Ionization of ionic liquids under laser desorption/ionization

Anastasiya Yu. Sholokhova; Svetlana A. Borovikova; Sergey A. Prikhod'ko; Alexey K. Buryak

doi:10.17308/sorpchrom.2020.20/3048

Anastasiya Yu. Sholokhova A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation
Svetlana A. Borovikova A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation
Sergey A. Prikhod'ko G.K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russian Federation; Novosibirsk State University, Novosibirsk, Russian Federation
Alexey K. Buryak A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation

DOI: https://doi.org/10.17308/sorpchrom.2020.20/3048

Keywords: ionic liquids,, mass spectrometry,, laser desorption / ionization

Abstract

Despite various studies of ILs as MALDI matrices, however, so far no relationship has been found
between the composition of ILs and their ability to serve as «good» matrices. For a preliminary experiment,
in order to evaluate the characteristics of ILs before being used as a matrix in MALDI-MS, it is necessary to
study the mass spectral behavior for the matrices themselves under LDI conditions. Therefore, the purpose of this work was to analyse ion liquids based on the cation imidazolium in combination with different types of
anions by the LDI method. Ionic liquids were synthesized in the Laboratory of catalytic processes for the
synthesis of organoelement compounds of G.K. Boreskov Institute of catalysis SB RAS (Novosibirsk). It
should be noted that this ionic liquid was first synthesized in this Laboratory. Analyses were performed using
a Bruker UltraFlex II time of-flight mass spectrometer. Eleven ion liquids based on substituted cation imidazolium in combination with different types of anions were analysed by method laser desorption/ionization in the paper. In all mass spectra of ionic liquids obtained in the positive ion mode, cation produced a major peak and its fragmented ions. Homologous series characterized by the loss of the methyl group have been recorded. According to the more stable carbon-carbon or nitrogen bond in the heterocyclic system than in the carbon-carbon bond in the aliphatic, ion peaks are observed in the mass spectra, characteristic of the loss of methyl fragments from the aliphatic chain. In the LDI spectra obtained in the negative ion mode, the signals of the anions of ionic liquids and their fragments were observed. The combined use of the spectra obtained in positive and negative mode makes it possible to increase the reliability of identification. This makes it possible to use the revealed patterns of fragmentation for the structural analysis of ionic liquids. The analyzed ILs can be used as MALDI matrices, because they do not form dimers, assassinates, are characterized by the absence of adducts with metal ions, which is important for their further use as matrices. BMIMC₆F₅BF₃ was first described by the LDI-MS method. It was shown that the observed fragmentation of the molecular ion of this IL is typical for most ILs with similar cations.

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Author Biographies

Anastasiya Yu. Sholokhova , A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation

junior researcher, laboratory of physicochemical principles of chromatography and chromatography – mass
spectrometry; Institute of Physical chemistry and electrochemistry, Moscow, e-mail:
shonastya@yandex.ru

Svetlana A. Borovikova, A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation

researcher, laboratory of physicochemical principles of chromatography and
chromatography – mass spectrometry; Institute of Physical chemistry and electrochemistry, Moscow, email:
borovikova7@mail.ru

Sergey A. Prikhod'ko, G.K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russian Federation; Novosibirsk State University, Novosibirsk, Russian Federation

senior researcher, Laboratory of catalytic processes for the synthesis of
organoelement compounds, G.K. Boreskov Institute of Catalysis SB RAS, Novosibirsk, e-mail:
spri@catalysis.ru

Alexey K. Buryak, A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation

prof., grand PhD (chemistry), laboratory of physicochemical principles of
chromatography and chromatography – mass
spectrometry; Institute of Physical chemistry and
electrochemistry, Moscow, e-mail: akburyak@mail.ru

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