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Published byRamon Lamison Modified over 9 years ago
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Performance of a Hybrid RF/DC Quadrupole-Linear Ion Trap Mass Spectrometer
James W. Hager MDS SCIEX ASMS, 2002
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Outline Linear ion trap mass spectrometer concept.
Mass selective axial ion ejection. Marriage with triple quad ms. Trapping and extraction efficiencies Space charge effects Performance characteristics. Future directions.
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Triple Quad. MS/MS --Tandem in Space
Only 1 ion pair is stable at any one time. Poor scanning efficiency. Very efficient for MRM. Very selective scans available.
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3D Ion Trap MS/MS --Tandem in Time
Full mass spectrum for each pulse of ions. High scanning efficiency. Scanning instrument only.
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Linear Ion Traps “Ion bottles” for optical spectroscopy.
Minimize fringing fields to maximize performance. Ion accumulation for enhanced ms sensitivity. Mass analyzers: RCM, 2002, 16, JASMS, 2002, 13,
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Linear Ion Trap Mass Spectrometer
Ions are trapped by barriers: Radially: RF potential Axially: DC barriers Radial RF determines the ion frequencies of motion. Radial and axial ejection demonstrated. Drive RF & auxiliary AC
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RF Fringing Fields Axial Ion Ejection:
Exit fringing fields couple radial/axial degrees of freedom of the trapped ions. Excite ions radially to eject them axially.
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Time Averaged Axial Electric Field
Dehmelt approx.: radial amplitude fringing field F. Londry, ASMS,
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Hybrid Instrument with Q3 Linear Ion Trap MS
N2 CAD Gas linear ion trap 3x10-5 Torr Aux AC IQ2 IQ3 Exit Skimmer Orifice LINAC IQ1 Q0 Q1 Q2 Q3
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Q3 Trapping Efficiency vs. Chamber Pressure
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Extraction Efficiency vs. Ejection q-Value
(4x10-5 Torr)
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Trapping & Extraction Efficiencies
5-inch long rod array: Trapping efficiency: ~45% 4x10-5 Torr background pressure Extraction efficiency: 16-20% q-value dependent Overall efficiency: ~8%
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Hybrid Approach to Product Ion MS/MS
RF/DC Q Q Q3 linear trap eV frags. Advantages: No time required to isolate the precursor ion. No loss for isolation of fragile precursor ions. The ion trap is filled with only precursor and fragment ions. Triple quad. fragmentation patterns. No inherent low mass cut-off.
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Product Ion Scanning Precursor ions selection in Q1.
N2 CAD Gas Aux AC Exit lens Ion accumulation Q0 Q1 Q2 Q3 Precursor ion selection Fragmentation linear ion trap 3x10-5 Torr Precursor ions selection in Q1. Fragmentation in Q2. Trap products in Q3. Mass scan. Concurrent trapping in Q0.
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Sensitivity Enhancements
Reserpine – Product Ion QqQ Q1 Open Resolution Enhanced Product Ion Scan > 350x
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Sensitivity Enhancements—Reserpine
Q1 Open Resolution QqQ Enhanced Product Ion Scan
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Enhanced Prod Ion Scan – 75eV
No Low Mass Cut-off Taurocholic Acid– Product Ion LCQ Deca – 45% CE 3 amu isolation width Enhanced Prod Ion Scan – 75eV
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Resolution and Scan Speed: Reserpine
4000 amu/sec ~0.55 amu wide 1000 amu/sec ~0.35 amu wide 250 amu/sec ~0.15 amu wide
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Mass Shift vs. Ejection q-Value
3.5x10-5 Torr 103X Change of Ion Current
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Mass Shift vs. Input Ion Intensity
q=0.86, m/z=609
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Space Charge Effects Q3 Space Charge Effects (3x10-5 Torr): D~0.02 amu
104x > ion current D~0.02 amu
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RF/DC Quadrupole-Linear Ion Trap Mass Spectrometer
Ion trap and triple quad capabilities on a single platform. High sensitivity ion trap scans: Single MS survey scans Product ion scans MS3 in Q3 Triple quad. Functionality: MRM Precursor ion scans Neutral loss scans
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Future Directions Tandem-in-space ion trap(s) approach allows for simultaneous ion processing while the primary mass analyzer is scanning. Increased sample utililization eff. and thus higher duty cycles. Very high resolution.
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Acknowledgments Yves LeBlanc Frank Londry Bill Stott Bruce Collings
John Vandermey
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