Stochastic dynamic quantitative and 3D structural matrix assisted laser desorption/ionization mass spectrometric analyses of mixture of nucleosides

The paper tackles issue of solid-state 3D structural analysis by means of matrix assisted laser desorp-tion/ionization mass spectrometry with a view of our innovative stochastic dynamic new simplistic formula D (SD) = 2.6388.10(-17).(< I-2 > -< I >(2)). It represents a universal law, which is obeyed by temporal behavior of experimental variable intensity of any analyte peak of ion, measured in solution under soft-ionization electrospray ionization, collision induced dissociation and atmospheric pressure chemical ion-ization conditions, respectively. The equation connects between so-called stochastic dynamic diffusion pa-rameter , D (SD), and variable intensity, I, determined per any span of scan time of a measurement. So far, it has been proven empirically, that D (SD) parameters of MS ions reflect exactly analyte concentration in solution - a claim independently verified via chromatography - and provide exact information about 3D molecular and electronic structure of molecular species in liquid phase. Herein, we urge that this simplistic formula is a fundamental law also valid to MALDI-MS phenomena; thus, providing exact quantitative and 3D molecular structural information about analytes in solid-state; or, mass spectrometric phenomena in condensed phases are governed by one and the same stochastic dynamic law, which is applicable both to quantitative and 3D analyses of analytes. The latter statement underlines a crucial advantage of the functional relation and emphasizes on incapability of other known fundamental MS theories and equation to deal with simultaneous exact quantitative and 3D structural analyses in the two condensed phases. A body of new empirical evidence is directed to favor the view of application of the model equation to MALDI-MS processes, examining guanosine (1) in mixture of N(2),N(2)-dimethyl guanosine, quan-titatively and 3D structurally, with respect to different experimental conditions without, and involving different sample matrix com ponents. The ultra-high accuracy mass spectrometric outcomes are treated by chemomerics. The same is true for utilizing high accuracy quantum chemical static and molecular dynamics in order to correlate experimental mass spectrometric with theoretical quantum chemical data on 3D molecular and electronic structures of nucleosides, their fragment species and energetics in gas and condensed phases. There are detailed subtle electronic effects on various tautomers, ionization processes, radical-ion formation MS reactions, chemical rearrangement, charge and (doubly) proton transfer effects; if any. (C)& nbsp;2022 Elsevier B.V. All rights reserved.

Automated summary

This paper introduces a simplified formula for solid-state 3D structural analysis using matrix assisted laser desorption/ionization mass spectrometry. The formula provides a universal law for analyzing the behavior of analyte peaks in solution and connects the stochastic dynamic diffusion parameter with variable intensity. The formula has been shown to accurately reflect analyte concentration and provide information about molecular and electronic structure. Its application to MALDI-MS phenomena is explored, demonstrating its advantages over other existing theories and equations.