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: ${{\text{D}}_{{\text{SD}}}}{\text{ }} = {\text{ }}1.3193{\text{ }} \times {\text{ }}{10^{ - 14}}{\text{ }} \times {\text{ }}A{\text{ }} \times {\text{ }}{{(\overline {{I^2}} - {{(\bar I)}^2})} \over {{{(I - \bar I)}^2}}}.$DSD = 1.3193 × 10−14 × A × (I2¯−(I¯)2)(I−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.

Keywords

• 3d structural analysis
• diffusion
• mass spectrometry
• quantum chemistry