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Mass Analyzers: Quadrupole ion trap?
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“Ideal” Geometry Quadrupole Trap
Theoretical “infinite” hyperbolic electrodes Actual physical electrodes
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Mass Analyzers: ION TRAPS
Three-dimensional quadrupole field Wolfgang Paul Nobel Prize1989 MSn capability.
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Generating Fields in an Ion Trap
RF Generator V t
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Trapping Ions RF Generator Range of masses trapped depends upon amplitude of rf voltage V t Sugar Salt Cocaine
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Trapping Ions RF Generator V t Increasing the rf amplitude means lower mass ions are not trapped
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Theory - Mathieu Stability Diagram
= 0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.1 0.3 a z q not trapped trapped proportional to frequency of ion motion in z direction Add 0.91
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Trapping a range of ions
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.1 0.3 a z q V= 600 volts
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Trapping a range of ions
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.1 0.3 a z q V= 1000 volts V= 600 volts
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Ion Trap as a Mass Spectrometer
RF Generator White powder analysis signal 56 57 58 59 mass Detector
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Ion Trap as a Mass Spectrometer
RF Generator White powder analysis signal 56 57 58 59 mass Detector
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Ion Trap as a Mass Spectrometer
RF Generator Eject mass 58 White powder analysis signal 56 57 58 59 mass Detector
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Ion Trap as a Mass Spectrometer
RF Generator White powder analysis signal 56 57 58 59 mass Detector
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Mass-selective instability
RF Generator signal 50 100 150 200 mass
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Resonance Ejection RF Generator Change the electric field by applying supplemental ac voltage across end cap electrodes V t
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Ion Motion in Resonance Ejection
without supplemental ac end cap voltage with supplemental ac end cap voltage z=z0 Push Define z somehow Apply supplemental ac voltage to end caps -z=z0
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Resonance Ejection a q Any ion in the ion trap can be ejected
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.1 0.3 a z q Any ion in the ion trap can be ejected Frequency of ac voltage applied to end caps Change ion positions
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Tandem MS in Ion Trap Trap a selected ion
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Mass Analyzers: ION TRAPS
Benefits High sensitivity Multi-stage mass spectrometry Compact mass analyzer Limitations Poor quantitation Very poor dynamic range (can sometimes be compensated for by using automatic gain control) Subject to space charge effects and ion molecule reactions Collision energy not well-defined in CID MS/MS Many parameters (excitation, trapping, detection conditions) comprise the experiment sequence that defines the quality of the mass spectrum Applications Benchtop GC/MS, LC/MS and MS/MS systems Target compound screening Ion chemistry
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ION TRAPS : Time related issues MS/MS/MS
A: ionization B: trapping C: protonation D: selection of parent ion E: stabilization F: CID G: selection of daughter H: stabilization +CID I: Scanning of grand-daughter ions and tetection
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