Electron ionization matrix

A connnon feature of all mass spectrometers is the need to generate ions. Over the years a variety of ion sources have been developed. The physical chemistry and chemical physics communities have generally worked on gaseous and/or relatively volatile samples and thus have relied extensively on the two traditional ionization methods, electron ionization (El) and photoionization (PI). Other ionization sources, developed principally for analytical work, have recently started to be used in physical chemistry research. These include fast-atom bombardment (FAB), matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ES). 

El = electron ionization Cl = chemical ionization ES = electrospray APCI = atmospheric-pressure chemical ionization MALDI = matrix-assisted laser desorption ionization PT = plasma torch (isotope ratios) TI = thermal (surface) ionization (isotope ratios). 

The method using GC/MS with selected ion monitoring (SIM) in the electron ionization (El) mode can determine concentrations of alachlor, acetochlor, and metolachlor and other major corn herbicides in raw and finished surface water and groundwater samples. This GC/MS method eliminates interferences and provides similar sensitivity and superior specificity compared with conventional methods such as GC/ECD or GC/NPD, eliminating the need for a confirmatory method by collection of data on numerous ions simultaneously. If there are interferences with the quantitation ion, a confirmation ion is substituted for quantitation purposes. Deuterated analogs of each analyte may be used as internal standards, which compensate for matrix effects and allow for the correction of losses that occur during the analytical procedure. A known amount of the deuterium-labeled compound, which is an ideal internal standard because its chemical and physical properties are essentially identical with those of the unlabeled compound, is carried through the analytical procedure. SPE is required to concentrate the water samples before analysis to determine concentrations reliably at or below 0.05 qg (ppb) and to recover/extract the various analytes from the water samples into a suitable solvent for GC analysis. 

Figure 2.1 Mass spectrometric approach. Dl, direct inlet GC, gas chromatography HPLC, high performance liquid chromatography CZE, capillary zone electrophoresis El, electron ionization Cl, chemical ionization ESI, electrospray ionization DESI, desorption electrospray ionization APCI, atmospheric pressure chemical ionization MALDI, matrix assisted laser desorption ionization B, magnetic analyzer E, electrostatic analyzer...

DGE a AC AMS APCI API AP-MALDI APPI ASAP BIRD c CAD CE CF CF-FAB Cl CID cw CZE Da DAPCI DART DC DE DESI DIOS DTIMS EC ECD El ELDI EM ESI ETD eV f FAB FAIMS FD FI FT FTICR two-dimensional gel electrophoresis atto, 10 18 alternating current accelerator mass spectrometry atmospheric pressure chemical ionization atmospheric pressure ionization atmospheric pressure matrix-assisted laser desorption/ionization atmospheric pressure photoionization atmospheric-pressure solids analysis probe blackbody infrared radiative dissociation centi, 10-2 collision-activated dissociation capillary electrophoresis continuous flow continuous flow fast atom bombardment chemical ionization collision-induced dissociation continuous wave capillary zone electrophoresis dalton desorption atmospheric pressure chemical ionization direct analysis in real time direct current delayed extraction desorption electrospray ionization desorption/ionization on silicon drift tube ion mobility spectrometry electrochromatography electron capture dissociation electron ionization electrospray-assisted laser desorption/ionization electron multiplier electrospray ionization electron transfer dissociation electron volt femto, 1CT15 fast atom bombardment field asymmetric waveform ion mobility spectrometry field desorption field ionization Fourier transform Fourier transform ion cyclotron resonance... 

Figure 14.4 Generation of ions by desorption methods. The sample is placed on a target and then hit either by accelerated electrons (secondary ion mass spectrometry), accelerated atoms (fast atom bombardment) or laser light (laser desorption/ ionization, matrix-assisted laser desorption/ionization). In the case of FAB and MALDl, the analyte is additionally embedded in a matrix, which also is desorbed during these processes.

Proceeding with the large-R analysis of the ionization matrix element, (f V i), we find that at large Kr2-X separations it decreases as 1/R r2 x. As a result, the contribution of the two-electron recombination - ionization pathway to the decay width depends on the cluster geometry as l/-R r Kr Kr2-x-Since the decomposition of the (Kr+)2X cluster along the Kr+-Kr+ coordinate automatically means elongation of the Kr2-X distance as well, the power law exponents are effectively summed, resulting in the l/R Kr dependence. A detailed analysis shows that this type of power law is characteristic of all the possible decay pathways. 

Combined electron ionization mass spectroscopy (EIMS) and matrix isolation FTIR spectroscopic data on vacuum pyrolysis of 1,1-dimethyl-l-germa-3-thietane assisted by theoretical calculations provide a reasonable foundation for mechanistic interpretation of its thermal decomposition (see Section 2.21.6.1, Equation 7) <1998JA5005>. 

Sample ionization. Requirements for sample ionization are much more severe in MS/MS than in GC/MS. For MS/MS, the ionization method should create one ion for each component, and the structure of the ion should be the same as that of the neutral surrogate. Electron ionization usually does not fulfill these requirements, since the ions formed often include those from rearrangement reactions, and the degree of fragmentation is excessive. Chemical ionization provides the requisite single ion for each component of the matrix in the form of the quasimolecular ion (MFH)+. 

An ideal interface should not cause extra-column peak broadening. Historical interfaces include the moving belt and the thermospray. Common interfaces are electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCl). Several special interfaces include the particle beam—a pioneering technique that is still used because it is the only one that can provide electron ionization mass spectra. Others are continuous fiow fast atom bombardment (CF-FAB), atmospheric pressure photon ionization (APPI), and matrix-assisted laser desorption ionization (M ALDl). The two most common interfaces, ESI and APCI, were discovered in the late 1980s and involve an atmospheric pressure ionization (API) step. Both are soft ionization techniques that cause little or no fragmentation hence a fingerprint for qualitative identification is usually not apparent. 

Other Methods of Ionization. There are several other methods for ionization in addition to ESI and MALDI. However, most of them are not commonly used in proteomics. Some of these include chemical ionization, electron ionization, fast atom bombardment (FAB), and many others. Most of these lead to disintegration or fragmentation of analyte molecules and are not commonly used in proteomics. However, FAB has some application in the analysis of proteins and peptides, because this is a soft ionization procedure and does not cause the fragmentation of molecules under analysis. In the FAB method, a nonvolatile matrix such as m-nitrobenzyle alcohol is used to hold the analyte molecules. Analyte molecules are vaporized and ionized by bombardment with the high-energy beam of xenon or cesium from a probe inserted directly into the device containing the sample. Ionized molecules thus obtained are then subjected to separation by the mass... 

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