A stochastic dynamic mass spectrometric diffusion method and its application to 3D structural analysis of the analytes

Abstract

There is a straightforward line in the recent development of the functional model connecting the experimental mass spectrometric variable intensity of a peak of an analyte ion with its thermodynamic, kinetic and diffusion parameters. It has been shown that the temporal behavior of the outcome intensity obeys a certain law: ${{\text{D}}_{{\text{SD}}}}{\text{ }} = {\text{ }}1.3193{\text{ }} \times {\text{ }}{10^{ - 14}}{\text{ }} \times {\text{ }}A{\text{ }} \times {\text{ }}{{(\overline {{I^2}} - {{(\bar I)}^2})} \over {{{(I - \bar I)}^2}}}.$ This formula is universally applicable and empirically testable and verifiable. It connects the intensity with the so-called stochastic dynamic diffusion “DSD” parameter. Its application to small-scale research, so far, using soft-ionization electrospray, atmospheric pressure chemical ionization, matrix-assisted laser desorption/ionization or collision-induced dissociation methods has shown that the DSD parameter is linearly connected with the so-called quantum chemical diffusion parameter “DQC,” obtained within Arrhenius’s theory. Therefore, the DSD parameter connects experimental measurable parameters of ions with their three-dimensional (3D) molecular and electronic structures. The corroborated empirical proof, so far, has convincingly argued that the mass spectrometry appears to be not only a robust instrumentation for highly accurate, precise and selective quantification but also is capable of providing the exact 3D molecular structure of the analytes, when it is used complementary to high accuracy methods of the computational quantum chemistry.

Electrospray ionization mass spectrometric solvate cluster and multiply charged ions: a stochastic dynamic approach to 3D structural analysis

“…Despite the empirical verifiability of model Eqs. (1)- (3), which has been demonstrated not only in this work, but also in few of our previous contributions devoted to the same issue, we shall have more to say about the functional relationship between the D SD -parameter and the statistical fitting parameter 'A' , which is obtained as a result from curve-fitting approach used to connect the experimental measurable outcome-intensity and diffusion parameters according to our formulas. This is a common approach to fit calculated diffusions to corresponding experimental data depending on the theoretical diffusion concept.…”

“…The current paper addresses the 3D structural analysis of solvate clusters and multiply charged species in presence of Zn II -ion containing metal-organics of small molecules by means of electrospray ionization mass spectrometry (ESI-MS) and our model formulas (1)- (4) developed more recently [1][2][3][4][5] as powerful approaches to treat quantitatively the experimental variable intensity (I) of analyte's peaks.…”

“…For the purposes of this study we would like to emphasise that the D SD -parameter correlates linearly with the D QC -one, thus, establishing a direct connection of MS outcomes and other experimental factors with 3D molecular and electronic structures of the analytes. The chemometrics of a small-scale research, so far, has shown correlation coefficients |r|= 0.9557 5 -0.9998 1 looking at D QC and D SD data of organics and metal-organics [3]. The correlation between theory and experiment according to Eq.…”

“…(3) yields to |r|> 0.9999 4 [6]. This contribution offers the reader a study of solvate species and multiply charged solvent containing complexes, which quantitative and structural determination by mass spectrometry represents significant analytical challenge, despite, superior method performances of the instrumentation [1][2][3][4][5] At first consideration the reader might suppose that the observation of such clusters and multiply charged cations are a typical phenomenon under ESI-MS conditions. Thus, this issue, presumably, can be regarded as a well-studied problem, due to enormous effort devoted to develop MS methodology for analytical purposes over decades [7][8][9][10][11][12][13][14][15][16].…”

“…To sum up, throughout this paper we puts a very strong emphasis on applicability of our stochastic dynamic (SD) concept [1][2][3][4][5][6] and Eqs. (1), (2) and (4) to quantity and determine 3D structurally not only molecular ions of analytes, but also very complex and challenging from the perspective of the experimental MS and theoretical quantum chemistry analytes such as clusters of charged solvents and multiply charged species.…”