Soft ion sources

The trade-off of this advantage is that identification and characterization of lipids using a mass spectrometer with such a soft-ion source depend heavily on tandem MS analysis. Conduction of tandem MS analysis requires the mass spectrometer possessing multiple mass analyzers or an ion trap. In fact, a variety of hybrid combinations of mass analyzers have been developed and have greatly facilitated lipidomic analyses [33, 59]. 

In summary, the ionization efficiency and analytical sensitivity of ICP is higher than other ion sources, and the matrix effect in ICP-MS is much smaller. It can be found that the ICP and other soft ion sources (e.g. ESI or MALDI) are really complementary techniques. Structural information is preferably obtained by means of ESI- or MALDI-MS, whereas ICP-MS is ideal to quantify elements in samples, even in the very low concentration ranges. 

MS-MS is a term that covers a number of techniques in which two stages of mass spectrometry are used to investigate the relationship between ions found in a mass spectrum. In particular, the product-ion scan is used to derive structural information from a molecular ion generated by a soft ionization technique such as electrospray and, as such, is an alternative to CVF. The advantage of the product-ion scan over CVF is that it allows a specific ion to be selected and its fragmentation to be studied in isolation, while CVF bring about the fragmentation of all species in the ion source and this may hinder interpretation of the data obtained. 

Recent attention has focused on MS for the direct analysis of polymer extracts, using soft ionisation sources to provide enhanced molecular ion signals and less fragment ions, thereby facilitating spectral interpretation. The direct MS analysis of polymer extracts has been accomplished using fast atom bombardment (FAB) [97,98], laser desorption (LD) [97,99], field desorption (FD) [100] and chemical ionisation (Cl) [100]. 

ESI and APCI are soft ionisation techniques which usually result in quasi-molecular ions such as [M + H]+ with little or no fragmentation molecular weight information can easily be obtained. However, experimental conditions can also be chosen in such a way that a sufficiently characteristic pattern is obtained, allowing verification [540]. ESI is amenable to thermally labile and nonvolatile molecules. Both ESI and APCI are much more sensitive than PB and very well suited for quantitative analysis, but less so for unknown samples. The choice among the two is usually determined by the application. Recently, nanoscale LC-ESI-MS has been developed [541]. The nano-electrospray ion source offers the highest sensitivity available for LC-MS (atto-to femtomole range) and can also be used as an off-line ion source. 

Field desorption (FD) was introduced by Beckey in 1969 [76]. FD was the first soft ionization method that could generate intact ions from nonvolatile compounds, such as small peptides [77]. The principal difference between FD and FI is the sample injection. Rather than being in the gas phase as in FI, analytes in FD are placed onto the emitter and desorbed from its surface. Application of the analyte onto the emitter can be performed by just dipping the activated emitter in a solution. The emitter is then introduced into the ion source of the spectrometer. The positioning of the emitter is cmcial for a successful experiment, and so is the temperature setting. In general, FI and FD are now replaced by more efficient ionization methods, such as MALDI and ESI. For a description of FD (and FI), see Reference 78. 

Note At first sight, there is no difference whether Qi or Q3 is switched to RF-only for MS mode. However, for El it seems better to operate Q3 in RF-only mode. Otherwise, the ion source would effectively extend up to the entrance of Q3 making fragment ions more abundant due to elongated time for dissociations. Soft ionization methods do not show such differences. 

In El mass spectrometry, the molecular ion peak can be increased to a certain degree by application of reduced electron energy and lower ion source temperature (Chap. 5.1.5). However, there are compounds that thermally decompose prior to evaporation or where a stable molecular ion does not exist. The use of soft ionization methods is often the best way to cope with these problems. 

Due to the increasing significance of soft ionization techniques for the analysis of phosphorus-, metal- and metalloid-containing biomolecules, matrix-assisted laser-induced desorption/ionization (MALDI) and electrospray ion sources (ESI) will be discussed briefly at the end of this chapter. 

A schematic of the basic principles of a matrix-assisted laser desorption/ion source is shown in Figure 2.35. By the interaction of a focused laser beam with short pulses and a suitable matrix, the energy of the photons is transferred to the matrix molecules. In MALDI mostly pulsed UV (e.g., nitrogen, X = 337 nm, pulse duration 3-10 ns), but also IR lasers (e.g., Er YAG, X = 2.94 (xm or C02, X = 10.6(xm with a higher pulse duration of up to 600 ns) are used. The MALDI mass spectra obtained during soft ionization by UV and IR lasers are identical. The energy density... 

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. 

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