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Combining chip-ESI with APLI (cESILI) as a multimode source for analysis of complex mixtures with ultrahigh-resolution mass spectrometry

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Abstract

Recently we have established atmospheric-pressure laser ionisation (APLI) as a method for coupling time-of-flight mass spectrometric detectors (TOF MS) with chromatographic systems (HPLC and GC) to allow two-photon ionisation of non-polar aromatic compounds. Here we demonstrate that APLI can be combined with chip-electrospray ionisation (cESI) coupled to Fourier-transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) for ultrahigh-resolution analysis of complex samples. With the laser turned off, the analytes are ionised only by ESI, whereas when the laser is switched on non-polar aromatic substances also are ionised. In combination with the extremely high mass resolution of an FT-ICR MS, simultaneous qualitative analysis of polar and non-polar analytes is possible in both positive and negative modes, as is exemplified with a crude oil sample. Nevertheless, ion suppression was observed (up to ca. 70% for D10-pyrene) and thus sample preparation with chromatographic or electrophoretic pre-separation is necessary for quantitative analysis of targets. In addition, for the first time, the dopant-assisted APLI method in combination with cESI (DA-cESILI) was used for determination of 1-nitrocoronene.

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Acknowledgements

We are grateful to Coherent Inc. (Munich, Germany) for the loan of the Existar XS laser. Silvia Marqués and Juan José González of the Instituto Español de Oceanografíais are acknowledged for kindly providing a sample of the crude oil.

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Correspondence to Oliver J. Schmitz.

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Philippe Schmitt-Kopplin, Klaus J. Brockmann and Oliver J. Schmitz contributed equally to the work.

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Schmitt-Kopplin, P., Englmann, M., Rossello-Mora, R. et al. Combining chip-ESI with APLI (cESILI) as a multimode source for analysis of complex mixtures with ultrahigh-resolution mass spectrometry. Anal Bioanal Chem 391, 2803–2809 (2008). https://doi.org/10.1007/s00216-008-2211-9

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  • DOI: https://doi.org/10.1007/s00216-008-2211-9

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