UVPD Spectroscopy of Differential Mobility-Selected Prototropic Isomers of Rivaroxaban

Two ion populations of protonated Rivaroxaban, [C19H18ClN3O5S + H](+), are separated under pure N-2 conditions using differential mobility spectrometry prior to characterization in a hybrid triple quadrupole linear ion trap mass spectrometer. These populations are attributed to bare protonated Rivaroxaban and to a proton-bound Rivaroxaban-ammonia complex, which dissociates prior to mass-selecting the parent ion. Ultraviolet photodissociation (UVPD) and collision-induced dissociation (CID) studies indicate that both protonated Rivaroxaban ion populations are comprised of the computed global minimum prototropic isomer. Two ion populations are also observed when the collision environment is modified with 1.5% (v/v) acetonitrile. In this case, the protonated Rivaroxaban ion populations are produced by the dissociation of the ammonium complex and by the dissociation of a proton-bound Rivaroxaban-acetonitrile complex prior to mass selection. Again, both populations exhibit a similar CID behavior; however, UVPD spectra indicate that the two ion populations are associated with different prototropic isomers. The experimentally acquired spectra are compared with computed spectra and are assigned to two prototropic isomers that exhibit proton sharing between distal oxygen centers.

Automated summary

Two ion populations of protonated Rivaroxaban are separated using differential mobility spectrometry under different conditions, showing similarities in CID behavior but distinct prototropic isomers based on UVPD spectra. The populations are attributed to bare protonated Rivaroxaban and to complexes with ammonia or acetonitrile, which dissociate prior to mass selection. Comparisons with computed spectra suggest proton sharing between distal oxygen centers in the identified prototropic isomers.