We report on the development of a new laser-ionization (LI) source operating at atmospheric pressure (AP) for liquid chromatography/mass spectrometry (LC/MS) applications. APLI is introduced as a powerful addition to existing AP ionization techniques, in particular atmospheric-pressure chemical ionization (APCI), electrospray ionization (ESI), and atmospheric pressure photoionization (APPI). Replacing the one-step VUV approach in APPI with step-wise two-photon ionization strongly enhances the selectivity of the ionization process. Furthermore, the photon flux during an ionization event is drastically increased over that of APPI, leading to very low detection limits. In addition, the APLI mechanism generally operates primarily directly on the analyte. This allows for very efficient ionization even of non-polar compounds such as polycyclic aromatic hydrocarbons (PAHs). The APLI source was characterized with a MicroMass Q-Tof Ultima II analyzer. Both the effluent of an HPLC column containing a number of PAHs (benzo[a]pyrene, fluoranthene, anthracene, fluorene) and samples from direct syringe injection were analyzed with respect to selectivity and sensitivity of the overall system. The liquid phase was vaporized by a conventional APCI inlet (AP probe) with the corona needle removed. Ionization was performed through selective resonance-enhanced multi-photon ionization schemes using a high-repetition-rate fixed-frequency excimer laser operating at 248 nm. Detection limits well within the low-fmol regime are readily obtained for various aromatic hydrocarbons that exhibit long-lived electronic states at the energy level of the first photon. Only molecular ions are generated at the low laser fluxes employed ($1 MW/cm 2 ). The design and performance of the laser-ionization source are presented along with results of the analysis of aromatic hydrocarbons.
Recently we introduced atmospheric pressure laser ionization (APLI) as a complementary ionization method for coupling LC-MS systems (HPLC and CEC), allowing ionization of nonpolar aromatic compounds via near-resonant two-photon excitation. In this paper, we demonstrate that APLI with the same source enclosure as for LC coupling is also suited for hyphenation of GC with atmospheric-pressure ionization mass spectrometry. This technique permits the qualitative and quantitative determination of aromatic compounds in an ultralow concentration range, as we show here with polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and hetero-PAHs as examples. The outstanding sensitivity is demonstrated for chrysene, with a detection limit of 22 amol. Polar functional groups reduce the sensitivity, but after methylation or silylation, the analytes can also be determined very sensitively in complex matrixes, as is shown with 1-hydroxypyrene in urine.
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