Abstract
The electrospray ionisation–ion-trap mass spectrometry (ESI–MSn) of selected drugs with nitrogen-containing saturated ring structures has been investigated. Sequential product-ion fragmentation experiments (MSn) have been performed to elucidate degradation pathways for the [M+H]+ ions and their predominant fragment ions. These MSn experiments result in characteristic fragmentations in which functional groups are generally cleaved from the ring systems as neutral molecules such as H2O, amines, alkenes, esters, carboxylic acids, etc. When such a nitrogen-containing drug molecule also contains a functional group, such as an ester, that on liberation as a neutral molecule has a significantly lower −ΔH f° value than that of the corresponding amine then the former is preferentially liberated. Furthermore, when an aromatic entity is present in these drug molecules together with the nitrogen-containing saturated ring structure fragmentation of the latter ring occurs with the former, predictably, being resistant to fragmentation. The structures of fragment ions proposed for ESI–MSn can be supported by electrospray ionisation–quadrupole time-of-flight mass spectrometry (ESI–QTOFMS). The data presented in this paper therefore provide useful information on the structure of these heterocyclic compounds which could be used to characterise unknown drug compounds isolated from natural sources, for example.
Similar content being viewed by others
References
Joyce C, Smyth WF, Ramachandran VN, O’Kane E, Coulter D (2004) Anal Bioanal Chem, submitted for publication
Long PW, Risperidone Drug Monograph, Internet Mental Healthhttp://www.mentalhealth.com/drug/p30-r05.html
Song FR, Cui M, Liu SY (1999) Rapid Commun Mass Spectrom 13:478
Ishii A, Tanaka M, Kurihara R, Watanabe-Suzuki K, Kumazawa T, Seno H, Suzuki O, Katsumata Y (2003) J Chromatogr B 792:117
Remmerie BMM, Sips LAA, de Vries R, de Jong J, Schothius AM, Hooijschuur EWJ, van de Merbel NC (2003) J Chromatogr B 783:461
Brown TL, LeMay HE (1985) Chemistry, The Central Science. Prentice–Hall, New Jersey, USA, p 201
Fuh M-R, Tai Y-L, Pan WHT (2001) J Chromatogr B 752:107
Aggarwal S, Ghosh NN, Aneja R, Joshi H, Chandra R (2002) Rapid Commun Mass Spectrom 16:923
Concannon S, Ramachandran VN, Smyth WF (2000) Rapid Commun Mass Spectrom 14:1157
Concannon S, Ramachandran VN, Smyth WF (2000) Rapid Commun Mass Spectrom14:2260
Alebic-Kolbah T, Zavitsanos AP (1997) J Chromatogr A 759:65
Eerkes A, Addison T, Naidong W (2002) J Chromatogr B 768:277
Bogusz MJ, Kruger KD, Maier RD, Erkwoh R, Tuchtenhagen (1999) J Chromatogr B 732:257
Dienes-Nagy A, Rivier L, Giroud C, Augsburger M, Mangin P (1999) J Chromatogr A 854:109
Patton E, O’Donnell F (2002 and 2003) MRes theses, University of Ulster
Smyth WF, Joyce C, Ramachandran VN, O’Kane E, Coulter D (2004) Anal Chim Acta, in print
McClean S, Robinson RC, Shaw C, Smyth WF (2002) Rapid Commun Mass Spectrom 16:346
Smyth WF, McClean S, Ramachandran VN (2000) Rapid Commun Mass Spectrom 14:2061
Conneely A, McClean S, Smyth WF, McMullan G (2001) Rapid Commun Mass Spectrom, 15:2076
Smyth WF (2003) Anal Chim Acta 492:1
Acknowledgements
The authors would like to thank The Forensic Science Agency of Northern Ireland, Carrickfergus, Northern Ireland for kind provision of drug samples.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Smyth, W.F., Ramachandran, V.N., O’Kane, E. et al. Characterisation of selected drugs with nitrogen-containing saturated ring structures by use of electrospray ionisation with ion-trap mass spectrometry. Anal Bioanal Chem 378, 1305–1312 (2004). https://doi.org/10.1007/s00216-003-2414-z
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-003-2414-z