Acetonitrile Adduct Formation as a Sensitive Means for Simple Alcohol Detection by LC-MS

Abstract

Simple alcohols formed protonated acetonitrile adducts containing up to two acetonitrile molecules when analyzed by ESI or APCI in the presence of acetonitrile in the solvent. These acetonitrile adducts underwent dissociation to form a nitrilium ion, also referred to as the substitution ion. Diols and triols behaved differently. In ESI, they formed only one acetonitrile adduct containing one acetonitrile. The S ion was not observed in ESI and was only weakly observed from the dissociation of the (M + ACN + H)(+) ion. On the other hand, the S ion was abundantly formed from the diols in APCI. This formation of acetonitrile adducts and substitution ion from simple alcohols/diols offers an opportunity to detect simple alcohols/diols sensitively by LC-MS interfaced by ESI or APCI. The utility of this chemistry was demonstrated in a method developed for the quantification of cyclohexanol in rat plasma by monitoring the CID-induced fragmentation from the S ion to a fragment ion.

Isolation of cytotoxic cycloartane triterpenoids from Dysoxylum malabaricum

“…Compounds featuring a basic alcohol moiety exhibited acetonitrile adducts, consistent with the prevalent use of acetonitrile as the primary solvent in mass spectrometry quantification. 19 The DNP database showed 17 hits, further narrowed to 14 by adding the search query ‘molecular formula’ corresponding to C30. Furthermore, several spectral properties were identical to compounds 1–3 and showed a fused cyclopropane ring.…”

Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors

“…Such a solvent specific mass spectral response gives an impression that the signal of [M+10] + might be an acetonitrile adduct ion [ 8 ]. A parallel experiment has been then conducted in water/d 3 -acetonitrile.…”

Comprehensive degradation profiling and influence of different oxidizing reagents on tinoridine hydrochloride: Structural characterization of its degradation products using HPLC and HRMS

“…The degradation of the drug to DP 1 is a typical ester hydrolysis under the basic condition 13,14 . DP 2 was formed in the presence of co‐solvent (acetonitrile) through a two‐step reaction: (i) Ritter reaction, followed by (ii) a new bond formation between amine and electron‐deficient carbon of nitrile 13–16 . DP 3 was formed by aromatic hydroxylation in the acidic condition, which was observed in the case of nadifloxacin 17 .…”