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sample
mass
introduction ion source detector computer
analyzer
/inlet
vaccum or atmospheric
pressure vaccum chamber
In those so-called double-focusing sector mass analyzers, the ions are focused in direction
as well as velocity.
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Ion source
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Ion acceleration
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Ion source Detection
e.g. a positively charged ion is attracted by the negatively charged rod, which leads to the ion
traveling towards the rod. Before the ion can reach the rod, the potential is changed, so that the ion is
repulsed by the now positively charged rod and changes direction and so on (stable trajectory).
- Ions with a defined m/z ratio will reach the detector, whereas other ions have unstable trajectories,
which results in their collision with the rods and their discharge.
- Quadrupole MS therefore allows either the selection of individual ions of interest or the detection
of a wide range of m/z-values.
PD Dr. J. Graßmann; PD Dr. T. Letzel
Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München
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The ions trajectories are affected by the ions mass. The applied alternating voltage results in the
acceleration of the ions, with heavy ions having a low velocity and vice versa.
Depending on their m/z, the ions reach the detector at particular and differing points of time.
Linear ToF MS
Ion focussing
Excitation plate
m/z
Central electrode
Picture source: https://commons.wikimedia.org/wiki/File:Orbitrap.png
PD Dr. J. Graßmann; PD Dr. T. Letzel
Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München
Tandem mass spectrometry, MS/MS or MS2 is a multiple-step mass spectrometric selection of ions,
which includes the fragmentation of one or several ions of interest.
Intensity
Intensity
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
Tandem mass spectrometry
Triple quadrupole MS (QqQ)
Single-ion scanning with partial fragmentation:
Q1 Q2 Q3
Precursor ion
Intensity
Intensity
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
Tandem mass spectrometry
Triple quadrupole MS (QqQ)
Produt-ion scanning with complete fragmentation:
Q1 Q2 Q3
Precursor ion
Intensity
Intensity
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
Tandem mass spectrometry
Triple quadrupole MS (QqQ)
Precursor-ion scanning to determine the precursor ion, which produces a specific
product ion of interest:
Q1 Q2 Q3
Product ion
Precursor ion
Intensity
Intensity
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
Tandem mass spectrometry
Triple quadrupole MS (QqQ)
Neutral loss ion scan is used to detect product ions, which originate from a precursor
ion, which has „lost“ a neutral part, i.e. they differ by a defined molecular weight.
Q1 Q2 Q3
Intensity
Intensity
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
Tandem mass spectrometry
Neutral Loss Scan
Both, Q1 and Q3 scan over a defined m/z range. Q3 however allows only ions to
pass, which differ by a fixed mass number from ions passed through Q1. This
scanning mode is particularly helpful to detect precursor ions that fragment via a
specific neutral loss (unionized, non-detectable fragment) during fragmentation in
Q2.
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
Parts of a mass spectrometer
vacuum
pump
sample
mass
introduction ion source detector computer
analyzer
/inlet
vaccum or atmospheric
pressure vaccum chamber
e.g.
Electron multiplier (discontinuous or continuous)
Faraday cup
Scintillation counter
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
MS detectors
Electron multiplier detects the presence of ions from the mass analyzer and multiplies
the charges. The ion strikes a surface, which results in the emission of secondary
electrons.
ion
Discontinuous EM Continuous EM
ion -
- first dynode -
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etc.
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etc.
Signal Signal
PD Dr. J. Graßmann; PD Dr. T. Letzel
Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
MS detectors
Within the Faraday cup the ions strike on the collector, which causes electrons to flow.
This results in a drop in potential, which reflects the intensity of the ion beam.
to amplifier
Mass Spectrometry
Mass Spectrometry – Mass Analyzer
MS detectors
The Scintillator „converts“ a signal caused by an ion, whose impact results in the
emission of electrons towards the scintillator, into the emission of photons. Those are
detected by a photomultplier and furthermore converted into an electric current.
Scintillator
Emitted photons
Photomultiplier
Signal
PD Dr. J. Graßmann; PD Dr. T. Letzel