Desorption ionization matrix compounds

Matrix-assisted laser desorption ionization (MALDI) A method used for the ionization of high-molecular-weight compounds. In this approach, the analyte is crystallized with a solid matrix and then bombarded with a laser of a frequency which is absorbed by the matrix material. 

The growing interest for the identification and characterization of polar and large compounds caused the development and the introduction of new ionization techniques, such as electrospray ionization (ESI)[4], and matrix assisted laser desorption ionization (MALDI),[5] and their more recent improvements, thus establishing new MS based approaches for studying large molecules, polymers and biopolymers, such as proteins, carbohydrates, nucleic acids. 

A lot of features of MALDI are conveyed by its name it is a desorption ionization, produced by a laser beam, and assisted by a matrix (Figure 2.5). The analyte (1 pmol or less) is mixed with a suitable matrix in a 1 1000 or higher molar ratio. The matrix is composed of a compound with a strong absorption at the wavelength of the laser used. These two factors, matrix excess and its strong absorption, ensure that the energy from the laser pulse is absorbed by the matrix and not by the analyte, thus avoiding its decomposition. Nicotinic acid, sinapinic acid (SA), 2,5-dihydroxy benzoic acid (2,5-DHB) and 2-(4-hydroxyphenylazo)benzoic acid (HABA) are some of the most commonly used matrices for MALDI. 

There is a special case of LDI worth mentioning, desorption/ionization on silicon (DIOS) [159, 160], in which analyte compounds are deposited on a surface of etched silicon. With this substrate the mass range can be extended to a few kilodaltons, allowing for analysis of, for example, small peptides without the involvement of a matrix. 

Fig. 11.6. Diagram depicting desorption ionization (MALDI, FAB or SIMS). The operating principles of the three techniques are similar. The initiating event is exposure of the analyte to a beam of photons, atoms or ions. In order to prevent damage to the fragile analyte molecules and enhance the conversion of the involatile molecules into gas-phase ions, a matrix is employed. For MALDI, the matrix compounds are UV absorbing compounds such as hydroxycinnamic acid. The most commonly used FAB matrix was glycerol and ammonium chloride was employed by some investigators in SIMS experiments (although at low ion beam fluxes molecular species could be effectively ionized for many analytes with minimal evidence of damage by the primary ion beam).

The advantages of supercritical fluid chromatography for polymer separations have been illustrated in the literature for many years. A recent example is the separation of long-chain polyprenols using SFC with matrix-assisted laser-desorption ionization TOF mass spectrometry [10]. The generic name for 1,4-polyprenyl alcohols is polyprenol these compounds generally have smaller polymerization chains of less... 

Example Peptides often contain sulfur from cysteine. Provided there are at least two cysteines in the peptide molecule, the sulfur can be incorporated as thiol group (SH, reduced) or sulfur bridge (S-S, oxidized). Often, both forms are contained in the same sample. At ultrahigh-resolution, the contributions of these compositions to the same nominal m/z can be distinguished. The ultrahigh-resolution matrix-assisted laser desorption/ionization (MALDI) FT-ICR mass spectrum of native and reduced [D-Pen jenkephalin gives an example of such a separation (Fig. 3.25). [39] The left expanded view shows fully resolved peaks due to and C2 isotopomers of the native and the all- C peak of the reduced compound at m/z 648. The right expansion reveals the peak of the native plus the... 

Desorption/ionization on porous silicon (DIOS) without any matrix has been described for the analysis of LRMM compounds with no chemical background [47,... 

Fukai, T., Kuroda, J., and Nomura, T., Accurate mass measurement of low molecular weight compounds by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, J. Am. Soc. Mass Spectrom., 11, 458, 2000. 

In initial work, a total of 17 different ILs were evaluated by the solvation parameter model [8]. Ten of these ILs were comprised of imidazolium or pyrolidinium cations paired with different anions. Many of these compounds represent the traditional class of IL solvents that have been used extensively in organic synthesis reactions or in other analytical uses. The remaining seven ILs consisted of substituted ammonium cations that have proven to be successful analyte matrices in matrix-assisted laser desorption ionization (MALDI) mass spectrometry [11]. 

In the last years, ILs have been applied as matrices for matrix-assisted laser desorption/ionization (MALDI) MS [42], thus expanding the use of MALDI. In Ref. 38 the suitability of alkylammonium- and alkylimidazolium salts of a-cyano-4-hydroxycinnamic acid was investigated as a MALDI matrix and at the same time as the additive of BGE. The alkylammonium salt produced better separation of phenolic compounds than the alkylimidazolium salt. The investigation suggests that it is possible to synthesize ILs suitable for electrophoretic analysis as well as for online MALDI-MS analysis. 

Zabet-Moghaddam, M., Heinzle, E. and Tholey, A., Qualitative and quantitative analysis of low molecular weight compounds by ultraviolet matrix-assisted laser desorption/ionization mass spectrometry using ionic liquid matrices. Rapid Commun. Mass Spec., 18,141, 2004. 

Duncan MYV, Matanovic G, Cerpa-Poljak A (1993) Quantitative analysis of low molecular weight compounds of biological interest by matrix-assisted laser desorption ionization. Rapid Commun Mass Spectrom 7 1090-1094... 

ToF mass spectrometers as dynamic instruments gained popularity with the introduction of matrix assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) as effective pulsed ion sources for the soft ionization of large biomolecules (up to 10s dalton) due to their high ion transmission.38 ToF mass spectrometers, quadrupole analyzers and/or magnetic sector fields can be combined in tandem mass spectrometers (MS/MS) for the analysis of organic compounds. 

Major methods for introducing proteins and other macromolecules into mass spectrometers are electrospray and matrix-assisted laser desorption/ionization (MALDI).18-27 Most often, MALDI is used with a time-of-flight mass spectrometer, which can measure mlz up to 106. Typically, 1 p,L of a 10 jxM solution of analyte is mixed with 1 p,L of a 1-100 mM solution of an ultraviolet-absorbing compound such as 2,5-dihydroxybenzoic acid (the matrix) directly on a probe that fits into the source of the spectrometer. Evaporation of the liquid leaves an intimate mixture of fine crystals of matrix plus analyte. 

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