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    Mass Spectrometry_ Ionization Part III

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    Suchismita Banerjee

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    © All Rights Reserved
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    Mass Spectrometry_ Ionization Part III

    Uploaded by

    Suchismita Banerjee
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    3 views5 pages

    Mass Spectrometry_ Ionization Part III

    Uploaded by

    Suchismita Banerjee

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    © All Rights Reserved
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    Other Desorption based Ionization methods:

    1. Fast Atom Bombardment Ionization

    ● It is an ionization technique in which the analyte and ​non-volatile liquid matrix mixture
    is bombarded by a high energy beam of inert gas such as ​Argon or Xenon​.
    ● This technique is used for ionization of polar high molecular weight compounds such as
    polypeptides.
    ● Commonly used matrices include :-
    Glycerol
    Monothioglycerol
    Carbowax
    2,4 – dipentyl phenol
    3 – nitrobenzyl alcohol (3 – NBA)
    ● These solvents easily dissolve organic compounds and do not evaporate in vacuum.

    Working Scheme:

    ● The ​bombarding beam ​consists of Xenon or Argon atoms of high translational energy.
    ● This beam is produced by ​first ionizing the Xenon ​(or Argon atoms with electrons to
    give Xenon radical cations.
    Xe+e​- ​=Xe​.+ ​+2e​-
    ● The radical cations are then ​accelerated to 6 – 10 KeV ​to give radical cations of high
    translational ​energy (Xe)​++ , which are then passed through a chamber containing Xenon
    atoms at a pressure of 10​-5 ​torr.
    ● During this passage high energy cations obtain electrons from Xenon atoms to become
    high energy atoms (Xe).
    ● The lower energy ions are removed by electrostatic deflector.
    (Xe)​++ ​=​ ​Xe​.+ ​+ Xe

    (Xe)​.+ ​+ Xe = (Xe) + Xe​.+


    Matrix Preparation:

    ● The analyte is ​dissolved in the liquid matrix ​such as glycerol and applied as a thin layer
    on the sample probe shaft.
    ● The mixture is bombarded with the high energy beam of Xenon atoms.
    ● Xenon ionizes the glycerol molecules to give glycerol ions.
    ● These ions react with the surrounding glycerol molecules to produce (G+H)​+ ​as reactant
    ions.
    ● The sample molecules then ​undergo proton transfer or hydride transfer or ion-pair
    interaction with reactant ions to give quasimolecular ion pseudomolecular ions such
    as (M+H)+ , (M-H)- or (M+G+H)+.
    ● These ions are then extracted from a slit lens system designed to collect ions and directed
    to a mass analyzer.
    ADVANTAGES
    Used for ionization of polar high molecular weight samples.
    Provides rapid heating of samples and reduces sample fragmentation. Rapid ionization.

    DISADVANTAGES
    Difficult to distinguish between low molecular weight compounds. Compounds must be
    soluble in a liquid matrix. Not good for multiply charged compounds.

    2. Secondary Ion Mass Spectrometry

    ● Secondary ion mass spectrometry is nearly ​identical to FAB ​except the primary ionizing
    beam is an ion beam rather than a neutral atom beam.
    ● The ​Cesium or Argon ions ​are most commonly used.

    ​Working Scheme:​

    ● The ​source consists of a cylindrical grid ​and a vertically placed ion gun or filament.
    ● Argon or Cesium gas ​is ionized by heating the filament to ​produce monoenergetic
    noble gas ions​.
    ● The ​ion gun ​can produce an ion beam of diameter ranging from 0.1mm to 1mm.
    ● The ions are ​accelerated to ​a potential of 300 to 3000 eV.
    ● This ion beam is then ​bombarded on to the surface of the sample​.
    ● This results in the ​formation of secondary sample ions ​by ​charge transfer interaction
    between the sample molecules and the primary gas ions.
    ● The ions formed in the cylindrical grid are ​then extracted from one end and focused on
    the target ​or mass analyzer by an electrostatic lens system.

    ​ADVANTAGES

    Higher sensitivity. Selection of Beam diameter permits for rapid transition from a small surface
    analysis with a small beam to a large surface area.

    3. Thermal ionization or Surface ionization


    ● Thermal surface ionization source is useful for ​inorganic solid materials​.
    ● Samples are ​coated on a tungsten ribbon filament ​and then the filament is heated until
    the sample evaporates .
    ● As the sample evaporates it undergoes ionization.
    ● The ​probability of ionization ​is predictable and is a ​function of work function ​of :-
    Ionization potential of the sample E​1

    Work function of the filament material Φ

    Filament temperature T

    ● This can be summarized as follows


    n​+​/n​0 ​= exp[z(Φ – E​1​)/KT]

    Where,z = electronic charge

    K = Boltzmann’s constant

    n​+ ​= Number of ions formed

    n​0 ​= Number of neutral species

    4. Laser Desorption ionization


    ● Laser desorption methods involve ​interaction of pulsed laser beams with the sample ​to
    produce both ​vaporization and ionization​.
    ● Laser beam is usually of different wavelengths from ​far U.V to far IR ​depending upon
    the sample to be analyzed.

    REQUIREMENTS:

    ● Laser wavelength must be at absorption wavelength of the molecule.


    ● In order to avoid decomposition absorbed energy must be quickly dispersed in the
    molecules.

    Working Scheme:

    Ionization is carried out by two techniques.

    Microprobe techniques

    Laser beam is focused to a very small spot on the back side of a thin metal foil that holds a thin
    film of sample.

    Ions emerge out on the front side from a ​small cratered hole in the foil​.

    Bulk analysis techniques


    The technique uses a ​less focused beam and larger samples​.

    The laser beam produces ​microplasma ​that consists of neutral fragments with elementary and
    fragment ions.

    The ions produced are largely ​protonated and deprotonated species ​that have a unit charge.

    ADVANTAGES
    Used for ​larger-molecules ​such as proteins and carbohydrates.

    DISADVANTAGE

    Laser pulse lasts only for a few microseconds​, suitable mass analyzers are limited to
    time-of-flight and fourier transform spectrometers.

    Molecules of molecular weight ​less than 1000 Da ​for biopolymers and ​9000 Da ​for
    synthetic polymers ​cannot be studied ​as they get decomposed.

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