James Edward Cooley

Determination of stimulants using gas chromatography/high-resolution time-of-flight mass spectrometry and a soft ionization source

RATIONALE The aim of this study was to investigate the mass spectral fragmentation of a small set of stimulants in a high-resolution time-of-flight mass spectrometer equipped with a soft ionization source using vacuum ultraviolet (VUV) photons emitted from different plasma gases. It was postulated that the use of a plasma gas such as Xe, which emits photons at a lower energy than Kr or Ar, would lead to softer ionization of the test compounds, and thus to less fragmentation. METHODS A set of nine stimulants: cocaine, codeine, nicotine, methadone, phenmetrazine, pentylenetetrazole, niketamide, fencamfamine, and caffeine, was analyzed by gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) in positive ion mode with this soft ionization source, using either Xe, Kr, or Ar as plasma gases. Working solutions of the test compounds at 0.1 to 100 ng/μL were used to establish instrument sensitivity and linearity. RESULTS All test compounds, except methadone and pentylenetetrazole, exhibited strong molecular ions and no fragmentation with Xe-microplasma photoionization (MPPI). Methadone exhibited significant fragmentation not only with Xe, but also with Kr and Ar, and pentylenetetrazole could not be ionized with Xe, probably because its ionization energy is above 8.44 eV. The Kr- and Ar-MPPI mass spectra of the test compounds showed that the relative intensity of the molecular ion decreased as the photon energy increased. CONCLUSIONS When coupled to a TOF mass spectrometer this soft ionization source has demonstrated signal-to-noise (S/N) ratios from 7 to 730 at 100 pg per injection (depending on the compound), and a dynamic range of three orders of magnitude (100 pg to 100 ng) for some of the test compounds.

Properties of microplasmas excited by microwaves for VUV photon sources

Microplasma sources typically take advantage of pd (pressure × size) scaling by increasing pressure to operate at dimensions as small as tens of microns. In many applications, low pressure operation is desirable, which makes miniaturization difficult. In this paper, the characteristics of low pressure microplasma sources excited by microwave power are discussed based on results from experimental and computational studies. The intended application is production of VUV radiation for chemical analysis, and so emphasis in this study is on the production of resonant excited states of rare gases and radiation transport. The systems of interest operate at a few to 10 Torr in Ar and He/Ar mixtures with cavity dimensions of hundreds of microns to 1 mm. Power deposition is a few watts which produces fractional ionization of about 0.1%. We found that production of VUV radiation from argon microplasmas at 104.8 nm and 106.7 nm saturates as a function of power deposition due to a quasi-equilibrium that is established between the electron temperature (that is not terribly sensitive to power deposition) and the population of the Ar(4s) manifold.