Mass Spectrometry
How is MS Done?
Basic MS Instrumentation
Magnetic Sector Mass Analyzers
Quadrupole Mass Analyzers
Reflector Time Of Flight
3D Quadrupole ion trap Linear Quadrupole ion trap 3D radio-frequency ion traps: ions are trapped in center point (single point) 2D Linear trap: rf field is zero along the whole central line of the electrode configuration Quadrupolar ion traps (Paul trap)
3 sets of parallel plates in a uniform magnetic field In a 7-Tesla magnetic field an ion with m/z =100 will spin 1,000,000 cycles (travel ~ 30 km) in a 1 sec. observation period Fourier transform ion cyclotron resonance (FTICR) MS
Linear trapping quadrupole FTICR
Mass Analyzers Instrument Mass analyzer2D trapQTOFFT-ICR/Orbitrap Mass accuracy500 ppm10 ppm1 ppm Resolution1,00010,000100,000 Sensitivity0.1 fmol1 fmol0.1 fmol Dynamic range ,000 Price$250K$450K$600K
Electron Impact Vs Chemical Ionization
Electrospray Ionization
Electrospray Vs Electron Impact
Proteins/Preteomics
Matrix Assisted Laser Desorption Iionization (MALDI)
Resolution/Sensitivity/Mass Accuracy Mass Mass Difference 5000 is typical unit resolution up to mass 5000 Proteins: 100 AA M = 15,000 R = 15,000 for unit resolution
Exact Mass/Mass Defect/Isotopic Abundance C 3 H 8 O C 2 H 8 N C 2 H 4 O CH 4 N 2 O R > 5300 required
base peak molecular ion Fragment isotope patterns The Mass Spectrum
Isotope Patterns CO N C 2 H M+1 M+2 M
Fragmentation
Alkanes
Cyclic Alkanes
Alkenes
Aromatics
Alcohols
Phenols
Aliphatic Ethers
Aromatic Ethers
Ketones
Aromatic Ketones
Aldehydes
Carboxylic Acids
Esters
Lactones
Thiols