Investigation of ion-solvent interactions in electrospray ionization mass spectrometry / vorgelegt von Christine Polaczek. Wuppertal, August 2021
Inhalt
- 1 Scope of this Work
- 2 Introduction
- 2.1 Transferring Ions from the Solution to the Gas Phase
- 2.1.1 Solvation of Ions in Solution
- 2.1.2 Production of Charged Droplets by Electrospray
- 2.1.3 Formation of Gas-Phase Ions from Charged Droplets
- Solvation and Location of Ions in Nanodroplets
- Ion Evaporation Model (IEM)
- Charged Residue Model (CRM)
- Chain Ejection Model (CEM)
- 2.1.4 Charge State Distribution of Gas-Phase Ions
- 2.2 Transferring Ions to the Mass Analyzer and Detector
- 3 Methods
- 3.1 Experimental Methods
- 3.2 Computational Methods
- 4 Results and Discussion: Substance P
- 4.1 Gas Phase Modification
- 4.2 Combined Solution Phase and Gas Phase Modification
- 4.3 Collision Induced Dissociation
- 4.4 Charge Retention/Charge Depletion Model
- 4.5 Summary and Conclusions
- 5 Results and Discussion: Terminal Alkyldiamines
- 5.1 Gas Phase Modification: Charge Depletion vs. Charge Retention
- 5.1.1 Observed Ion Population
- Influence of the Solution Composition
- Impact of Gas Phase Modification by ACN and MeOH
- Influence of the Chemical Structure of the Diamines
- Average Cluster Number of [M(ACN)nH2]2+
- 5.1.2 Average Charge State
- Impact of the Alkyl Chain Length in Terminal Alkyldiamines
- Impact of the Location of Modifier Addition: Source vs. Capillary
- 5.1.3 Impact of Gas Phase Modification on CID
- 5.2 Chemical Modification of the Collision Gas
- 5.2.1 Measurement Procedure
- 5.2.2 Variation of the Cooling Time: Gas Phase Modification
- 5.2.3 Variation of the Cooling Time: Collision Gas Modification
- 5.2.4 Investigation of the Reaction Kinetics
- 5.2.5 Implications of Chemical Modification of the Collision Gas for Mass Analysis
- 5.3 Theoretical Investigations of Ion-Solvent Clusters
- 5.3.1 Cluster Structures and Thermochemistry
- 5.3.2 Cluster Distributions
- 5.3.3 Collision Cross Sections and Ion Mobilities
- 5.4 Proton Transfer Processes to Solvent Clusters
- 5.5 Summary and Conclusions
- 6 Conclusions and Outlook
- List of Tables
- List of Figures
- List of Abbreviations
- Bibliography