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@PHDTHESIS{Bergmann:354739,
author = {Bergmann, Julian},
title = {{H}igh-{R}esolution {T}andem {M}ass {S}pectrometry of
complex mixtures with a {M}ultiple-{R}eflection
{T}ime-of-{F}light {M}ass-{S}pectrometer},
school = {Justus Liebig University Giessen},
type = {Dissertation},
publisher = {Universitätsbibliothek Gießen},
reportid = {GSI-2024-01213},
pages = {119},
year = {2024},
note = {Dissertation, Justus Liebig University Giessen, 2024},
abstract = {In this work, a multiple-reflection time-of-flight mass
spectrometer (MR-TOF-MS) was adapted and employed, for the
first time, for ultra-high resolution analytical tandem mass
spectrometry. The device was deployed to analyze isobaric
molecules in a heavy crude oil sample and to derive new
structure formulas thanks to the device's ultra-high
separation power and advanced data analysis techniques. A
new atmospheric pressure interface (API) was built to
operate multiple ion sources in parallel and to optimize the
transmission for viscous samples, like crude oil residue. A
radio-frequency carpet funnels the ions to the RFQ transport
line, providing a compact, efficient, and fast method to
combine ions from different sources in parallel to introduce
calibrants, while avoiding chemical reactions with the
analyte. Ion sources of three different types, nano-ESI,
micro-ESI, and thermal 133Cs, were designed, built, coupled
to the API, and operated to acquire the data shown in this
thesis. A software package was developed for operating the
device and for acquiring and analyzing mass spectra. The
software allows automatically setting up the measurement by
converting parameters like the desired mass range to
voltages and HV pulse sequences in real time. Further
automated measurement features are a time-of-flight drift
correction, a scanning of measurement parameters, and an
automatic gain control. In addition, its calibration
technique and its enhanced elemental composition
identification further assist in analysis. Furthermore, data
analysis procedures were developed to increase the mass
range, while retaining a high mass accuracy and mass
resolving power for closed-path MR-TOF-MS. The software is
also used together with MR-TOF-MS devices at particle
accelerators, i.e. the MR-TOF-MS of the FRS Ion Catcher at
GSI, Darmstadt, and the MR-TOF-MS of the TITAN experiment at
TRIUMF in Vancouver. The device in this work features a mass
resolving power (FWHM) of up to 300000, a sensitivity down
to 10 mol/l, a linear dynamic range of five orders of
magnitude, and mass accuracy of 0.3 ppm. Its re-trapping
technique allows for a precursor mass separation power of up
to 250000 at an efficiency of 10 $\%$ or up to 100000 with
an efficiency of 80 $\%$ for tandem mass spectrometry. These
capabilities were shown for tandem mass spectrometry
measurements up to the fourth stage $(MS^4).$ Furthermore,
molecules as heavy as human insulin (5810 u) have been
analyzed. Tandem mass spectrometry of a sample of
medium-heavy crude oil residue was performed and four
isobaric mass signals close to 322.2 u/e were isolated with
an isolation window of 10 mu and a suppression factor of
200. This was only possible thanks to this device's
ultra-high mass separation power. The resulting fragments
within a mass range of 300 - 500 u were measured at a mass
resolving power of 200000 and a mass accuracy of better than
1 ppm, and their elemental compositions were identified.
With the help of our collaboration with the workgroup Mass
Spectrometry of Prof. Dr. Wolfgang Schrader at the Max
Planck Institute für Kohleforschung in Mülheim an der
Ruhr, 26 molecular structures for the two isobaric precursor
molecules, C23H32N+ and C23H28ON+, were identified. For
future applications of the device, investigation of less
understood crude oil samples as well as applications in life
sciences are envisioned.},
keywords = {Massenspektrometrie (Other) / analytische
Massenspektrometrie (Other) / MR-TOF-MS (Other) /
Multiple-reflection time-of-flight mass spectrometers
(Other) / crude oil (Other) / Rohöl (Other) / Ionenoptik
(Other) / Software (Other) / Gerätesteuerung (Other) /
Datenanalyse (Other) / Geräteentwicklung (Other) /
Simulationen (Other) / Experiment (Other) / Tandem
Massenspektrometrie (Other) / Massenselektiver Wiedereinfang
(Other) / Mass-selective re-trapping (Other) / IONAS (Other)
/ Scheidenberger (Other) / ddc:530 (Other)},
cin = {FRS / SuperFRS-EC@FAIR},
cid = {I:(DE-Ds200)FRS-20110310OR124 /
I:(DE-Ds200)Coll-FAIR-SuperFRS-EC},
pnm = {612 - Cosmic Matter in the Laboratory (POF4-612)},
pid = {G:(DE-HGF)POF4-612},
experiment = {$EXP:(DE-Ds200)Experiment_without_proposal_number-20200803$},
typ = {PUB:(DE-HGF)11},
doi = {10.22029/JLUPUB-18381},
url = {https://repository.gsi.de/record/354739},
}