Matrix (mass spectrometry)

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In mass spectrometry, a matrix is a compound that promotes the formation of ions. Matrix compounds are used in matrix-assisted laser desorption/ionization (MALDI), matrix-assisted ionization (MAI), and fast atom bombardment (FAB).

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Matrix-assisted laser desorption/ionization

MALDI is an ionization technique where laser energy is absorbed by a matrix to create ions from large molecules without fragmentation. The matrix, typically in excess, is mixed with the analyte molecule and deposited on a target. A table of matrix compounds, their structures, laser wavelengths typically used, and typical application is shown below.

MALDI Matrix List
CompoundAbbreviationStructureWavelength (nm)Applications
9-aminoacridine [1] 9AA 9-aminoacridine.png 337lipids, metabolites
α-cyano-4-hydroxycinnamic acid [2] CHCA Alpha-cyano-4-hydroxycinnamic acid.svg 337, 355peptides, lipids, nucleotides
ferulic acid [3] [4] FA Ferulic acid acsv.svg 337, 355, 266proteins
2,5-dihydroxy benzoic acid| [5] DHB Gentisinsaure.svg 337, 355 peptides, nucleotides, oligonucleotides, oligosaccharides
3-hydroxy picolinic acid [6] HPA 3 hydroxypicolinic acid.svg 337, 355oligonucleotides
picolinic acid [7] PA Picolinic acid.svg 266oligonucleotides
sinapinic acid [3] [4] SA Sinapic acid.png 337, 355, 266peptides, proteins, lipids

Matrix-assisted ionization

Matrix-assisted ionization is an ionization method in mass spectrometry that creates ions via the creation of particles at atmospheric pressure and transfer to the vacuum of the mass analyzer. [8]

List of Matrix-assisted Ionization Compounds [9]
CompoundAbbreviationStructure
2,5-dihydroxybenzoic acid DHB Gentisinsaure.svg
2-aminobenzyl alcohol
anthranilic acid Anthranilsaure.svg
2-hydroxyacetophenone 2-hydroxyacetophenone.png

Fast atom bombardment

FAB uses a high energy beam of atoms directed at a surface to create ions. [10] FAB matrix compounds are typically liquids.

FAB Matrix List
CompoundAbbreviationStructure
glycerol Glycerin Skelett.svg
thioglycerol Thioglycerol.png
3-nitrobenzyl alcohol NBA 3-nitrobenzyl alcohol.svg
18-crown-6 ether 18-c-6.png
2-nitrophenyloctyl ether NPOE Nitrophenoxyoctane.png
diethanolamine Diethanolamine.png
triethanolamine Triethanolamine.png

See also

Related Research Articles

<span class="mw-page-title-main">Ion source</span> Device that creates charged atoms and molecules (ions)

An ion source is a device that creates atomic and molecular ions. Ion sources are used to form ions for mass spectrometers, optical emission spectrometers, particle accelerators, ion implanters and ion engines.

<span class="mw-page-title-main">Matrix-assisted laser desorption/ionization</span> Ionization technique

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 biomolecules and various organic molecules, which tend to be fragile and fragment when ionized by more conventional ionization methods. It is similar in character to electrospray ionization (ESI) in that both techniques are relatively soft ways of obtaining ions of large molecules in the gas phase, though MALDI typically produces far fewer multi-charged ions.

<span class="mw-page-title-main">Fast atom bombardment</span>

Fast atom bombardment (FAB) is an ionization technique used in mass spectrometry in which a beam of high energy atoms strikes a surface to create ions. It was developed by Michael Barber at the University of Manchester in 1980. When a beam of high energy ions is used instead of atoms, the method is known as liquid secondary ion mass spectrometry (LSIMS). In FAB and LSIMS, the material to be analyzed is mixed with a non-volatile chemical protection environment, called a matrix, and is bombarded under vacuum with a high energy beam of atoms. The atoms are typically from an inert gas such as argon or xenon. Common matrices include glycerol, thioglycerol, 3-nitrobenzyl alcohol (3-NBA), 18-crown-6 ether, 2-nitrophenyloctyl ether, sulfolane, diethanolamine, and triethanolamine. This technique is similar to secondary ion mass spectrometry and plasma desorption mass spectrometry.

<span class="mw-page-title-main">Sinapinic acid</span> Chemical compound

Sinapinic acid, or sinapic acid (Sinapine - Origin: L. Sinapi, sinapis, mustard, Gr., cf. F. Sinapine.), is a small naturally occurring hydroxycinnamic acid. It is a member of the phenylpropanoid family. It is a commonly used matrix in MALDI mass spectrometry. It is a useful matrix for a wide variety of peptides and proteins. It serves well as a matrix for MALDI due to its ability to absorb laser radiation and to also donate protons (H+) to the analyte of interest.

<span class="mw-page-title-main">History of mass spectrometry</span>

The history of mass spectrometry has its roots in physical and chemical studies regarding the nature of matter. The study of gas discharges in the mid 19th century led to the discovery of anode and cathode rays, which turned out to be positive ions and electrons. Improved capabilities in the separation of these positive ions enabled the discovery of stable isotopes of the elements. The first such discovery was with the element neon, which was shown by mass spectrometry to have at least two stable isotopes: 20Ne and 22Ne. Mass spectrometers were used in the Manhattan Project for the separation of isotopes of uranium necessary to create the atomic bomb.

<span class="mw-page-title-main">3-Hydroxypicolinic acid</span> Chemical compound

3-Hydroxy picolinic acid is a picolinic acid derivative and is a member of the pyridine family. It is used as a matrix for nucleotides in MALDI mass spectrometry analyses.

Soft laser desorption (SLD) is laser desorption of large molecules that results in ionization without fragmentation. "Soft" in the context of ion formation means forming ions without breaking chemical bonds. "Hard" ionization is the formation of ions with the breaking of bonds and the formation of fragment ions.

Sample preparation for mass spectrometry is used for the optimization of a sample for analysis in a mass spectrometer (MS). Each ionization method has certain factors that must be considered for that method to be successful, such as volume, concentration, sample phase, and composition of the analyte solution. Quite possibly the most important consideration in sample preparation is knowing what phase the sample must be in for analysis to be successful. In some cases the analyte itself must be purified before entering the ion source. In other situations, the matrix, or everything in the solution surrounding the analyte, is the most important factor to consider and adjust. Often, sample preparation itself for mass spectrometry can be avoided by coupling mass spectrometry to a chromatography method, or some other form of separation before entering the mass spectrometer. In some cases, the analyte itself must be adjusted so that analysis is possible, such as in protein mass spectrometry, where usually the protein of interest is cleaved into peptides before analysis, either by in-gel digestion or by proteolysis in solution.

<span class="mw-page-title-main">Laser spray ionization</span>

Laser spray ionization refers to one of several methods for creating ions using a laser interacting with a spray of neutral particles or ablating material to create a plume of charged particles. The ions thus formed can be separated by m/z with mass spectrometry. Laser spray is one of several ion sources that can be coupled with liquid chromatography-mass spectrometry for the detection of larger molecules.

<span class="mw-page-title-main">Matrix-assisted laser desorption electrospray ionization</span>

Matrix-assisted laser desorption electrospray ionization (MALDESI) was first introduced in 2006 as a novel ambient ionization technique which combines the benefits of electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). An infrared (IR) or ultraviolet (UV) laser can be utilized in MALDESI to resonantly excite an endogenous or exogenous matrix. The term ‘matrix’ refers to any molecule that is present in large excess and absorbs the energy of the laser, thus facilitating desorption of analyte molecules. The original MALDESI design was implemented using common organic matrices, similar to those used in MALDI, along with a UV laser. The current MALDESI source employs endogenous water or a thin layer of exogenously deposited ice as the energy-absorbing matrix where O-H symmetric and asymmetric stretching bonds are resonantly excited by a mid-IR laser.

<span class="mw-page-title-main">Desorption atmospheric pressure photoionization</span>

Desorption atmospheric pressure photoionization (DAPPI) is an ambient ionization technique for mass spectrometry that uses hot solvent vapor for desorption in conjunction with photoionization. Ambient Ionization techniques allow for direct analysis of samples without pretreatment. The direct analysis technique, such as DAPPI, eliminates the extraction steps seen in most nontraditional samples. DAPPI can be used to analyze bulkier samples, such as, tablets, powders, resins, plants, and tissues. The first step of this technique utilizes a jet of hot solvent vapor. The hot jet thermally desorbs the sample from a surface. The vaporized sample is then ionized by the vacuum ultraviolet light and consequently sampled into a mass spectrometer. DAPPI can detect a range of both polar and non-polar compounds, but is most sensitive when analyzing neutral or non-polar compounds. This technique also offers a selective and soft ionization for highly conjugated compounds.

<span class="mw-page-title-main">Delayed extraction</span>

Delayed extraction is a method used with a time-of-flight mass spectrometer in which the accelerating voltage is applied after some short time delay following pulsed laser desorption/ionization from a flat surface of target plate or, in other implementation, pulsed electron ionization or Resonance enhanced multiphoton ionization in some narrow space between two plates of the ion extraction system. The extraction delay can produce time-of-flight compensation for ion energy spread and improve mass resolution.

<span class="mw-page-title-main">Ambient ionization</span>

Ambient ionization is a form of ionization in which ions are formed in an ion source outside the mass spectrometer without sample preparation or separation. Ions can be formed by extraction into charged electrospray droplets, thermally desorbed and ionized by chemical ionization, or laser desorbed or ablated and post-ionized before they enter the mass spectrometer.

<span class="mw-page-title-main">Franz Hillenkamp</span>

Franz Hillenkamp was a German scientist known for his development of the laser microprobe mass analyzer and, with Michael Karas, matrix-assisted laser desorption/ionization (MALDI).

<span class="mw-page-title-main">Surface-assisted laser desorption/ionization</span>

Surface-assisted laser desorption/ionization (SALDI) is a soft laser desorption technique used for mass spectrometry analysis of biomolecules, polymers, and small organic molecules. In its first embodiment Koichi Tanaka used a cobalt/glycerol liquid matrix and subsequent applications included a graphite/glycerol liquid matrix as well as a solid surface of porous silicon. The porous silicon represents the first matrix-free SALDI surface analysis allowing for facile detection of intact molecular ions, these porous silicon surfaces also facilitated the analysis of small molecules at the yoctomole level. At present laser desorption/ionization methods using other inorganic matrices such as nanomaterials are often regarded as SALDI variants. As an example, silicon nanowires as well as Titania nanotube arrays (NTA) have been used as substrates to detect small molecules. SALDI is used to detect proteins and protein-protein complexes. A related method named "ambient SALDI" - which is a combination of conventional SALDI with ambient mass spectrometry incorporating the direct analysis real time (DART) ion source has also been demonstrated. SALDI is considered one of the most important techniques in MS and has many applications.

<span class="mw-page-title-main">Robert J. Cotter</span>

Robert J. Cotter was an American chemist and mass spectrometrist. His research contributed to many early advances in the field of time-of-flight mass spectrometry. From 1998 to 2000 he was president of the American Society for Mass Spectrometry. Cotter was also a co-investigator on the Mars Organic Molecule Analyzer (MOMA) project, developing a miniaturized, low power consumption ion trap/time-of-flight mass spectrometer that was to be deployed with the ExoMars rover, now the Rosalind Franklin rover.

<span class="mw-page-title-main">Michael Barber (chemist)</span> British chemist and mass spectrometrist

Michael (Mickey) Barber, FRS was a British chemist and mass spectrometrist, best known for his invention of fast atom bombardment ionisation.

<span class="mw-page-title-main">Desorption/ionization on silicon</span> Soft laser desorption method

Desorption/ionization on silicon (DIOS) is a soft laser desorption method used to generate gas-phase ions for mass spectrometry analysis. DIOS is considered the first surface-based surface-assisted laser desorption/ionization (SALDI-MS) approach. Prior approaches were accomplished using nanoparticles in a matrix of glycerol, while DIOS is a matrix-free technique in which a sample is deposited on a nanostructured surface and the sample desorbed directly from the nanostructured surface through the adsorption of laser light energy. DIOS has been used to analyze organic molecules, metabolites, biomolecules and peptides, and, ultimately, to image tissues and cells.

<span class="mw-page-title-main">Matrix-assisted ionization</span>

In mass spectrometry, matrix-assisted ionization is a low fragmentation (soft) ionization technique which involves the transfer of particles of the analyte and matrix sample from atmospheric pressure (AP) to the heated inlet tube connecting the AP region to the vacuum of the mass analyzer.

References

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