A pitfall of using 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile as a matrix in MALDI TOF MS: chemical adduction of matrix to analyte amino groups
Article first published online: 20 SEP 2010
Copyright © 2010 John Wiley & Sons, Ltd.
Journal of Mass Spectrometry
Volume 45, Issue 10, pages 1195–1202, October 2010
How to Cite
Lou, X., de Waal, B. F. M., van Dongen, J. L. J., Vekemans, J. A. J. M. and Meijer, E. W. (2010), A pitfall of using 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile as a matrix in MALDI TOF MS: chemical adduction of matrix to analyte amino groups. J. Mass Spectrom., 45: 1195–1202. doi: 10.1002/jms.1814
- Issue published online: 12 OCT 2010
- Article first published online: 20 SEP 2010
- Manuscript Accepted: 23 AUG 2010
- Manuscript Received: 30 JUN 2010
- matrix adduction;
- MALDI TOF MS;
- analyte-matrix reaction
2-[(2E)-3-(4-tert-Butylphenyl)-2-methylprop-2-enylidene]malononitrile (DCTB) has been considered as an excellent matrix for matrix-assisted laser desorption/ionization (MALDI) of many types of synthetic compounds. However, it might provide troublesome results for compounds containing aliphatic primary or secondary amino groups. For these compounds, strong extra ion peaks with a mass difference of 184.1 Da were usually observed, which might falsely indicate the presence of some unknown impurities that were not detected by other matrices. On the basis of the possible mechanisms proposed, these extra ions are the products of nucleophilic reactions between analyte amino groups and DCTB molecules or radical cations. In these reactions, an amino group replaces the dicyanomethylene group of DCTB forming a matrix adduct via a CN-bond. An aliphatic primary amine could react easily with DCTB and the reaction could start once they are mixed in a MALDI solution. For an aliphatic secondary amine, on the other hand, the reaction most likely occurs in the gas phase. Protonation of amino groups by adding acid seems to be a useful way to stop DCTB adduction for compounds with one single amino group, but not for compounds with multiple amino groups. Unlike aliphatic primary or secondary amines, aliphatic tertiary amines and aromatic amines do not yield DCTB adducts. This is because tertiary amines do not have the required transferrable H-(N) atom to form an extra CN-bond, while aromatic amines are not sufficiently nucleophilic to attack DCTB. In view of the possible matrix adduction, care should be taken in MALDI time-of-flight mass spectrometry (TOF MS) when DCTB is used as the matrix for compounds containing amino group(s). Copyright © 2010 John Wiley & Sons, Ltd.