Utility of solution electrochemistry mass spectrometry for investigation the formation and detection of biologically important conjugates of acetaminophen

A Thin-Layer Electrochemical Flow Cell Coupled On-Line with Electrospray-Mass Spectrometry for the Study of Biological Redox Reactions

“…Our experiment reacting benzene thiol with oxidized dopamine showed that this nucleophile produced monodi-, and tri-addition products like that observed in the reaction of oxidized dopamine with the biogenic nucleophile glutathione. This experiment demonstrates that addition of these or other nucleophiles to the analyte solution before or after [13] the analyte¯ows through the cell should be a powerful means to study such biologically relevant chemical followup reactions. Post-cell addition of nucleophilic reagents would allow easy to oxidize species to be reacted because they do not have to travel through the cell.…”

“…All of their work made use of a commercially available, three electrode¯ow through cell, comprised of a porous reticulated vitreous carbon (RVC) working electrode, and Pd counter and reference electrodes. Using the same type of cell, Getek, et al [13] studied the electrochemical generation of biologically relevant acetaminophen-glutathione conjugates with ECaTS-MS. Volk, Yost and Brajter-Toth [14] reviewed the ®eld of ECaMS up to 1992 as applied to the analysis of nonvolatile solution species.…”

On-line Liquid Chromatography and Circular Dichroism Detection of Stereo-isomers of α-Tocopherol Derivatives Generated by an Electrochemical Reaction

“…An electrochemical cell (EC) can be directly connected to a liquid chromatography/mass spectrometry (LC-MS) system; thus, the on-line oxidation-separation of a drug can be performed by EC-LC-MS. Reactive oxidation products with a short lifespan can be detected by the system, which can also provide similar oxidation products to drug metabolites by CYPs. [3][4][5] Without authentic standards of the metabolites, it may not be possible to elucidate the structure of oxidation products by MS, or MS/MS alone; therefore, we have improved the electrochemical reaction system to obtain sufficient oxidation products for a NMR study. 6 The electrochemical reaction has also been used to prepare a chiral compound.…”

On-line electrochemistry/liquid chromatography/mass spectrometry for the simulation of pesticide metabolism

“…Soon it became clear that this newly developed technique offers interesting features for the simulation of drug metabolism. While off-line electrochemical models for cytochrome P450 metabolism reactions were investigated by Shono et al [6,7], and Hanzlik et al [8,9], Getek et al reported first achievements in the on-line coupling of electrochemistry to mass spectrometry for the simulation of drug metabolism [10]. They studied the electrochemical oxidation of paracetamol to N-acetyl-p-quinoneimine in a commercially available flow-through cell comprising a glassy carbon working electrode with a large surface area and the subsequent reaction of the quinoneimine with the bioavailable thiols glutathione and cysteine.…”