Kong, Pokfulam Road, Hong Kong.
authors.forename: Xuechen
authors.initials: X
authors.lastname: Li
authors.affiliation: Department of Chemistry, the University of Hong Kong, Pokfulam Road, Hong Kong.
authors.forename: David Lee
authors.initials: DL
authors.lastname: Phillips
mesh_terms: D000838:Anions / Q000737:chemistry*; D002021:Buffers; D007660:Ketoprofen / Q000737:chemistry*; D007700:Kinetics; D008027:Light; D010710:Phosphates / Q000737:chemistry; D055668:Photochemical Processes; D011789:Quantum Theory; D012996:Solutions / Q000528:radiation effects; D013059:Spectrum Analysis, Raman; D014732:Vibration; D014867:Water / Q000737:chemistry*
chemical_list: D000838:Anions; D002021:Buffers; D010710:Phosphates; D012996:Solutions; D014867:Water; D007660:Ketoprofen