Vaikkinen , A , Kauppila , T J & Kostiainen , R 2016 , ' Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization ' , Journal of the American Society for Mass Spectrometry , vol. 27 , no. 8 , pp. 1291-1300 . https://doi.org/10.1007/s13361-016-1399-8
Title: | Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization |
Author: | Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto |
Contributor organization: | Faculty of Pharmacy Division of Pharmaceutical Chemistry and Technology Tiina Kauppila / Principal Investigator Risto Kostiainen / Principal Investigator Drug Research Program |
Date: | 2016-08 |
Language: | eng |
Number of pages: | 10 |
Belongs to series: | Journal of the American Society for Mass Spectrometry |
ISSN: | 1044-0305 |
DOI: | https://doi.org/10.1007/s13361-016-1399-8 |
URI: | http://hdl.handle.net/10138/174484 |
Abstract: | The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. |
Subject: |
Atmospheric pressure photoionization
Atmospheric pressure chemical ionization Dopant Charge exchange CHROMATOGRAPHY-MASS-SPECTROMETRY DISCHARGE ION-SOURCE PROTON-TRANSFER AROMATIC-HYDROCARBONS SOLVENT FLOW APPI AFFINITY CLUSTERS WATER ELECTROSPRAY 116 Chemical sciences 1182 Biochemistry, cell and molecular biology 114 Physical sciences |
Peer reviewed: | Yes |
Usage restriction: | openAccess |
Self-archived version: | submittedVersion |
Funder: | SUOMEN AKATEMIA |
Grant number: |
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