Abstract
An improved atmospheric pressure chemical ionization (APCI II) source for gas chromatography–high-resolution time-of-flight mass spectrometry (GC–HRTOFMS) was compared to its first-generation predecessor for the analysis of fatty acid methyl esters, methoxime-trimethylsilyl derivatives of metabolite standards, and cell culture supernatants. Reductions in gas turbulences and chemical background as well as optimized heating of the APCI II source resulted in narrower peaks and higher repeatability in particular for late-eluting compounds. Further, APCI II yielded a more than fourfold median decrease in lower limits of quantification to 0.002–3.91 μM along with an average 20 % increase in linear range to almost three orders of magnitude with R 2 values above 0.99 for all metabolite standards investigated. This renders the overall performance of GC–APCI–HRTOFMS comparable to that of comprehensive two-dimensional gas chromatography (GC × GC)–electron ionization (EI)–TOFMS. Finally, the number of peaks with signal-to-noise ratios greater than 20 that could be extracted from metabolite fingerprints of pancreatic cancer cell supernatants upon switching from the APCI I to the APCI II source was more than doubled. Concomitantly, the number of identified metabolites increased from 36 to 48. In conclusion, the improved APCI II source makes GC–APCI–HRTOFMS a great alternative to EI-based GC–MS techniques in metabolomics and other fields.
Similar content being viewed by others
References
Dunn WB (2008) Phys Biol 5:011001
McEwen CN, McKay RG (2005) J Am Soc Mass Spectrom 16:1730–1738
Schiewek R, Lorenz M, Giese R, Brockmann K, Benter T, Gab S, Schmitz OJ (2008) Anal Bioanal Chem 392:87–96
Carrasco-Pancorbo A, Nevedomskaya E, Arthen-Engeland T, Zey T, Zurek G, Baessmann C, Deelder AM, Mayboroda OA (2009) Anal Chem 81:10071–10079
Pacchiarotta T, Nevedomskaya E, Carrasco-Pancorbo A, Deelder AM, Mayboroda OA (2010) J Biomol Tech 21:205–213
Wachsmuth CJ, Almstetter MF, Waldhier MC, Gruber MA, Nürnberger N, Oefner PJ, Dettmer K (2011) Anal Chem 83:7514–7522
Strehmel N, Kopka J, Scheel D, Böttcher C (2014) Metabolomics 10:324–336
Jaeger C, Tellström V, Zurek G, König S, Eimer S, Kammerer B (2014) Metabolomics 10:859–876
Wachsmuth CJ, Dettmer K, Lang SA, Mycielska ME, Oefner PJ (2014) Anal Chem 86:9186–9195
Barrow MP, Peru KM, Headley JV (2014) Anal Chem 86:8281–8288
David F, Sandra P, Hancock P (2011) LC-GC Eur 24:16–19
Garcia-Villalba R, Pacchiarotta T, Carrasco-Pancorbo A, Segura-Carretero A, Fernandez-Gutierrez A, Deelder AM, Mayboroda OA (2011) J Chromatogr A 1218:959–971
Portoles T, Mol JG, Sancho JV, Hernandez F (2012) Anal Chem 84:9802–9810
Matysik S, Schmitz G, Bauer S, Kiermaier J, Matysik FM (2014) Biochem Biophys Res Commun 446:751–755
Bristow T, Harrison M, Sims M (2010) Rapid Commun Mass Spectrom 24:1673–1681
Klee S, Thinius M, Brockmann KJ, Benter T (2014) Rapid Commun Mass Spectrom 28:1591–1600
Östman P, Luosujärvi L, Haapala M, Grigoras K, Ketola RA, Kotiaho T, Franssila S, Kostiainen R (2006) Anal Chem 78:3027–3031
Almstetter MF, Appel IJ, Dettmer K, Gruber MA, Oefner PJ (2011) J Chromatogr A 1218:7031–7038
Benjamini Y, Hochberg Y (1995) J Roy Stat Soc Ser B 57:289–300
R-Development Core-Team (2007) R: a language and environment for statistical computing. R Foundation for Statistical Computing: Vienna, Austria
van den Dool H, Kratz PD (1963) J Chromatogr 11:463–471
Dettmer K (2014) Anal Bioanal Chem 406:4931–4939
Pacchiarotta T, Derks RJ, Hurtado-Fernandez E, van Bezooijen P, Henneman A, Schiewek R, Fernandez-Gutierrez A, Carrasco-Pancorbo A, Deelder AM, Mayboroda OA (2013) Bioanalysis 5:1515–1525
Villas-Bôas SG, Smart KF, Sivakumaran S, Lane GA (2011) Metabolites I:3–20
Kaspar H, Dettmer K, Gronwald W, Oefner PJ (2008) J Chromatogr B Anal Technol Biomed Life Sci 870:222–232
Sumner LW, Amberg A, Barrett D, Beale MH, Beger R, Daykin CA, Fan TW, Fiehn O, Goodacre R, Griffin JL, Hankemeier T, Hardy N, Harnly J, Higashi R, Kopka J, Lane AN, Lindon JC, Marriott P, Nicholls AW, Reily MD, Thaden JJ, Viant MR (2007) Metabolomics 3:211–221
Strehmel N, Hummel J, Erban A, Strassburg K, Kopka J (2008) J Chromatogr B Anal Technol Biomed Life Sci 871:182–190
Acknowledgments
We are grateful to Dr. Maria Mycielska and Dr. Sven Lang from the Department of Surgery/University Hospital Regensburg (Regensburg, Germany) for providing the supernatant samples. Funding by DFG (KFO 262, DE 835/2-1) is gratefully acknowledged. We thank Dr. Thomas Arthen-Engeland from Bruker Daltonics (Bremen, Germany) for fruitful discussions and support throughout the study and the provision of Fig. 1.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Additional information as noted in text. This material is available free of charge via the Internet at http://pubs.acs.org.
ESM 1
(PDF 58 kb)
Rights and permissions
About this article
Cite this article
Wachsmuth, C.J., Hahn, T.A., Oefner, P.J. et al. Enhanced metabolite profiling using a redesigned atmospheric pressure chemical ionization source for gas chromatography coupled to high-resolution time-of-flight mass spectrometry. Anal Bioanal Chem 407, 6669–6680 (2015). https://doi.org/10.1007/s00216-015-8824-x
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-015-8824-x