mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...

, matrix-assisted ionization (also inlet ionization) is a low fragmentation (soft)

ionization Ionization, or Ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule i ...

technique which involves the transfer of particles of the analyte and

matrix Matrix most commonly refers to: * ''The Matrix'' (franchise), an American media franchise ** ''The Matrix'', a 1999 science-fiction action film ** "The Matrix", a fictional setting, a virtual reality environment, within ''The Matrix'' (franchis ...

sample from

atmospheric pressure Atmospheric pressure, also known as barometric pressure (after the barometer), is the pressure within the atmosphere of Earth. The standard atmosphere (symbol: atm) is a unit of pressure defined as , which is equivalent to 1013.25 millibars, 7 ...

(AP) to the heated inlet tube connecting the AP region to the vacuum of the

mass analyzer Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...

. Initial ionization occurs as the pressure drops within the inlet tube. Inlet ionization is similar to

electrospray ionization Electrospray ionization (ESI) is a technique used in mass spectrometry to produce ions using an electrospray in which a high voltage is applied to a liquid to create an aerosol. It is especially useful in producing ions from macromolecules becaus ...

in that a reverse phase solvent system is used and the ions produced are highly charged, however a voltage or a laser is not always needed. It is a highly sensitive process for small and large molecules like

peptides Peptides (, ) are short chains of amino acids linked by peptide bonds. Long chains of amino acids are called proteins. Chains of fewer than twenty amino acids are called oligopeptides, and include dipeptides, tripeptides, and tetrapeptides. A p ...

proteins Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. Proteins perform a vast array of functions within organisms, including catalysing metabolic reactions, DNA replication, respo ...

and lipids that can be coupled to a liquid chromatograph. Inlet ionization techniques can be used with an

Orbitrap In mass spectrometry, Orbitrap is an ion trap mass analyzer consisting of an outer barrel-like electrode and a coaxial inner spindle-like electrode that traps ions in an orbital motion around the spindle. The image current from the trapped ions is ...

mass analyzer, Orbitrap fourier transform mass spectrometer, linear trap quadrupole and

MALDI-TOF In mass spectrometry, matrix-assisted laser desorption/ionization (MALDI) is an ionization technique that uses a laser energy absorbing matrix to create ions from large molecules with minimal fragmentation. It has been applied to the analysis of b ...

Types of inlet ionization

Matrix-assisted inlet ionization

In Matrix-assisted inlet ionization (MAII), a

which can be a solvent is used at ambient temperature with the analyte of interest as a mixture. The matrix/analyte mixture is inserted into the heated inlet tube through tapping the mixture at the opening end of the tube. For the highly charged ions of the analyte to be produced from ionization, desolvation of the matrix molecules needs to occur. Matrices that can be used include:

2,5-dihydroxybenzoic acid Gentisic acid is a dihydroxybenzoic acid. It is a derivative of benzoic acid and a minor (1%) product of the metabolic break down of aspirin, excreted by the kidneys. It is also found in the African tree ''Alchornea cordifolia'' and in wine. Pro ...

, 2,5-dihydroxyacetophenone, 2-aminobenzyl alcohol,

anthranilic acid Anthranilic acid is an aromatic acid with the formula C6H4(NH2)(CO2H) and has a sweetish taste. The molecule consists of a benzene ring, ''ortho''-substituted with a carboxylic acid and an amine. As a result of containing both acidic and basic f ...

, and 2-hydroxyacetophenone.

Laserspray inlet ionization

Laserspray inlet ionization (LSII) is a subset of MAII and uses a matrix-assisted laser desorption/ionization (

MALDI In mass spectrometry, matrix-assisted laser desorption/ionization (MALDI) is an ionization technique that uses a laser energy absorbing matrix to create ions from large molecules with minimal fragmentation. It has been applied to the analysis of ...

) method. It was originally called atmospheric pressure matrix-assisted laser desorption/ionization however was renamed as LSII to avoid confusion with MALDI and as it was found to be a type of inlet ionization. As all inlet ionization techniques, highly multiply charged ions are produced. A nitrogen laser is used to

ablate Ablation ( la, ablatio – removal) is removal or destruction of something from an object by vaporization, chipping, erosive processes or by other means. Examples of ablative materials are described below, and include spacecraft material for a ...

the solid matrix/analyte into the heated inlet tube, the observed ions are generated at the surface of the matrix/analyte and so the laser is not directly involved in the ionization as was originally thought. LSII can determine protein molecular weights and has been found to detect masses of proteins up to 20,000 Da. The sensitivity of LSII, for protein detection, is higher by an order of magnitude compared to ESI.

Solvent assisted inlet ionization

Solvent assisted inlet ionization (SAII) is similar to matrix-assisted inlet ionization however the matrix is a solvent such as water,

acetonitrile Acetonitrile, often abbreviated MeCN (methyl cyanide), is the chemical compound with the formula and structure . This colourless liquid is the simplest organic nitrile (hydrogen cyanide is a simpler nitrile, but the cyanide anion is not clas ...

and

methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is a ...

. This ionization technique is highly sensitive to small molecules, peptides and proteins. The analyte is dissolved in the solvent and can either be introduced to the heated inlet tube by a capillary column or directly injected into the inlet tube with a syringe or by pipetting. The capillary column is made of fused silica particles with one end submerged in the sample solvent and the other in the end of the heated inlet tube. The solvent flows through the capillary column without the use of a pump due to the pressure difference between ambient pressure and the vacuum. The temperature can vary in the inlet tube from 50 °C to 450 °C, with the lower temperature being used if the results obtained from a higher temperature are of good resolution. Solvent assisted inlet ionization can be coupled not only to

liquid chromatography In chemical analysis, chromatography is a laboratory technique for the Separation process, separation of a mixture into its components. The mixture is dissolved in a fluid solvent (gas or liquid) called the ''mobile phase'', which carries it ...

(LC) but also to nano LC.

Advantages of inlet ionization

Ionization at atmospheric pressure often leads to a loss of ions during the transfer of the ions from the

ambient pressure Ambient or Ambiance or Ambience may refer to: Music and sound * Ambience (sound recording), also known as atmospheres or backgrounds * Ambient music, a genre of music that puts an emphasis on tone and atmosphere * ''Ambient'' (album), by Moby * ...

region to the vacuum of the mass analyzer. Ions are lost due to dispersion of analyte spray and 'rim loss' causing fewer ions to reach the vacuum for m/z separation to occur. Initial ionization occurs in the sub-atmospheric pressure region of the heated inlet tube which is directly attached to the vacuum of the mass analyzer and so ion loss is reduced as transfer of the ions does not occur. In LSII the use of the laser increases the image quality of the results by producing better

spatial resolution In physics and geosciences, the term spatial resolution refers to distance between independent measurements, or the physical dimension that represents a pixel of the image. While in some instruments, like cameras and telescopes, spatial resolutio ...

. This is where more

pixels In digital imaging, a pixel (abbreviated px), pel, or picture element is the smallest addressable element in a raster image, or the smallest point in an all points addressable display device. In most digital display devices, pixels are the sm ...

are created and so a clearer image is obtained. Multiply charged ions are produced further extending mass range. Multiple methods can be used to fragment molecules producing fragmentation for structural information:

electron transfer dissociation Electron-transfer dissociation (ETD) is a method of fragmenting multiply-charged gaseous macromolecules in a mass spectrometer between the stages of tandem mass spectrometry (MS/MS). Similar to electron-capture dissociation, ETD induces fragmenta ...

(ETD),

collision-induced dissociation Collision-induced dissociation (CID), also known as collisionally activated dissociation (CAD), is a mass spectrometry technique to induce fragmentation of selected ions in the gas phase. The selected ions (typically molecular ions or protonated ...

(CID), and

electron capture dissociation Electron-capture dissociation (ECD) is a method of fragmenting gas-phase ions for structure elucidation of peptides and proteins in tandem mass spectrometry. It is one of the most widely used techniques for activation and dissociation of mass sel ...

(ECD). When using a laser, only small volumes are needed.

References

{{reflist Ion source