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)

Mass Analyzers
Resolution
R = m / m

Accuracy/Precision
mass measurement accuracy/reproducibility

Transmission
% of ions allowed through the analyzer

Mass Range
Highest m/z that can be analyzed

Scan Speed
How many spectra per unit of time

Double-Focusing Magnetic Sector

Double-Focusing Magnetic Sector

Magnetic Sector
m
r2B2
=
q
2V
B = magnetic field strength
r = radius of curvature in magnetic field
V = accelerating voltage
m = ion mass
q = ion charge
All ions of the same m/z will have the same radius
Only if the Ion kinetic energy is constant

Double-Focusing Magnetic Sector

Electric Sector
2E
k
r =
qE
Ek = ion kinetic energy
r = radius of curvature in electric field
E = magnitude of electric field
q = ion charge

All ions exiting the electric sector have the same kinetic energy

Double-Focusing Magnetic Sector

Magnetic Sector
Typically a voltage of 5-10kV is used to
accelerate ions
To obtain a full spectrum, magnetic field is
scanned
To obtain a HR scan, voltage is scanned
at constant magnetic field
To gain maximum sensitivity at one mass
SIM scan is done
B and E are constant for one or more masses

Double-Focusing Magnetic Sector

Advantages
Very High Resolution
(60,000)
High Accuracy (<5
ppm)
10,000 Mass Range

Disadvantages
Very Expensive
Requires Skilled
Operator
Difficult to Interface to
ESI
Low resolution MS/MS
without multiple
analyzers

Quadrupole Mass Filter

http://www.asms.org

Quadrupole
E = U - Vcos(2t)
E = potential applied to the rods
U = DC potential
V = RF amplitude
= RF frequency
t = time

Quadrupole is scanned at a constant U/V

Quadrupole Mass Filter

http://www.asms.org

Quadrupole
Typically U varies from 500-2000 V
V varies from 0 - 3000V (-3000 to +3000)
Scanning U/V at a fixed ratio gives a full
scan
Higher values of U/V give higher resolution

RF only (U=0) transmits all ions

Higher sensitivity through SIM scan
Jumping to specific points on the U/V line

Quadrupole Mass Filter

Advantages
Inexpensive
Easily Interfaced to
Many Ionization
Methods

Disadvantages
Low Resolution (<4000)
Low Accuracy
(>100ppm)
MS/MS requires multiple
analyzers
Low Mass Range
(<4000)
Slow Scanning

Quadrupole Ion Trap

Quadrupole Ion Trap

QuickTime and a
YUV420 codec decompressor
are needed to see this picture.

Quadrupole Ion Trap

Ions are injected into the trap and all ions
are trapped
RF and DC are scanned to sequentially
eject ions for detection
Specific ions can be trapped while others
are ejected
Ion velocity can be increased to induced
fragmentation

Quadrupole Ion Trap

Advantages
Inexpensive
Easily Interfaced to
Many Ionization
Methods
MS/MS in one analyzer

Disadvantages
Low Resolution (<4000)
Low Accuracy
(>100ppm)
Space Charging Causes
Mass Shifts
Low Mass Range
(<4000)
Slow Scanning

Time-of-Flight (TOF)
mv
= zVs = Ek
2
2

d
= v
t

m
2
t = z

d2
2Vs

Ek = kinetic energy
v = ion velocity
d = flight distance
t = flight time
Vs = accelerating voltage
m = ion mass
q = ion charge
All ions of the same m/z will have the same flight time
Only if the Ion kinetic energy is constant

Linear Time-of-Flight (TOF)

Advantages
Extremely High Mass
Range (>1 MDa)
Fast Scanning

Disadvantages
Low Resolution (4000)
Low Accuracy
(>200ppm)
MS/MS not possible

TOF
Ions are accelerated with 5-35 kV
Space focusing of source ions is
accomplished by delayed extraction
An electrostatic analyzer (reflectron) is
used correct for kinetic energy spread

Reflectron Time-of-Flight
(MALDI-TOF)

Reflectron Time-of-Flight (ESI-TOF)

Courtesy Bruker Datonics BioTOF users Manual

Reflectron Time-of-Flight (TOF)

QuickTime and a
YUV420 codec decompressor
are needed to see this picture.

Reflectron Time-of-Flight (TOF)

Advantages
High Resolution
(>20,000 in some
models)
High Accuracy (<3ppm)
10,000 Mass Range
Fast Scanning >100 Hz

Disadvantages
Low Resolution for
MS/MS (PSD)

FT-ICR-MS

FT-ICR-MS
mv2
qvB =
r
Centripital
Force

v
qB
=
= f
2r
2m
r and v drop out

v
= 2f
r
Circular
Path

B = magnetic field strength

v = ion velocity
f = orbital frequency
m = ion mass
q = ion charge
r= orbital radius
At constant B, orbital frequency is inversely related to m/z
Frequency is independent of kinetic energy

FT-ICR-MS
Ions are all trapped radially by a magnetic
field (typically 3-15 T)
Axial trapping by DC potential
Ion radius is increased by RF pulse
also brings orbits into phase

Orbiting ions induce RF current in receiver

plates
Image current is a composite of all frequences
in time domain

FFT gives frequency (mass) spectrum

FT-ICR-MS
Actively shielded
magnet
ESI source

capillary

source chamber

transfer
stage

analyzer
stage

ion
guide

cell

ESI needle
(atmosphere)

5 L/sec
rotary vane
10-1 mbar

250 L/sec
turbo-drag
pump
10-4 mbar

500 L/sec
turbo pump
10-6 mbar

70 L/sec
turbo pump
10-8 mbar

500 L/sec
turbo pump
10-10 mbar

FT-ICR-MS

QuickTime and a
YUV420 codec decompressor
are needed to see this picture.

FT-ICR-MS

FT-ICR-MS

FT-ICR-MS

FT-ICR-MS

FT-ICR-MS

FT-ICR-MS
Electrospray: Broadband Spectrum of Bovine Serum
Albumin (66kDa) 7.0T Actively Shielded Magnet
m = 0.01933 a.u.
1/m = 51.7308 a.u.
mass = 64428 a.u.

52+
52+

1278.3

1278.8

m/z

60+
36+

1200

1400

1600

1800

m/z

FT-ICR-MS
Electrospray: Deconvoluted Spectrum of Bovine
Serum Albumin (66kDa) 7.0T Actively Shielded Magnet
m = 1.004 a.u.

66410

66430

66450

m/z

FT-ICR-MS
Advantages
Extremely High
Resolution (>500,000)
Very Good Accuracy
(<1 ppm)
MS/MS in one analyzer

Disadvantages
Expensive
Requires
Superconducting Magnet
Slow MS/MS