Development of an inverse low-temperature plasma ionization source for liquid chromatography/mass spectrometry.

RATIONALE: An argon inverse low-temperature plasma (iLTP) ionization source for liquid chromatography/tandem mass spectrometry was developed. The iLTP is constructed from simple chromatographic supply materials and is implemented into an atmospheric pressure chemical ionization (APCI) source replacing the APCI discharge needle electrode. The newly developed ion source was coupled to an ultra-high-performance liquid chromatography (UHPLC) system. METHODS: The argon iLTP was characterized by optical emission spectroscopy. The soft ionization of selected standards was also demonstrated by direct infusion experiments. In addition to the use of argon as the discharge gas, helium, synthetic air, and oxygen were used, which were tested for their performance using testosterone and vitamin D3 . RESULTS: Spectroscopic measurements of the argon plasma were conducted, demonstrating the main emission band of argon metastables with corresponding energies of 11.53 eV and 11.72 eV. Infusion experiments indicate a gentle ionization by iLTP, e.g. caffeine, testosterone, reserpine, vitamin D3 , and 25-hydroxyvitamin D3 , which resulted in the corresponding protonated molecules. The splitless coupling with UHPLC (possible flow rates >1000 µL min-1 ) shows promising results in interday repeatability (n = 10) for the substances with a relative standard deviation of less than 5% and limits of detection for caffeine, testosterone, reserpine, vitamin D3 , and 25-hydroxyvitamin D3 of 10 ng L-1 , 50 ng L-1 , 500 ng L-1 , 5 µg L-1 , and 5 µg L-1 , respectively. CONCLUSIONS: The argon iLTP ion source presented in this work shows promising approaches in the field of ionization of small organic molecules. The mechanism related to the discharge gas argon has not been elucidated so far and further investigations are needed. The iLTP ion source shows a very good performance with UHPLC coupling, even at increased flow rates. It could be shown that an argon iLTP can compete with the helium dielectric barrier discharge (DBD) preferred in the literature, making it a more economical choice.