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Ambient desorption/ionization (ADI) sources coupled to mass spectrometer have gained increasing interest in the field of analytical chemistry for its fast and direct analysis of samples. Among many ADI sources, plasma-based ADI sources are an important branch. Despite its extensive use in mass spectrometry analysis, the ionization mechanism of these sources still remain uncertain. The study on ionization mechanism is of great significance to optimize the design of ion sources and to improve ionization efficiency. In this study, targeted research on a better understanding of afterglow distance effects on ionization process was conducted. Based on the quantified signal expression of reagent ions in mass spectrum, the concept that optimal atmospheric analysis distance of plasma ADI source is defined for the first time. From the perspective of mutual restriction effect between atmospheric components, the formation progress of reagent ions was visually revealed in detail, which involved the initial step of forming precursor reagent ions, the clusters reaction for increasing production of reagent ions, and the matrix effect results in reagent ion depletion. The formation mechanism of reagent ions further clarified the explicit reason for abundant reagent ions generated at an optimal distance. Most importantly, the analyte analysis results verified the significant impact of appropriate distance on ionization efficiency in afterglow region. It was confirmed that the quantity and type of reagent ions intimately influenced the status of analyte ions in mass spectrum.

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Proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) has proven to be more and more essential in online monitoring technologies of volatile organic compounds (VOCs). A key component in the PTR-TOFMS instrument is...