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The use of hydrazine-based derivatization reagents for improved sensitivity and detection of carbonyl containing compounds using MALDI-MSI

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Abstract

Hydrazine-based derivatization reagents have been used to detect the presence of the carbonyl containing glucocorticoid fluticasone proprionate in rat lung tissue by MALDI-MSI. Such reagents also act as a matrix for analysis by MALDI-MS and have been termed “reactive matrices”. Cryosections of rat lung tissue (12 μm), spotted with a range of concentrations of fluticasone proprionate, were derivatized in situ with 2,4-dinitrophenylhydrazine (DNPH) and 4-dimethylamino-6-(4-methoxy-1-naphthyl)-1,3,5-triazine-2-hydrazine (DMNTH) by the use of an acoustic reagent spotter. It has been demonstrated that DMNTH gave superior results compared to DNPH and that analysis of samples immediately after application of DMNTH resulted in the detection of the protonated hydrazone derivative ([MD + H]+) of fluticasone propionate at a concentration of 500 ng/μL. It has been further shown that a prolonged reaction time (~48 h) improves the detection limit of the protonated hydrazone derivative to 50 ng/μL and that improvements in sensitivity and limits of detection are obtained when a conventional MALDI matrix CHCA is employed in conjunction with the DNPH/DMNTH reactive matrix.

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Acknowledgments

This work was supported by a MRC case studentship from GlaxoSmithKline. The authors would also like to thank Professor Uwe Karst (University of Münster, Germany) for the kind donation of the reactive matrix DMNTH.

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Authors and Affiliations

  1. Biomedical Research Centre, Sheffield Hallam University, City Campus, Sheffield, S1 1WB, UK

    Bryn Flinders & Malcolm R. Clench

  2. GlaxoSmithKline, Gunnels Wood Road, Stevenage, Hertfordshire, SG1 2NY, UK

    Josie Morrell, Peter S. Marshall & Lisa E. Ranshaw

Authors
  1. Bryn Flinders
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  2. Josie Morrell
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  3. Peter S. Marshall
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  4. Lisa E. Ranshaw
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  5. Malcolm R. Clench
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Corresponding author

Correspondence to Malcolm R. Clench.

Additional information

Published in the topical collection Mass Spectrometry Imaging with guest editors Andreas Römpp and Uwe Karst.

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Flinders, B., Morrell, J., Marshall, P.S. et al. The use of hydrazine-based derivatization reagents for improved sensitivity and detection of carbonyl containing compounds using MALDI-MSI. Anal Bioanal Chem 407, 2085–2094 (2015). https://doi.org/10.1007/s00216-014-8223-8

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  • DOI: https://doi.org/10.1007/s00216-014-8223-8

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