IONISATION TECHNIQUES IN MASS SPECTROSCOPY

Field Ionisation (FI) and Field Desorption (FD)

FIELD IONISATION (FI) AND FIELD DESORPTION (FD)

H. D. Becky in 1969 introduced the concept of FDMS for analysis of large organic molecules. FI and FD are "soft" ionisation methods; i.e. the increase in the internal energy transferred to the analyte molecules during ionisation is minimal and the sunsequent fragmentation is largely reduced.

FIELD IONIZATION (FI)

Field ionization (FI) is the generation of M+ ions by removal of electrons, primarily from gas sample molecules, using a high electric field. This generally occurs at a sharp edge or tip that is biased to a high electrical potential

During Field Ionization, sample molecules become ionized by the quantum tunneling of a valence electron as they pass close to the tips of emitter electrodes.

The electrodes are essentially a large collection of carbon micro-needles, deposited on tungsten wire, surrounded by a very high electric field within the ion source. These micro-needles allow very high electric field strengths to be applied to a molecule.

The mechanism of ionisation is based on the fact that when a molecule is subjected to a very high electric field, a valence electron tunnels through the potential barrier and is removed from the molecule. The resulting ion is therefore M+.

FIELD IONIZATION
Field Ionization offers the following benefits: Suitable for substances that can be introduced into the source via a gas chromatograph or heated direct insertion probe Energetically gentle ionization process providing a large proportion of molecular ions from many different substances Spectra exhibit some fragmentation due to the heat used for sample volatilization

FIELD DESORPTION (FD)

Field desorption (FD) is a method for emitting ions into the gas phase. Sample spread on an emitter is heated while a high electric field is applied. Ions are then emitted by the tunneling, ion-molecule reactions, thermal fusion effects, and other phenomenon occurring on the emitter surface and around the whisker ends. The ionization phase depends strongly on the sample material and the spread condition.

FIELD DESORPTION
Field Desorption analysis feature the following: Suitable for high molecular mass and/or thermally labile substances such as polymers, peptides, carbohydrates and organic or inorganic salts A solution of the sample is applied to the emitter before it is introduced into the ion source The emitter is mounted on the tip of the axial sample introduction probe Samples undergo little or no fragmentation during FD ionization Ionization maximizes the production of high-quality molecular mass information for improved compound identification/confirmation FD-MS has proven capabilities in analyzing nonionic low- to medium polarity compounds

FIELD IONIZATION (FI) VERSUS FIELD DESORPTION (FD)

FIELD IONIZATION (FI) VERSUS FIELD DESORPTION (FD)

FI : sample is heated in a vacuum so as to volatilize it onto an ionization surface. FI is suited for use with volatile, thermally stable compounds. FI sources are arranged to function also as FD sources FD : the sample is placed directly onto the surface (dipping emitter in an analyte solution) before ionization but FD is needed for nonvolatile and/or thermally labile substances.

FIELD IONIZATION (FI) VERSUS FIELD DESORPTION (FD)

FI Spectrum for D-Glucose

FD Spectrum for D-Glucose

LIQUID INTRODUCTION FIELD DESORPTION IONISATION (LIFDI)

A major advance was made by H B Linden in 2000 by incorporating a fused silica capillary to allow liquid introduction of the analyte onto the FD emitter, hence the acronym LIFDI. LIFDI is regarded as a convenient tool to ionize any solid, liquid, or gaseous species transferred to the emitter inside of the ion source through a capillary without breaking vacuum. This development made the FD technique much more user friendly and, because the emitter remains in place, the fragile emitters last much longer. The fused silica capillary also enables air and moisture sensitive molecules to be easily introduced without exposure to ambient air.

The entire LIFDI sample preparation is done by dipping the capillary into the sample solution for 1-2 s. A volume of 40 nL is aspirated automatically and forced through the capillary. Upon arrival at the emitter, osmotic and capillary forces between the dendrites distribute the solution over the entire emitter. The small volume of solvent is evaporated in the vacuum within seconds, followed by acquiring spectra at a total sample prep of less than 30 s.

APPLICATIONS
Identification of Organometallic compounds using Field Desorption Ionization Technique. Qualitative and quantitative analysis for drugs and endogenous compounds, e.g., tranquillizers, immunosuppressive and antitumour agents and free amino acids, in human body fluids, biocides, e.g., phenylureas, carbamates, organophosphorus and organometallic compounds, in river water, and natural and synthetic products, e.g., saponins, chlorophyll and deoxyribonucleotides, can be performed Field desorption mass spectrometric profile analysis can be used as a technique for the detection of biotransformation products of xenobiotics in crude urine extracts.