The idea for this contribution has its root in exact formulas connecting between measurable variable intensity of mass spectrometric peak of analyte ion and its stochastic dynamic diffusion parameter introduced, more recently in our works devoted to quantitative mass spectrometry. Herein, we present innovative functional relations connecting among not only DSD- and I-parameters, but also the experimental factor temperature and the concentration of analyte in solution. The temperature is one of the most important parameter determining the ionization efficiency of analytes under soft-ionization mass spectrometric conditions.
The focus of the work is not only on outlining quantitative conjunctions among experimental factors, respectively, parameters; measurable outcomes; and molecular properties, but also to help readers achieve in-depth understanding of governing factors determining the ionization efficiency of analyte ions with respect to temperature at a molecular level. Another important aspect for studying is that, all theoretical proposals introduced, so far, are based on stochastic dynamics. The latter field, however, is very broad. It encompasses a large set of mathematical methods applicable to explain diverse phenomena not only in the Chemistry, but also in the Physics, Astronomy, Economy, and many more research areas.
The methodology used to our principle theory behind the derivation of model functional relations; our innovative empirical modification of known relationship; and corresponding definition of the DSD parameter as a function of the measurable variable intensity are based on Box-Müller method, Einstein’s concept of diffusion within his molecular kinetic theory of heat; the forward Fokker-Planck equation (or the forward Kolmogorov equation,) where we empirically modify the characteristic function diffusion and its (their) application to Ornstein-Uhlenbeck process; approximations to a Wiener process; Gillespie’s interpretation of Ornstein-Uhlenbeck process and its exact numerical solution, respectively.
Due to, complexity of many of the soft-ionization mass spectrometric phenomena and the interconnection of different concepts behind our stochastic dynamic theory of exact quantification of the variable intensity, we hope that the readers will be able to gain the background to the different mass spectrometric phenomena and theories to more advanced primary literature sources, which can be found in the corresponding reference sections.
Inhaltsverzeichnis (Table of Contents)
- Preface
- Acknowledgements
- Abbreviations
- Chapter 1. Temperature dependence on stochastic dynamic diffusion coefficients of heated electrospray ionization and atmospheric pressure chemical ionization mass spectrometric intensities of analyte ions of configurationally locked polyenes
- Abstract
- Introduction
- Experimental
- Materials and methods
- Chemometrics
- Method performances
- Results
- Mass spectrometric data
- Qualitative analysis
- Determination of the stochastic dynamic diffusion parameters
- Temperature dependence on stochastic dynamic diffusion parameters
- Mutual correlation between stochastic dynamic diffusion parameters and total intensity of analyte ions
- Discussion
- Conclusion
- Mass spectrometric data
- Reference
- Chapter 2. Quantification of the experimental mass spectrometric variable intensity with respect to the analyte concentration in solution — the stochastic dynamic approach
- Abstract
- Introduction
- Experimental
- Materials and methods
- Chemometrics
- Results
- Quantitative mass spectrometric analysis of steroids
- Figure of merits
- Mass spectrometric diffusion parameters according to the stochastic dynamic concept
- Quantitative mass spectrometric analysis of drug
- Quantitative mass spectrometric analysis of steroids
- Discussion
- Conclusion
- Reference
- Abstract
- Introduction
- Results and discussion
- Mass spectrometric analysis
- Figures of merit
- Determination of stochastic dynamic mass spectrometric diffusion parameters
- Correlative analysis between stochastic dynamic diffusion parameters and kinetics
- Temperature dependency of the stochastic dynamic diffusion parameters
- Theoretical analysis
- Assignment of experimental mass spectrometric peaks to molecular ions of organics
- Metal-organics of AgI -ion
- Thermodynamics of fragment reactions
- Correlations between stochastic dynamic and quantum chemical diffusion parameters
- Mass spectrometric analysis
- Conclusion
Zielsetzung und Themenschwerpunkte (Objectives and Key Themes)
This book focuses on the development of novel functional relationships between measurable mass spectrometric parameters and molecular properties, specifically the stochastic dynamic diffusion parameter (DSD). This parameter provides insights into the 3D structure and dynamics of molecules and offers a highly accurate, precise, and sensitive approach to quantitative analysis. The work aims to provide a theoretical framework and empirical validation for these relationships, bridging the gap between theory and experimental data.
- Quantitative connection between the DSD parameter and the intensity of analyte ions in mass spectrometry.
- Impact of temperature on the DSD parameter and its influence on ionization efficiency.
- Correlation between DSD parameters and kinetic parameters of fragment reactions.
- Use of the DSD parameter for 3D structural analysis in conjunction with quantum chemical calculations.
- Application of the developed methods to a diverse range of molecular systems, including steroids, drugs, and glycylhomopenta and glycylhomohexa peptides.
Zusammenfassung der Kapitel (Chapter Summaries)
Chapter 1 explores the relationship between the DSD parameter, temperature, and the intensity of analyte ions in mass spectrometry. The authors introduce a new functional relationship that accounts for temperature dependence and provides empirical evidence using heated electrospray ionization (HESI) and atmospheric pressure chemical ionization (APCI) mass spectra of configurationally locked polyenes.
Chapter 2 investigates the applicability of the DSD parameter for quantifying analyte concentrations in solution. The chapter presents a new formula that relates the DSD parameter to concentration and intensity, demonstrating its effectiveness using APCI and collision-induced dissociation (CID) mass spectra of steroids and a drug.
Chapter 3 delves into the use of the DSD parameter for 3D structural analysis of oligomeric associates of glycylhomopeptides and their AgI - complexes. The chapter explores correlations between DSD parameters and kinetic parameters, analyzes temperature dependence, and combines the DSD parameter with quantum chemical calculations for detailed 3D structural determination.
Schlüsselwörter (Keywords)
The key topics explored in this book include stochastic dynamics, mass spectrometry, diffusion, temperature, analyte concentration, 3D structural analysis, and quantitative analysis. The book delves into theoretical frameworks and empirical evidence for the novel DSD parameter, which offers a powerful tool for understanding molecular properties and carrying out precise quantitative analysis of various compounds.
- Arbeit zitieren
- Prof. Dr. Bojidarka Ivanova (Autor:in), Michael Spiteller (Autor:in), 2020, Quantitative Relations Among Temperature, Analyte Concentration in Solution, Stochastic Dynamic Diffusions and Mass Spectometric Variable Intensity, München, GRIN Verlag, https://www.grin.com/document/520262
