Going beyond electrospray: mass spectrometric studies of chemical reactions in and on liquids

Abstract

Recently developed and applied ionization techniques have brought mass spectrometry to bear on previously inaccessible chemistry. We offer our perspective on this field and its application for studying reaction mechanisms.

Catalytic Carbonylative Spirolactonization of Hydroxycyclopropanols

“…Elimination of the spirolactone 16a and reoxidation of intermediate L would regenerate the [(neoc)PdOAc] + D . To provide support for this mechanism, the catalytic reactions were monitored by high resolution electrospray ionization mass spectrometry (ESI-MS) 31 in the presence of both O 2 and BQ using methods described previously. 32 ESI-MS was also performed on the reaction of partially deuterated substrate 15a-d 4 (Figure 4) to provide further evidence for structures of side products and reactive intermediates.…”

Ambient Mass Spectrometry Imaging Using Direct Liquid Extraction Techniques

“…21,138 In situ derivatization enables sensitive analysis of molecules that are not readily ionized using soft ionization techniques. 139,140 For example, reactive DESI experiments with Girard T (GT) reagent 140 and betaine aldehyde (BA) 141 (shown in Scheme 1) have been used for detecting and imaging cholesterol in tissue sections.…”

Electrospray Modifications for Advancing Mass Spectrometric Analysis

“…Some of the important parameters which determine the ion signals in DESI-MS are incident angle of spray, collection angle of secondary droplets, distance between sprayer and surface, composition and ow rate of spray solvent, and type of surface. 107) Over the years, DESI-MS has been applied in wide areas such as forensics, 106,108) biology, [109][110][111] chemistry, [112][113][114][115][116] imaging, 117,118) and cancer diagnostics. [119][120][121][122] Another related technique known as desorption sonic-spray ionization (DeSSI) 123) also uses the desorption phenomena like DESI.…”