Analyte and matrix evaporability - key players of low-temperature plasma ionization for ambient mass spectrometry.

The introduction of ambient ionization at atmospheric pressure for mass spectrometry (AI-MS) attracted the interest of many researchers in the field and various ionization techniques have been described in recent years that allow a quick and easy-to-handle analysis of samples under ambient conditions without or with only minor sample preparation. Among those, plasma-based techniques including the low-temperature plasma probe require very little resources thereby providing great potential for implementation in mobile analytical devices. However, systematic studies on signal responsiveness with this technique, such as the influence of the analyte and matrix characteristics on relative signal intensity, are still rare. Therefore, we used a low-temperature plasma source based on dielectric barrier discharge with helium as process gas to assess influencing factors on signal intensity in mass spectrometry. Among 12 tested molecular descriptors, in particular a low vaporization enthalpy and a large molecular nonpolar surface area improve the relative signal intensity. In addition, we show that the impact of compound characteristics strongly outperforms the influence of simple sample matrices such as different organic solvents and water, with a weak trend that volatile solvents tend to decrease the signal responsiveness of the analytes. However, several specific solvent-analyte interactions occurred, which have to be considered in targeted applications of this method. Our results will help further in improving the implementation and standardization of low-temperature plasma ionization for ambient mass spectrometry and understanding the requirements and selectivity of this technique. Graphical abstract Influencing factors (analyte and matrix characteristics) on signal intensity in dielectric-barrier discharge plasma for ionization in mass spectrometry.