Mass - Spectrometry - Sample Inlet - Ion Source

Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt

Technische Universität München
Mass Spectrometry – Sample Inlet & Ion Source
PD Dr. J. Graßmann; PD Dr. T. Letzel


Definition
A mass spectrometer measures the abundance and mass-to charge ratio (m/z) of ions.
An ion is an atom or molecule with a higher or lower number of electrons compared to

its number of protons. The atom or molecule possesses a positive (less electrons than
protons) or negative (more electrons than protons) net charge.
- +
H+ Hydrogen H (neutral) H-
(cation) with 1 valence electron (anion)
(see also slides „Polarity-Basics“)


Parts of a Mass Spectrometer
vacuum
pump
sample
mass
introduction ion source detector computer
analyzer
/inlet
vaccum or atmospheric
pressure vaccum chamber
e.g. Chromatographic separation (compare slides „Chromatography“) like

„High performance liquid chromatography“ (HPLC),
„Ultra-high performance liquid chromatography“ (UHPLC)
„Gas chromatotography“
or direct injection of a non-separated sample via syringe pump

Sample Inlet


Parts of a Mass Spectrometer
vacuum
pump
sample
mass
introduction ion source detector computer
analyzer
/inlet
vaccum or atmospheric
pressure vaccum chamber
Electron (impact) ionization (EI)

ionization of the analytes Electron capture ionization (ECI)
i.e. generation of ions Fast atom bombardment (FAB)
Electrospray ionization (ESI)
&
Atmospheric pressure ionization (APCI)
evaporation of solvent and Atmospheric pressure photo-ionization (APPI)
transfer of analytes into the Matrix Assisted Laser Desorption Ionization (MALDI)
gas phase

Electron ionization
Definition
A beam of electrons (e-) passes through a gas phase sample containing the analytes
(M). The collision of the beams electrons with a neutral molecule can cause an electron
from the molecule to be knocked off. The result is a positively charged molecule (M•+), a
radical cation.
M + e- M•+ + 2 e-
Electron capture ionization

Creation of a radical anion by attachment of an electron
M + e- M•-

Electron ionization
Definition „Radical“
Atom, molecule or ion with unpaired valence electron(s) (compare slides
Polarity_Basics).
Examples:
„Oxygen O2“ (radical anion) Acetaldehyl (radical cation)
H O H O+
a)
H C C H H C C H
O O O O
H c) b) H
unpaired electron
...)
O2 O2•- H O H O+
oxygen superoxide anion H C C H H C C H
+
PD Dr. J. Graßmann; PD Dr. T. Letzel H H

Electron (capture) ionization
Character of ionization technique

- M•+/M•- has the same molecular composition and molecular weight as M.
- EI /ECI are hard ionisation technique, which often results in molecular fragmentation of
an analyte (fragments, i.e. smaller pieces of M have a different molecular weight and
molecular composition than M)
 via the analysis of individual and unique fragmentation patterns („fingerprint“), EI and
ECI provide information about the structure of an analyte and enables the identification
of unknown compounds

Chemical ionization
Definition
Ions are produced through ion-analyte collision. A reagent gas (R) present in the ion
source (e.g. methane CH4, ammonia NH3) is ionised by electrons. Positively or
negatively charged analyte ions (M) are then generated through collision of the analyte
with the ionised reagent gas.
R + e- R+ + 2 e- Ionisation of
R+ + RH RH+ + R reagent gas R
RH+ + M [M+H]+ + R (protonation) or

MH + RH+ RH2 + M+ (H- abstraction) or Ionisation of
M + R2+ [M + R2+]+ (adduct formation) or Analyte M
M + R+ M+ + R (charge exchange)
Chemical ionization

- The molecular weight of the analyte M may be increased due to adduct formation with
the reagent gas or due to protonation (molecular weight of M +1).
- CI is a soft ionisation technique, which usually leaves the analytes intact
 although no fragmentation pattern („fingerprint“) is generated, the techniques

provides information about the molecular weight of the analytes


Electrospray ionization
Definition
Electrospray ionization is a atmospheric pressure ionization method, in which high
voltage is applied to create a spray of fine droplets (aerosol) containing the analytes. In
this process the solvent in desolvated/evaporated, i.e. removed, by heat and gas flows.
positive ionization mode:

M+H [M+H]+
negative ionization mode
M+H [M-H]-


- The analyte M can carry more than one charge, whereby the likelihood of multiple
charged ions tend to increase the higher the analytes molecular weight [M+nH]n+
or [M- nH]n-
- Ionization occurs in the liquid phase.
- ESI is a soft ionisation technique for thermally labile analytes, which usually leaves the
analytes intact (low fragmentation rate)
- Likely occurrence of adducts with e.g. sodium [M+Na]+ or potassium [M+K]+
- Requires the presence of ionisable functional groups like e.g. R–NH2  R–NH3+
or R–COOH  R–COO-
- Generation of ions can be enhanced by pH adjustment (low pH  high H+
concentration  improvement of positive ionization and vice versa)

Sample inlet
Generation of aerosol
& evaporation of solvent
Analyte ion
[M+H]+
Author: Evan Mason

Picture source: https://en.wikipedia.org/wiki/Electrospray_ionization

Atmospheric pressure chemical ionization
Definition
Atmospheric pressure ionization is a method in which the the solvent-analyte mixture is
converted into small droplets (aerosol) and vapourised by means of a nitrogen gas flow
(nebulizer gas). Similar to CI the solvent and/or buffer is charged to create primary ions
(reagent gas) by a corona discharge electrode which is emitting electrons. The solvent/
buffer-ions (S) then charge the ionisable analytes (M) by collision, either through
protonation/ deprotonation, electron capture mechanisms or charge exchange.
S + e- S•+ + 2e- Ionisation of
S•+ + S [S+H]+ + [S-H]• solvent
[S+H]+ + M [M+H]+ + S proton transfer/protonation
S•+ + M M•+ +S charge transfer

Atmospheric pressure ionization

-APCI is a soft ionisation technique, which usually leaves the analytes intact (low
fragmentation rate). It is however less soft than ESI.
- Analytes must be thermally stable
- Ionization occurs in the gas phase (unlike ESI, where ionization occurs in the liquid
phase)
-Since APCI can be performed with a modified ESI source, it is a good alternative
method for analytes, which are unlikely to be ionised and insufficiently detectable with
ESI
- Allows high flow rates up to 2 mL/min to be introduced to the ion source (e.g. from
HPLC)

Atmospheric pressure ionization


APPI (Atmospheric pressure photo-ionization)
Definition and character of ionization technique
APPI uses a krypton lamp to produce gas phase photoionized analytes. The sample is
vaporized by means of a nebulizing gas (e.g. Nitrogen). The ionization is either direct by
photoionization of the analyte or indirect via the ionization the solvent, which then
ionizes the analyte. A third option of ionization works through the addition of a dopant (D)
(e.g. Toluene), which increases the quantity of analyte molecules to be ionized. The
dopant molecules are ionized, followed either by the protonation of the analyte or the
transfer of an electron from the analyte to the dopant.
M + hv M•- + e- direct ionization
M + S + hv [M+S]+ + [S-H]- indirect ionization (via solvent)
D•+ + M [M+H]+ + [D-H]• or D•+ + M M•+ + D indirect ionization (via
PD Dr. J. Graßmann; PD Dr. T. Letzel dopant)

Atmospheric pressure photo-ionization


MALDI (Matrix-assisted Laser Desorption/Ionization)
Definition
For MALDI analysis the sample is embedded into a suitable matrix material, which is
then applied to a metal plate. A pulsed laser irraditates the sample, which triggers the
release (desorption) of matrix and analyte molecules from the surface by vaporization.
The analyte is then ionized by protonation or deprotonation.
to MS analyzer
Author: Mikayé
Picture source: https://de.wikipedia.org/wiki/Matrix-
unterstützte_Laser-Desorption/Ionisation

MALDI (Matrix-assisted Laser Desorption/Ionization)

- Soft ionization technique (low fragmentation rate)
- Employed for the analysis of large and complex biopolymers/biomolecules such as
DNA, proteins, peptides and sugars.
- Compared to ESI, MALDI produces less multiple charged ions.
- Suitable for labile, prone to fragmentation analytes
- Occurrence of Na- and K-adducts


FAB (Fast Atom Bombardment)
Definition and character of ionization technique

FAB is similar to techniques like ESI or MALDI. The analyte is mixed with a non-volatile
matrix and is bombarded with a high energy beam of atoms (typically inert gases like
argon or xenon) or ions (e.g. Cs+). Analytes are hereby released from the matrix.
Ionization occurs through protonation or deprotonation.


Summary ionization techniques
Technique Hard/Soft Ionization through Mainly coupled to
(fragmentation)
EI / ECI Hard Electrons (gas phase GC
ionization)
CI Soft Reagent gas (gas phase GC
ionization)
ESI Soft e.g. by pH adjustment of LC, CE
solvent (liquid phase
ionization)
APCI Soft Reagent gas (gas phase LC, CE
ionization)
APPI Soft Photoionization -
MALDI Soft Desorption and ionization LC, CE
FAB Soft Bombardment with atoms LC

or ions


Summary ionization techniques
105
Molecular weight of analyte
ESI
104
103 APCI
EI/CI
102 APPI
101
low medium high
Polarity of analyte

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Lehrstuhl für Siedlungswasserwirtschaft

Ingenieurfakultät Bau Geo Umwelt

Mass Spectrometry – Sample Inlet & Ion Source

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

An ion is an atom or molecule with a higher or lower number of electrons compared to

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

e.g. Chromatographic separation (compare slides „Chromatography“) like

Mass Spectrometry – Sample Inlet & Ion Source

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

Electron (impact) ionization (EI)

Mass Spectrometry – Sample Inlet & Ion Source

Electron capture ionization

Mass Spectrometry – Sample Inlet & Ion Source

Mass Spectrometry – Sample Inlet & Ion Source

Character of ionization technique

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

RH+ + M [M+H]+ + R (protonation) or

Mass Spectrometry – Sample Inlet & Ion Source

Character of ionization technique

 although no fragmentation pattern („fingerprint“) is generated, the techniques

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

positive ionization mode:

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

Mass Spectrometry – Sample Inlet & Ion Source

Author: Evan Mason

Mass Spectrometry – Sample Inlet & Ion Source

Mass Spectrometry – Sample Inlet & Ion Source

Character of ionization technique

Mass Spectrometry – Sample Inlet & Ion Source

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

Mass Spectrometry – Sample Inlet & Ion Source

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

Mass Spectrometry – Sample Inlet & Ion Source

Character of ionization technique

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

Definition and character of ionization technique

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

MALDI Soft Desorption and ionization LC, CE

FAB Soft Bombardment with atoms LC

PD Dr. J. Graßmann; PD Dr. T. Letzel

Mass Spectrometry – Sample Inlet & Ion Source

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