Search

This study uses a rapid tandem mass‐spectrometry method to determine water content in complex organic solutions. Emphasis is placed on trace‐water analysis by a fast and accurate alternative to the Karl–Fischer method. In this new method, water is captured by a charge‐labeled molecular probe. Water binds strongly with high specificity to the strongly electrophilic aldehyde site in a charge‐labelled molecule (N‐methylpyridinium); competitive binding by other analytes is effectively discriminated against in the mass‐measurement step. Quantitative determinations are made over a wide concentration range, 0.001 % (10 ppm) to 99 %, with better than 10 % relative standard deviation, along with short (1 min) analysis times using small sample volumes (several μL). Applications include water measurement in simple organic solvents, for example, deuterated solvents, as well as in complex mixtures, for example, organic reaction mixtures. Additionally, this method allows for water monitoring in levitated droplets. Mechanistic investigations into the impact of water on important chemical processes in organic synthesis and environmental science are reported. [ABSTRACT FROM AUTHOR]