Towards the electrospray ionization mass spectrometry ionization efficiency scale of organic compounds

An approach that allows setting up under predefined ionization conditions a rugged self-consistent quantitative experimental scale of electrospray ionization (ESI) efficiencies of organic compounds is presented. By ESI ionization efficiency (10 we mean the efficiency of generating gas-phase ions from analyte molecules or ions in the ESI source. The approach is based on measurement of relative ionization efficiency (RIE) of two compounds (B-1 and B-2) by infusing a solution containing both compounds at known concentrations (C-1 and C-2) and measuring the mass-spectrometric responses of the protonated forms of the compounds (R-1 and R-2). The RIE of B-1 and B-2 is expressed as logRIE(B-1, B-2) = log[(R-1 - C-2)/(C-1 - R-2)]. The relative way of measurement leads to cancellation of many of the factors affecting IE (ESI source design, voltages in the source and ion transport system, solvent composition, flow rates and temperatures of the nebulizing and drying gases). Using this approach an ESI IE scale containing ten compounds (esters and aromatic amines) and spanning over 4 logRIE units has been compiled. The consistency of the scale (the consistency standard deviation of the scale is s = 0.16 logRIE units) was assured by making measurements using different concentration ratios (at least 6-fold concentration ratio range) of the compounds and by making circular validation measurements (the logRIE of any two compounds was checked by measuring both against a third compound). Copyright (c) 2008 John Wiley & Sons, Ltd.