Reactive Olfaction Ambient Mass Spectrometry.

Chemical ionization of organic compounds with negligible vapor pressures (VP) is achieved at atmospheric pressure when the proximal sample is exposed to corona discharge. The vapor-phase analyte is produced through a reactive olfaction process, which is determined to include electrostatic charge induction in the proximal condensed-phase sample, resulting in the liberation of free particles. With no requirement for physical contact, a new contained nano-atmospheric pressure chemical ionization (nAPCI) source was developed that allowed direct mass spectrometry analysis of complex mixtures at a sample consumption rate less than nmol/min. The contained nAPCI source was applied to analyze a wide range of samples including the detection of 1 ng/mL cocaine in serum and 200 pg/mL caffeine in raw urine, as well as the differentiation of chemical composition of perfumes and beverages. Polar (e.g., carminic acid; estimated VP 5.1 × 10-25 kPa) and nonpolar (e.g., vitamin D2; VP 8.5 × 10-11 kPa) compounds were successfully ionized by the contained nAPCI ion source under ambient conditions, with the corresponding ion types of 78 other organic compounds characterized.