Abstract
A new set of reactions that involve fluorine have been investigated in chemical reaction interface mass spectrometry (CRIMS). The primary goal of this study was to provide a means to selectively detect phosphorus-containing compounds, which fluorine does by generating PF 5 . P F 4 + , the main fragment ion of PF 5 , provides a sensitive (10 pg/s), selective, and linear (> 10 5 dynamic range) channel for phosphorus-containing analytes. This fluorine-rich environment also provides new ways to selectively and simultaneously detect hydrogen isotopes, chlorine, and sulfur. NF 3 as a reactant gas provides the most comprehensive array of elemental and isotopic detection yet available for CRIMS. An application of phosphorus-selective detection was attempted by examination of a plasma sample from a patient who had been treated with cyclophosphamide. The phosphorus-selective channel showed six peaks: one is derivatized phosphate, two are t -butyldimethylsilyl (TBDMS) derivatives of cyclophosphamide, another two are TBDMS derivatives of 4-hydroxy-yclophosphamide, and one is from underivatized cyclophosphamide. The simultaneous detection of chlorinecontaining compounds confirmed our results for those peaks related to cyclophosphamide and its metabolite.
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