Mass Spectrometry - Essays and Tutorials

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Mass Spectrometers

Tandem Mass Spectrometry (MS/MS)

Mass spectrometers are commonly combined with separation

devices such as gas chromatographs (GC) and liquid
chromatographs (LC). The GC or LC separates the components in
a mixture, and the components are introduced, one by one, into

GC separates components Mass spectrum of eluting component

MS GC/MS
GC

Simple Schematic of a Mass Spectrometer Interfaced to a GC

the mass spectrometer. MS/MS is an analogous technique where

the first-stage separation device is another mass spectrometer.

Suppose that we analyze a mixture of components by a "soft"

ionization method (such as chemical ionization, fast atom
bombardment, or electrospray ionization). Each component
produces characteristic ionic species such as [M+H]+. To keep the
discussion simple, let's assume that each component of the
mixture has a unique molecular weight. The mass spectrum of
the mixture contains peaks for each compound present in the
mixture. Now, suppose that we would like to identify one of the
mixture components. All the mass spectrum tells us is the

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molecular weight, but we would really like to see fragment ions

that provide structural information for the component of interest.

The simplest form of tandem mass spectrometry combines two

mass spectrometers. The first mass spectrometer is used to

Set MS1 to select this mass, m1 Fragments of m1

MS1 MS2 MS/MS

CID: Gas-filled collision chamber.

m1 breaks apart to produce fragments

Simple Schematic of a Two Mass Spectrometer Tandem MS/MS

select a single (precursor) mass that is characteristic of a given

analyte in a mixture. The mass-selected ions pass through a
region where they are activated in some way that causes them to
fall apart to produce fragment (product) ions. This is usually done
by colliding the ions with a neutral gas in a process called
collisional activation (CA) or collision-induced dissociation (CID).
The second mass spectrometer is used to separate the fragment
ions according to mass. The resulting "MS/MS" spectrum consists
only of product ions from the selected precursor. Chemical
background and other mixture components are absent.

Kinds of MS/MS experiments

Consider a precursor ion, m1+ that decomposes to produce a

product ion, m2+, and a neutral loss, N:

+ +
m1 → m2 + N

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MS/MS experiments can be classified according to which of these

species (product, precursor, or neutral loss) is a constant. Note
that there is no requirement that the product and precursor ions
be positively charged; the terminology is identical for negative
ions.

Product-ion scan (m1+ specified)

If we do an MS/MS experiment to find out all of the product ions,

m2+ that result from the decomposition of a specified parent ion
m1+, then this is called a product-ion scan. This is the most
common and well-known MS/MS experiment. It is used to
determine structurally significant fragment ions for a selected
precursor ion.

Precursor-ion scan (m2+ specified)

If we perform an MS/MS experiment that tells us all of the

possible precursor ions m1+ that decompose to produce a
specified product ion m2+, then this is called a precursor-ion
scan. This is useful when you know that a particular product
(fragment) ion mass is characteristic of a class of compounds,
and you would like to identify the mixture components that
belong to that compound class.

Constant neutral-loss scan (N specified)

An MS/MS experiment that looks for all pairs of precursor ions

and product ions that differ by a constant neutral loss, N, then
this is called a constant neutral loss scan. This is useful when you
know that a particular neutral loss mass is characteristic of a
class of compounds, and you would like to identify the mixture
components that belong to that compound class. Note that the
peaks in a constant neutral loss scan can be labeled with either
the product ion mass or the precursor ion mass. Both naming
conventions are valid, but it is more common to label the peaks

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with the precursor mass because it is assumed that you are

interested in the identity of the intact analyte molecules.

Selected reaction monitoring

Selected reaction monitoring (SRM) is an MS/MS experiment that

is analogous to selected ion monitoring (SIM) for target
compound identification. In SIM, one only measures a set of
preselected analyte masses. Other masses and the baseline noise
between peaks are not detected. Compare to scanning
experiments, SIM experiments provide improved selectivity and
sensitivity for target compound identification and quantitative
analysis. In SRM, one specifies sets of product and precursor
masses that are known to be characteristic of certain target
compounds.

Ion activation methods

There are many different ways to increase the internal energy of

ions so that chemical bonds will break and fragments will be
formed. The various ion activation methods differ in how the
energy is imparted to the ions, how much energy is imparted,
and how the energy is distributed in the activated ions. These
factors affect the selectivity, efficiency and reproducibility of the
mass spectra, and they can have dramatic effects on which
product ions are formed from an activated ion. The best way to
characterize an ion activation method is to look at a plot of the
internal energy distribution of the activated ion (Wysocki, V. H.;
Kenttamaa, H. I. ; Cooks, R. G. Int. J. Mass Spectrom. Ion Proc.
75 (1987), 181-208). The internal energy distribution can be
estimated from the relative abundances of fragment ions from
well-characterized test compounds such as tungsten carbonyl. A
broad internal energy distribution will result in many different
kinds of fragmentations and an information-rich MS/MS spectrum.
A narrow internal energy distribution will result in efficient
conversion of the precursor ions to only a few specific product
ions. Note that a low, narrow internal energy distribution will

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Wysocki, Kettämaa, & Cooks, IJMSIP, 75 (1987), 181-208

MS/MS High-energy vs. Low-energy Conversion

favor bond rearrangements while a high, narrow internal energy

distribution will favor simple bond cleavage. The experimental
time scale is important. It takes a certain amount of time for an
activated ion to decompose. Mass analyzers such as time of flight
and magnetic sector mass spectrometers may detect activated
ions before they have time to decompose. In that case, the
precursor ions may require additional internal energy to cause
them to decompose fast enough for the product ions to be
observed. This is called a kinetic shift.

Metastable ions

The majority of ionization methods form some ions that have

enough excess energy to decompose spontaneously. Some ions
are stable and long-lived, such as molecular ions that are
observed in electron ionization (EI) mass spectra, or [M+H]+
ionsobserved in chemical ionization (CI) mass spectra. Some ions
are unstable and decompose rapidly in the ion source, such as

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fragment ions observed in EI mass spectra. Metastable ions are

ions that survive long enough to leave the ion source but
decompose before they are detected. There are techniques for
detecting and analyzing metastable ion decompositions. Strictly
speaking, metastable ions do not result from an ion activation
method, but it is usually hard to distinguish ions that are formed
with excess internal energy from those that undergo collisions
with background gas in the ion source.

Collision-induced disassociation (CID)

If an ion collides with a neutral atom or molecule, some of the

ion's kinetic energy can be converted into internal energy. This is
called collisional activation. If there is enough excess internal
energy to break chemical bonds, the ion will decompose. This is
called collision-induced dissociation (CID) or collisionally
activated dissociation (CAD). Both terms mean the same
thing. Only a fraction of the ion kinetic energy, Elab, can be
converted to internal energy. This fraction can be derived from
looking at the physics of the ion-neutral collision from a center-
of-mass reference frame,

E cm = E lab × m2 /(m1 + m2 )
Increasing the ion kinetic energy and/or using a more massive
target can increase the amount of kinetic energy that can be
converted to internal energy. Multiple collisions with the target
molecules can increase the internal energy, but they can also
result in randomization of the internal energy and increase the
€ probability of undesirable rearrangements. The collision process
can also affect the target. It can be activated or even ionized;
polyatomic target molecules can fragment. This is why noble
gases such as helium, argon, and xenon are usually used as
target gases. They are monoatomic and have high ionization
potentials.

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High-energy collisions

This refers to collisions where the precursor ion is accelerated to

kinetic energies of approximately one kilovolt or higher, resulting
in the excitation of electronic states in the precursor ion. High-
energy collisions produce a broad internal energy distribution.
Virtually all structurally possible fragmentations have some
probability of occurring. The target mass does not have a large
influence on the MS/MS spectrum for high-energy CID because
the center-of-mass energy is a small fraction of a large kinetic
energy. This means that changes in the collision conditions
(collision gas, pressure, and temperature) do not produce large
changes in the product-ion mass spectrum. Therefore, high-
energy CID is very reproducible. Helium is often used as the
target gas for high-energy CID because it is inexpensive, it has a
high ionization potential, and it does not cause large scattering of
the precursor ions.

Low-energy collisions

This refers to collisions where the precursor ions have kinetic

energies in the range of a few eV to a few hundred eV. Low-
energy collisions are thought to excite vibrational states, and they
produce narrower internal energy distributions. The product ions
that are observed depend strongly on the internal energy
distribution. Increasing the collision energy shifts the center of
the internal energy distribution to a higher value, and changes
the product ions that are observed. A product-ion mass spectrum
resulting from 10 eV collisions can be dramatically different from
one resulting from 25 eV collisions. The target mass does have a
strong influence on the MS/MS spectrum for low-energy CID.
Xenon and argon are often used as target gases for low-energy
CID to increase the center-of-mass energy and increase the
probability of observing high-energy fragments. The target gas
pressure and temperature will also affect the number of collisions
and therefore the internal energy distribution and the resulting

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mass spectrum. For these reasons, low-energy CID is less

reproducible than high-energy CID.

High-energy CID mass spec-

trum is more reproducible,
shows less rearrangement and
is easier to interpret.

189 136
CH2
166
HO
CH3 N
In-source (low energy CID)
310 O

160 (H rearr.)
294 N

Quinine (ESI+)

MS/MS (high energy, 2.5kV)

Low-Energy CID vs. High-Energy CID

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Polyoxin D (MW 521) COOH

NH

N O
175 +
387 O OH 232 O
O OH O 306
461 COOH COOH

H2N C O CH2 CH CH CH C NH CH H2N C O CH2 CH CH CH C NH CH

60 OH NH2 366 60 OH NH2 102

134 O 134 O
191

HO OH HO OH

More fragmentation at high

collision energies, therefore
more structural information.

MS/MS of Polyoxin D at Different Collision Energies

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Ion-molecule reactions (reactive collisions)

Ions can undergo chemical reactions with neutral molecules. Such

ion-molecule reactions have been explored at length by
techniques such as ion cyclotron resonance spectrometry and
flow techniques. Ion-molecule reactions are the basis for chemical
ionization, but they can also be used as an MS/MS technique;
however, the chemistry involved is beyond the scope of this
article. Reactive collisions are not in wide use as an analytical MS/
MS method at this time.

Neutralization-reionization mass spectrometry (NRMS)

Tandem mass spectrometers have been developed in which an ion

beam is converted to neutral molecules which may undergo
chemical reactions prior to a reionization step. The resulting ion
beam can be analyzed by the second-stage mass spectrometer.
NRMS provides a method for creating and studying species which
could not otherwise be formed in or analyzed by mass
spectrometry.

Surface-induced dissociation (SID)

If we substitute a target surface for a collision gas chamber, we

can scatter ("bounce") ions off the surface. Ions can gain internal
energy from the ion-surface collisions and will subsequently
decompose. This process is referred to as surface-induced
dissociation (SID).

SID is very efficient. High internal energies can be achieved with

low collision energies. The internal energy distributions are quite
narrow, but it is possible to vary the collision energy to observe
all possible fragment types.

SID can be performed by bouncing ions off a surface

perpendicularly or at an angle, or it can be accomplished by
passing ions through narrow channels so that ions bounce off the

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channel surfaces ("in-line SID"). The nature of the surface affects

the SID process, so a variety of surfaces and surface materials
have been used in SID experimentation.

Photodissociation

If ions are irradiated with photons (light), they can absorb light
and undergo electronic excitation. This requires that (1) the ions
must have a chromophore that allows them to absorb light at the
given wavelength and (2) the photons must have energies higher
than the energy required to break a chemical bond. This usually
means ultraviolet light. Furthermore, the light intensity must be
high enough that the rapidly moving ions will actually interact
with the photons. This usually means that a highly focused laser
must be used.

Trapped ion mass spectrometers are usually very effective for

photodissociation experiments because the ions can be trapped in
the region irradiated by the light, increasing the probability that
an ion will encounter a photon. Two-photon processes can also be
observed if an ion absorbs a wavelength that is not energetic
enough to break a chemical bond. However, the activated ion can
be trapped in the irradiating light and absorb a second photon
which adds enough energy to induce fragmentation. Unlike
molecules in solution the trapped ions are not cooled by solvent
interactions, and so they can often be trapped for a long time
without losing energy.

Photodissociation is very efficient if all of the above conditions are

met. It is also a selective process because activation will only
occur for ions that have an absorption band corresponding to the
wavelength of the irradiating light.

Electron-induced dissociation

If ions encounter a high-current electron beam, the ion-electron

collisions can result in ion activation. This has been observed for

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positive ions trapped in the negatively charged electron beam in

an ion cyclotron resonance mass spectrometer. As the electron
current is increased, unexpected fragment ions begin to appear.
The technique has been referred to as "electron impact excitation
of ions from organics" (EIEIO). Electron-induced dissociation has
also been attempted by using high-current electron sources in
sector and quadrupole mass spectrometers, and referred to as "El
CID" and "EID". To date it has not achieved widespread use as an
analytically valuable activation method.

MS/MS Instrumentation
Magnetic sector MS: How can you do MS/MS with only one
MS?

Metastable ions are frequently observed in magnetic sector mass

spectrometers as broad, low-intensity peaks at apparent m/z
values that do not correspond to an expected fragment.
Metastable ions that decompose in the first field-free region
(between the ion source and the first sector) appear at an
apparent mass of m22/m1 where m2 is the mass of the product ion
and m1 is the mass of the precursor ion. Double-focusing
magnetic sector mass spectrometers can be used to perform MS/
MS analyses. Collision cells can be placed between the ion source
and the first sector (the first field-free region) or between the
magnetic sector and the electric sector (the second field-free
region).

Reverse-geometry mass spectrometer (MIKES)

Some of the earliest MS/MS work was done with reverse-

geometry double focusing mass spectrometers. A reverse-
geometry mass spectrometer is one in which the magnetic sector
precedes the electric sector. A magnetic sector alone can be used
as a mass spectrometer, with roughly unit resolution. Therefore,
one can adjust the magnetic field strength to select a given
precursor mass. The precursor mass is then activated by

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collisions in the second field-free region (just between the

magnetic and electric sectors) and then the electric sector is used
to analyze the kinetic energies of the product ions. This is
referred to as "mass-analyzed ion kinetic energy spectrometry" or
"MIKES". MIKES experiments are characterized by good (unit
resolution) precursor mass selection and poor product-ion
resolution. The latter results from the fact that we are measuring
product ion kinetic energies instead of product-ion mass-to-
charge ratios. MIKES spectra provide a "fingerprint" that can be
used to identify a given analyte, and they are useful for ion
chemistry studies.

Magnet Electric sector Detector

Select m1 KE of m2

Ion source
Collision chamber 2nd
Field-free region

Mikes: Hold B Constant, Scan E

Linked scans

Most magnetic sector analyses are done by setting the

accelerating voltage and electric sector to a fixed accelerating
voltage and electric sector. MS/MS experiments can also be done
by scanning the electric and magnetic sectors together according
to certain scan laws. Consider what happens to ions during a
product-ion linked scan where collisions occur in the first field-
free region (just after the ion source).Ions leaving the ion source

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are accelerated to a kinetic energy that depends only on the

accelerating potential and the number of charges on the ion:

mv 2
T = eV =
2
All ions with the same number of charges will have the same
kinetic energy. For the moment, let's assume that the ions have
only a single charge. It is apparent from the above expression
that ions with€ different masses must have different velocities if
their kinetic energies are the same. Let's assume that precursor
ions with mass m1 fall apart in the first field-free region to for
product ions with mass m2. Lets also assume that the velocity
does not change when the ions fall apart. This is a safe
assumption because we will only be observing ions that undergo
grazing collisions, and any change in velocity will be small
compared to the total velocity of ions accelerated to, say, 10
kilovolt kinetic energies. The product ions will still have the
same velocity as the precursor ions. If we can select ions
according to their velocities, we can tell which product ions were
formed from precursor ions with known velocities. This is easily
done. Recall that the magnetic sector separates ions according to
their momentum (mv) and the electric sector selects ions
according to their kinetic energy (mv2/2). The ratio of B to E is
related to the velocity:

B mv 2
= =
E mv 2 /2 v
One can choose a B/E ratio to select ions with a given velocity. If
we scan B and E together, always keeping a constant B/E ratio,
we will detect product ions from the precursor ion with the
specified velocity.
€ This means that a B/E scan is a product ion
scan. Like the metastable ions discussed earlier, the product ions
will appear at an apparent mass of m22/m1. The product ion

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resolution can be quite good for a B/E linked scan, but the
precursor ion resolution (selectivity) is poor. The reason is that
we are only relying on ion velocity differences to distinguish
between the different precursor masses. Suppose that we scan
the two sectors while keeping B2/E constant. Again, the magnetic
field is related to the ion momentum (mv) and the electric field is
related to the ion kinetic energy (mv2/2), so:

B2 m 2v 2
∝ 2
= 2m
E mv /2
All ions that pass through B and E must have the product ion
mass m, but their velocities may differ according to the precursor
ion velocities. A linked scan that keeps B2/E constant can be used
€ ion scan. The precursor peaks are very broad for
as a precursor
this kind of linked scan. One can also perform a linked scan to
detect product and precursor ions that differ by a constant
neutral loss. In this case, the linked scan relation is:

B2
E (1− E) = k

Tandem (4-sector) MS
In one sense, this is the simplest MS/MS method to describe. Two
high-resolution double focusing mass spectrometers are
€
combined with a collision chamber in between. The first mass
spectrometer (MS-I) is set to pass mass-selected precursor ions
into the collision chamber. The second mass spectrometer (MS-II)
is scanned to detect product ions produced by the collision-
induced dissociation of the precursor ions. Because MS-I is a
high-resolution mass spectrometer, precursor ions can be
separated if they have can be resolved by MS-I. MS-II is scanned
with a linked scan at a constant B/E ratio to pass the product
ions. The reason for this similar to the reason given for linked-
scan MS/MS of a two sector mass spectrometer. Let’s assume

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Magnet Electric Detector

mv sector
mv2/2
Ion source
B/E = mv / mv2/2 = 2/v
KE = mv2/2 = qE

m1+->m2+ Collision chamber

v1 ~ v2 1st Field-free region

Linked Scans Schematic

that the collision chamber in the third field-free region is

grounded. Precursor ions that leave MS-I with a mass m1 have a
kinetic energy mv2/2 and a momentum mv. Assume that these
ions decompose to produce product ions with mass m2 in the
collision chamber between MS-I and MS-II (the third field-free
region). It is also safe to assume that the velocity of these ions
does not change (see the discussion of 2-sector linked scans).
The ions will have a kinetic energy of m2v12/2 and a momentum
of m2v1, or m2/m1 times less than the original momentum for the
precursor ions. We will still have to scan MS-II to pass all product
ions that have velocity v1 if we want to detect the product ions
resulting from the dissociation of precursor ions with mass m1.
This requires a B/E linked scan for MS-II, just like the one
described for two-sector MS/MS. One problem with this approach
is that the product ions have less kinetic energy, velocity, and
momentum compared to ions of mass m2 that might be formed
in the MS-I ion source. These larger the mass difference between
m1 and m2, the lower the detector response for the product ions.
This can be improved by using a floated collision cell. If we set
the collision cell to a higher potential (say +3 kV for positive-ion
MS/MS), the product ions will be decelerated to 7 kV as they
enter the collision chamber, but the positively charged product
ions leaving the collision chamber will be accelerated by the +3

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kV potential. These accelerated product ions will produce a

greater detector response, and sensitivity for low-mass product
ions will be enhanced. An efficient 4-sector mass spectrometer
requires efficient ion optics. The interface region between MS-I
and MS-II must ensure that ions are transported without loss
through the collision chamber into MS-II.

Note improvement in signal

for low-mass products.

Effect of Floated Collision Cell

Other MS/MS Systems

A comprehensive discussion of all MS/MS instrumentation is well
beyond the scope of this note. However, a brief description of
several common approaches follows.

Triple quadrupole MS

Triple quadrupole mass spectrometers are among the most

common MS/MS systems, and they are in wide use for

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quantitative analysis in the pharmaceutical industry. A minimal

configuration for a triple quadrupole mass spectrometer consists
of an ion source and:

1. A first-stage quadrupole mass analyzer that acts as MS-I.

2. An RF-only quadrupole ion guide that acts as the collision
chamber.
3. A second-stage quadrupole mass analyzer that acts as
MS-II.

The ion detector is placed at the exit of MS-II. Triple quadrupole

mass spectrometers operate in the low-energy collision range
using a collision gas such as argon. Fragmentation efficiency
tends to be high, but reproducibility can be a problem, especially
between different mass spectrometers. Triple quadrupole mass
spectrometers can perform all of the common kinds of MS/MS
analysis: product-ion scans, precursor-ion scans, constant
neutral-loss scans, and selected reaction monitoring.

Trapped-ion MS

The MS/MS experiment is done in a different way for trapped ion

mass spectrometers. Instead of having separate mass
spectrometers in for MS-I and MS-II, a single trapped-ion mass
spectrometer performs the functions of precursor-ion selection,
collisional activation, and product-ion mass analysis. Sequential
operations are performed by manipulating the ions contained in
the trap. This is referred to as "tandem-in-time" MS/MS as
opposed to the "tandem-in-space" MS/MS analysis performed on
magnetic sectors and triple quadrupoles.

Trapped-ion mass spectrometers can only perform product-ion

scans. Constant neutral-loss scans and precursor-ion scans
cannot be performed as a tandem-in-time experiment.

Trapped-ion mass spectrometers can perform multi-stage mass

spectrometry (MSn, or MS/MS/MS...) where the number of

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successive reaction or fragmentation stages can be very large.

This can be useful for elucidating ionic structures. However, one
should be aware that long trapping times and multiple reaction
stages can lead to ion-molecule reactions, ion rearrangements
and similar artifact ions that may be difficult to interpret.

Fourier transform ion cyclotron resonance (FTICR)

1. Precursor-ion selection In FTICR, precursor ions are selected

by applying an RF waveform to eject all other ions from the
trapped-ion cell, so that only the precursor ions remain. Precursor
selectivity depends on the waveform used for ejection. High-
resolution precursor selection is possible by using carefully
tailored ejection waveforms, although one must beware of
frequency shifts due to changing numbers of ions in the trapping
cell.

2. Collisional activation The isolated precursor ions are

accelerated to a higher kinetic energy by applying another RF
pulse or waveform that increases the precursor ion's radius (and
kinetic energy). The maximum kinetic energy that can be
achieved is limited by ejection when the radius becomes large
enough for the ion to collide with the trapping cell walls. The
maximum kinetic energy that can be achieved decreases with
increasing mass-to-charge ratio, and increases with increasing
magnetic field strength. The accelerated precursor ions are
trapped for a period of several milliseconds or longer to allow
them to collide with the target gas. The collision gas is either
introduced continuously or added with a pulsed valve.

4. Product-ion detection The product ions are then excited into

coherent motion with another RF waveform and the ion image
currents are detected to produce a time-varying signal. The
Fourier transform of the ion signal produces the mass spectrum.
Several unique experiments can be performed with FTICR. The
number of possible experiments is very large, but includes:
• Multiple reaction stages

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• Ion cooling followed by reacceleration and redetection

• Photodissociation of trapped ions
• Ion-molecule reaction studies
• Ion-electron collisions
• High-resolution analysis of product ions

Although there have been some exceptions, FTICR experiments

generally involve low-energy CID under multiple collision
conditions.

Quadrupole ion traps

The MS/MS experiment in a quadrupole ion trap is analogous to

the FTICR experiment.

1. A waveform is applied to eject all ions except the precursor

ion.

2. The trapped precursor ions are accelerated in the presence of a

collision gas (continuous or pulsed). See the note below for more
about this step.

3. A scan ejects the product ions allowing them to hit the

detector.

Collisional activation in an ion trap is somewhat different from

collisional activation in other mass spectrometers. The ions can
be momentarily accelerated to a higher kinetic energy, but they
are then deaccelerated by the "excitation" waveform. This
acceleration/deacceleration process is allowed to continue in the
presence of a collision gas for periods of milliseconds or longer.
Because of this, the collision energy is not a single value, and the
collision process involves multiple collisions. This is analogous to
refluxing a liquid in a reaction vessel until a reaction occurs.
Fragmentation tends to favor a few low-energy reaction
processes. Hence, it is common to observe only a few fragment-

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ion types in an ion trap MS/MS spectrum. This is the reason that
multi-stage mass spectrometry (MSn) is often needed to obtain
structural information with ion traps. In interpreting the MSn mass
spectra of unknowns, one rearrangement reactions, which may be
difficult to interpret in terms of the original precursor-ion
structure.

Time-of-flight MS
True tandem mass spectrometry is not common with time-of-
flight mass spectrometry at present, although the observation of
metastable ions ("post-source decay") is in wide use for peptide
analysis, and hybrid mass spectrometers with time-of-flight
components are available. However, efforts to develop MS/MS
systems with TOF have begun to show promise, especially with
MALDI/TOF systems involving tandem TOF systems or gated ion
selection followed by post-acceleration and TOF analysis. These
systems offer the possibility of simplicity of design and high-
energy CID.

Hybrid mass spectrometers

Hybrid mass spectrometers combine two unlike mass analyzers to
make an MS/MS system. A large number of combinations are
possible, including:

MS-I MS-II

Sector Quadrupole

Sector Orthogonal-TOF

Sector In-line-TOF

Sector Ion Trap

Quadrupole Time-of-flight (TOF)

Hybrid mass spectrometers combine the characteristic

advantages and disadvantages of their component mass

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analyzers. A detailed discussion of hybrid mass spectrometers is

beyond the scope of this article.

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