The formation of [M-H]+ ions in N-alkyl-substituted thieno[3,4-c]-pyrrole-4,6-dione derivatives during atmospheric pressure photoionization mass spectrometry
Kharbatia, Najeh M.
Amad, Maan H.
KAUST DepartmentAnalytical Chemistry Core Lab
Analytical Core Lab
Biological and Environmental Sciences and Engineering (BESE) Division
Center for Desert Agriculture
Chemical Science Program
Desert Agriculture Initiative
KAUST Solar Center (KSC)
Materials Science and Engineering Program
Physical Sciences and Engineering (PSE) Division
Supercomputing, Computational Scientists
Online Publication Date2014-10-09
Print Publication Date2014-11-30
Permanent link to this recordhttp://hdl.handle.net/10754/563793
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AbstractRESULTS [M-H]+ ions were observed under APPI conditions. The type of dopant and the length of the alkyl chain affected the formation of these ions. MS/MS fragmentation of [M-H]+ and [M + H]+ ions exhibited completely different patterns. Theoretical calculations revealed that the loss of hydrogen molecules from the [M + H]+ ions is the most favourable condition under which to form [M-H]+ ions.CONCLUSIONS [M-H]+ ions were detected in all the TPD derivatives studied here under the special experimental conditions during APPI, using a halogenated benzene dopant, and TPD containing substituted N-alkyl side chains with a minimum of four carbon atoms. Density functional theory calculations showed that for [M-H]+ ions to be formed under these conditions, the loss of hydrogen molecules from the [M + H]+ ions is proposed to be necessary.RATIONALE The formation of ions during atmospheric pressure photoionization (APPI) mass spectrometry in the positive mode usually provides radical cations and/or protonated species. Intriguingly, during the analysis of some N-alkyl-substituted thieno[3,4-c]pyrrole-4,6-dione (TPD) derivatives synthesized in our laboratory, unusual [M-H]+ ion peaks were observed. In this work we investigate the formation of [M-H]+ ions observed under APPI conditions.METHODS Multiple experimental parameters, including the type of ionization source, the composition of the solvent, the type of dopant, the infusion flow rate, and the length of the alkyl side chain were investigated to determine their effects on the formation of [M-H]+ ions. In addition, a comparison study of the gas-phase tandem mass spectrometric (MS/MS) fragmentation of [M + H]+ vs [M-H]+ ions and computational approaches were used.
SponsorsThe research reported here was supported by King Abdullah University of Science and Technology. In addition, the authors gratefully acknowledge Dr. Misjudeen Raji and research support from the Analytical Core Lab of King Abdullah University of Science and Technology, Saudi Arabia.