Exact Quantifying of Mass Spectrometric Variable Intensity of Analyte Peaks with Respect to Experimental Conditions of Measurements – A Stochastic Dynamic Approach

Abstract

The study provides new function tested on labetalol in large infusion volumes (Vinf = 80-115 µL) via electrospray ionization mass spectrometry, tandem MS2–MS7 operation modes and collision energy: 0, 0.1, 10, 20, 25, 26, 30 and 35 eV, respectively. It is derived from the stochastic dynamic mass spectrometric equation D”SD = 2.6388.10-17.(<I2>-<I>2), which exactly quantifies analyte concentration in solution. Also, it determines 3D conformations and electronic structures. The description of mass spectrometric intensity data as random variables and the shown relation, there are written two new linear functions among D”SD parameters, average total intensity values of fragmentation peaks, infusion volume, and collision energy. They introduce covariance of datasets of variables per short span of scan time of ions in any experimental conditions “l” and “m”. They are: D”SD;m,l = D”SD,l + D”SD,m + 5.2776.10-17.{<Il.Im>–<Il>.<Im>}≈<Il>+<Im> and <Il>+<Im>≈|rl,m|.sd(yEr±)1.sd(yEr±)m. Those relations yields to new formula D”SD,l+ D”SD,m = |rl,m|.sd(yEr±)l.sd(yEr±)m, providing exact function of mass spectrometric variable intensity of any peaks of analyte ion in any two sets of experimental conditions of measurements and diffusion parameters according to the first formula. Correlation between theory and experiment of fragmentation processes of labetalol shows |r|=1–0.99999. Chemometrics is used.