Determination of phenols by flow injection and liquid chromatography with on-line quinine-sensitized photo-oxidation and quenched luminol chemiluminescence detection

An on-line quinine-sensitized photo-oxidation with quenched chemiluminescence (CL) detection method is developed for phenols using flow injection (171) and liquid chromatography (LC). This detection method is based on the decrease of light emission from the luminol CL reaction due to the photo-oxidation of phenols that scavenge the photogenerated reactive oxygen species (e.g. singlet oxygen (O-1(2)) and superoxide (O-2(.-))). On-line photo-oxidation is achieved using a coil photo-reactor made from fluoroethylene-propylene copolymer tubing (3048 mm x 0.25 mm i.d.) coiled around a mercury UV lamp. A buffer of pH 7 and a concentration of 350 muM for quinine sulfate are determined optimum for the sensitized photo-oxidation. Using a carrier system flow rate of 60 mul/min, calibration curves taken by FI for 10 phenolic compounds in aqueous solutions showed this decreasing sensitivity order: 4-chlorophenol, phenol, 4-nitrophenol, 3-hydroxy-L-kynurenine, 2-nitrophenol, salicylate, 3-nitrophenol, catechol, 2,4-dinitrophenol, and 2,4-dichlorophenol. This detection method using two tandem coil photo-reactors is also applied for the LC separation of phenol, 4-nitrophenol and 4-chlorophenol on an octadecyl (C18) silica LC column using acetonitrile-H2O (40:60, v/v) as a mobile phase. The quenched CL detection limits (about 1 muM or 20 pmol) for phenol and 4-chlorophenol are comparable to those for UV detection at 254 nm. Some selectivity in the quenched CL detection is evident by no interference in the FI phenol response even when benzaldehyde and phenethanol concentrations are 8 and 15 times that of phenol. (C) 2003 Elsevier B.V. All rights reserved.