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Mass Spectrometry
Ionization Techniques
and
Mass Analyzers
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Mass Spectrometer
All Instruments Have:
1. Sample Inlet
2. Ion Source
3. Mass Analyzer
4. Detector
5. Data System
http://www.asms.org
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Ionization Techniques
Gas-Phase Methods Electron Impact (EI)
Chemical Ionization (CI)
Desorption Methods Matrix-Assisted Laser Desorption Ionization (MALDI)
Fast Atom Bombardment (FAB)
Spray Methods Electrospray (ESI)
Atmospheric Pressure Chemical Ionization (APCI)
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Electron Impact
http://www.noble.org/PlantBio/MS/ion_tech_main.html
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Electron Impact
Advantages
Well-Established
Fragmentation Libraries No Supression
Insoluble Samples
Interface to GC
Non-Polar Samples
Disadvantages
Parent Identification
Need Volatile Sample Need Thermal Stability
No Interface to LC
Low Mass Compounds
(
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Chemical Ionization
http://www.noble.org/PlantBio/MS/ion_tech_main.html
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Chemical Ionization
Advantages
Parent Ion
Interface to GC Insoluble Samples
Disadvantages
No Fragment Library
Need Volatile Sample Need Thermal Stability
Quantitation Difficult
Low Mass Compounds
(
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FAB
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FAB
Advantages
Parent Ion
High Mass Compounds(10,000 amu)
Thermally Labile
Compounds (R.T.)
Disadvantages
No Fragment Library
Solubility in Matrix(MNBA, Glycerol)
Quantitation Difficult
Needs Highly SkilledOperator
Relatively LowSensitivity
(nanomole)
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MALDI
http://www.noble.org/PlantBio/MS/ion_tech_main.html
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MALDI
Advantages
Parent Ion
High Mass Compounds(>100,000 amu)
Thermally Labile
Compounds (R.T.)
Easy to Operate
Disadvantages
No Fragment Library
Wide variety of matrices Quantitation Difficult
(low femtomole)
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ESI
http://www.noble.org/PlantBio/MS/ion_tech_main.html
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ESI
Advantages
Parent Ion
High Mass Compounds(>100,000 amu)
Thermally LabileCompounds (
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APCI
http://www.rzuser.uni-heidelberg.de/~bl5/ency/ency.html
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APCI
Advantages
Parent Ion
Insensitive to Salts Interface to HPLC
Can use Normal Phase
Solvents
Handles High FlowRates
Disadvantages
Need Volatile Sample
Need Thermal Stability
(high femtomole)
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Mass Analyzers
Double Focusing Magnetic Sector
Quadrupole Mass Filter
Quadrupole Ion Trap
Linear Time-of-Flight (TOF)
Reflectron TOF Fourier Transform Ion Cyclotron
Resonance (FT-ICR-MS)
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Double-Focusing Magnetic Sector
http://www.asms.org
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Advantages
Very High Resolution
(60,000)
High Accuracy (
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Quadrupole Mass Filter
http://www.asms.org
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Advantages
Inexpensive
Easily Interfaced toMany Ionization
Methods
Disadvantages
Low Resolution (100ppm)
MS/MS requires
multiple analyzers
Low Mass Range(
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Quadrupole Ion Trap
http://www.asms.org
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Advantages
Inexpensive
Easily Interfaced toMany Ionization
Methods
MS/MS in one analyzer
Disadvantages
Low Resolution (100ppm)
Space Charging
Causes Mass Shifts
Low Mass Range(
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Linear Time-of-Flight (TOF)
http://www.asms.org
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Advantages
Extremely High Mass
Range (>1 MDa)
Fast Scanning
Disadvantages
Low Resolution (4000)
Low Accuracy(>200ppm)
MS/MS not possible
Linear Time-of-Flight (TOF)
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Reflectron Time-of-Flight (TOF)
Courtesy Bruker Datonics BioTOF users Manual
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Advantages
High Resolution
(>20,000 in some
models)
High Accuracy (
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FT-ICR-MS
http://www.asms.org
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Advantages
Extremely High
Resolution (>500,000)
Very Good Accuracy
(