Overview of A Mass Spectrometry

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Overview of a Mass Spectrometer

GC-MS Instrument

Instrument footprint

GC
MS
Electron Multiplier Detector

An electron multiplier consists of many dynodes. A progressively decreasing


negative voltage (more positive) is applied to each dynode in series by dividing the
high voltage applied to the first dynode with resisters. A few secondary electrons
are emitted from the first dynode by ion impingement. An electron multiplier is put
in an off-axis position to reduce noise signals by direct hit of neutral particles.
Different Mass Analyzers
A mass analyzer is the component of the mass spectrometer that takes
ionized masses and separates them based on charge to mass ratios and
outputs them to the detector where they are detected and later
converted to a digital output.

There are five general types of mass analyzers that can be used for the
separation of ions in a mass spectrometry.

1. Quadrupole Mass Analyzer


2. Time of Flight Mass Analyzer
3. Magnetic /Electrostatic Double Sector Mass Analyzer
4. Quadrupole Ion Trap Mass Analyzers
5. Ion Cyclotron Resonance
Mass Analyzers

Quadrupole Time-of-Flight (TOF)

L m
K .E.  zV Tf 


z
Quadrupole Ion Trap Mass Analyzers
The ions enter the area between the electrodes through one of the end caps. After entry,
the electric field in the cavity due to the electrodes causes the ions of certain m/z values
to orbit in the space. As the radio frequency voltage increases, heavier mass ion orbits
become more stabilized and the light mass ions become less stabilized, causing them to
collide with the wall, and eliminating the possibility of traveling to and being detected by
the detector.

The quadrupole ion trap usually runs a mass selective ejection, where selectively it
ejects the trapped ions in order of in creasing mass by gradually increasing the applied
radio frequency voltage.

ChemWiki
Matrix-Assisted Laser Desorption Ionization

Laser radiation of this matrix-analyte preparation results in desorption of the matrix as


a plume, which carries the analyte along with it into gas phase. Thus, the matrix plays a
key role by strongly absorbing the laser light energy and causing, indirectly, the analyte
to vaporize. The matrix also serves as a proton donor and acceptor, acting to ionize
analyte in both positive and negative ionization modes, respectively.
Dept. of Chemistry, Univ. of Pittsburgh
LC-MS Instrument
Dual Ion Source for LC-MS (ESI and APCI)

Shimadzu Scientific Instruments


Electrospray Ionization (ESI)

ESI draws sample solutions to the tip of a capillary tube, where it applies a high voltage
of about 3 to 5 kV. A nebulizer gas flows from outside the capillary to spray the sample.
This creates a fine mist of charged droplets with the same polarity as the applied
voltage. As these charged particles move, the solvent continues to evaporate, thereby
increasing the electric field on the droplet surface. When the mutual repulsive force of
the charges exceeds the liquid surface tension, then fission occurs.
Most of the generated ions are protonated molecules (or deprotonated molecules),
complicated fragment ions are not generated. It generates multivalent ions, depending
on the compound, even if a compound has a molecular mass of 10,000, for example,
ions with a valence of 20 would only have an m/z ratio of 501.
Electrospray Ionization (ESI)
ESI is very suitable for a wide range of biochemical compounds including peptides and
proteins, lipids, oligosaccharides, oligonucleotides, bio-organic compounds, synthetic
polymers.

Dept. of
Chemistry,
Univ. of
Pittsburgh

ESI can produce singly or multiply charged ions. The number of charges retained by a
particular analyte depends on several factors such as the size, chemical composition,
and higher order structure of the analyte molecule, the solvent composition, the
presence of co-solutes, and the instrument parameters. For small molecules (< 2000
Da) ESI typically generates singly, doubly, or triply charged ions, while for large
molecules (> 2000 Da) ESI can produce a series of multiply charged ions.
Atmospheric Pressure Chemical Ionization (APCI)
Low polarity analytes

APCI vaporizes solvent and sample molecules by spraying the sample solution into a
heater (heated to about 400 °C) using a gas, such as N2. Solvent molecules are ionized
by corona discharge to generate stable reaction ions.

Protons are transferred between these reaction ions and sample molecules (ion-
molecule reaction) to ionize sample molecules by either adding or removing a proton.
These ion-molecule reactions are known to involve several patterns, such as proton-
transfer reactions and electrophilic addition reactions. As with ESI, mainly protonated
molecules (or deprotonated molecules) are detected.
Atmospheric Pressure Chemical Ionization (APCI)
Typically single charged analytes produced

Dept. of
Chemistry,
Univ. of
Pittsburgh

Sample solution undergoes nebulization to form an aerosol spray of fine droplets and it is
rapidly heated in a stream of nitrogen desolvation gas before emerging from the probe as
a desolvated/vaporized sample plume. Solvent/Reagent ions are formed in the region of
the corona discharge needle. These ions react with analyte molecules to form singly
charged protonated or deprotonated analyte ions.
Dual ESI and APCI

Shimadzu
Mass Spectrometry Imaging

Shimadzu Scientific Instruments


Desorption Electrospray Ionization (DESI) -MS
+ electrolyte

Desorption electrospray ionization minimizes the requirements for sample


preparation by enabling investigation of samples in their native environment.
Prosolia
Desorption Electrospray Ionization (DESI) -MS
Selected ion images of phosphatidylcholine (PC) species in a 10 μm
coronal section of rat brain. A)PC(32:0) [M+K] m/z 772.3 B)PC(36:1)
[M+K] m/z 826.4.

A B

MALDI is primarily suited for detection of large molecules such as peptides


and proteins, and DESI is well suited for detection of small molecules such as
lipids, metabolites and drug molecules.
Fast Scanning Speeds
0.1 m/z ~15,000 amu/s

Ultrafast HPLC requires


fast detector response.
Fast Scanning Speeds
Scan and SIM Mode

You can use either scan mode or SIM mode for GC/MS analysis. The choice depends on the
aim of the analysis. If you identify the sample components using a mass spectrum, scan
mode is indispensable. SIM mode is suitable for quantitative analysis of trace
components.When the mass spectra pf the trace components are known.

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