Stochastic dynamic electrospray ionization mass spectrometric diffusion parameters and 3D structural determination of complexes of AgI–ion – Experimental and theoretical treatment

Abstract

The paper deals with determination of mass spectrometric diffusion parameters (DSD) based on our stochastic dynamic approach to treat quantitatively the experimental variable “intensity” of observable peaks of analyte ions with respect to different spans of the scan time. There has been derived, more recently, the following model equation DtotSD=Sum/in(DiSD)=Sum/in{1.3194.10−17·Ai·((<I2i>−<Ii>2)/<(Ii−<Ii>)2>)}. Our next interpretation of the mutual relations among mass spectrometric DSD parameter according to the equation written above, the experimental outcome “intensity” and the temperature “T” results in new model equation ln{<(Ii−<Ii>)2>}=−ln{−(ln(kB·T/m))3·((2·Δt·T·kB)/(m·DSD))}, which is applied to metal organics for the first time in the literature in this paper. Therefore, the ultimate goal of this study is twofold. First, we examine how empirical arguments of electrospray ionization mass spectra of metal–organics of AgI–ion of mandelic acid (1) and (3) as well as 2-hydroxy-4-sulfo-benzoic (2) acid support for validity of the new theoretical model, which is tested on metal–organics for the first time in the literature. Second, one of the aims is to provide a reliable approach to quantify exactly the isotope MS shape of complexes of AgI–ion allowing for an unambiguous determination of such analytes in mixture. Thus, we detail the intensity ration of the mass spectrometric isotope shapes over the time within different experimental conditions, making correlation among diffusion parameters based on the equations written above and the “quantum chemical diffusion parameter” (DQC) of ions obtained within the Arrhenius's approximation. Our model equations have ambition of providing exact methodological tool to determine experimentally the 3D molecular and electronic structures of the analytes on the base on a correlative study between DSD and DQC parameters or by a complementary use to high resolution mass spectrometric and high accuracy theoretical quantum chemical methods. In this context, we tackle the problematic on the correlation between the intensity ratio of the isotope sub peaks and the multidimensional molecular structure of complex species with each of the isotopes of 107,109Ag–ion. As a corollary, our research shows excellent coefficient of statistical correlation among the mentioned above theoretical models. The contribution provides, therefore, very important insights into the mutual connections among experimental measurable mass spectrometric outcomes; experimental factors, for instance, the temperature, as among the most important factor determining the ionization efficiency of the analyte ions; and 3D molecular conformational and electronic structure of AgI–containing metal–organics. The contribution, therefore, addresses serious shortcomings with the applicability of the mass spectrometry to exact multidimensional structural analysis and to quantify the intensity of the isotope shapes, unambiguously. Because of, the model equations written above and universally applicable, empirically testable and credible models applicable to not only different mass spectrometric methods, but also to different analytes and a broad spectrum of experimental parameters.