Techniques and Mass Spectrometers

Ionization Techniques and Mass Spectrometers A. Ionization Techniques 

In 1988-1989, two processes were discovered that allowed the transfer of large molecules into the gas phase matrix-assisted laser desorption and ionization (MALDI) and electrospray ionization (Karas and Hillenkamp, 1988 Fenn et al., 1989). 

Both ionization techniques are cold ionization techniques. They can transfer molecules or molecular assemblies of unlimited mass into the 

The two ionization techniques can be used with all types of mass spectrometers. Here, only those that are the most commonly used in proteomics will be described. Because mass spectrometers use electric and magnetic fields to separate ions, they can only measure mass divided by charge values. In the examples used this is assumed implicitly. In most cases the charge state of an ion can be determined from the mass spectrum. 

Usually ion trap mass spectrometers are combined with an electrospray ionization source (Fig. 1). Ions are transferred into a region that is 

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Prokai and Simonsick [4] examine the use of hyphenated SEC-ESI-MS to obtain information abont chemical composition, resolution of overlapping charge and accurate SEC calibration. Various SEC techniques and mass spectrometers, which yield differences in chromatographic and mass spectroscopic performance of the method and the rnggedness of online coupling, are implemented. SEC-ESI-MS is a powerful technique to address the need for more extensive analysis and characterisation of complex polymer systems. 

VDU screen via suitable electronic amplifying circuitry where the data are presented in the form of an elution profile. Although there are a dozen or more types of detector available for gas chromatography, only those based on thermal conductivity, flame ionization, electron-capture and perhaps flame emission and electrolytic conductivity are widely used. The interfacing of gas chromatographs with infrared and mass spectrometers, so-called hyphenated techniques, is described on p. 114 etseq. Some detector characteristics are summarized in Table 4.11. 

In addition to the diversity of ionisation techniques available, mass spectrometers offer a selection of mass analyser configurations. Of note are single (MS) and triple quadrupole (MS—MS) instruments, ion trap analysers (MS)n, time-of-flight (ToF) analysers, sector field analysers, and Fourier transform-ion cyclotron resonance (FTICR) instruments. 

In secondary-ion mass spectrometery (SIMS) and its sister technique fast atom bombardment mass spectrometry (FARMS), a surface is bombarded with energetic particles, and the kinetic energy of the particles converts substrate and chemisorbed atoms and molecules to gas-phase species. The ejected (or sputtered) material is subsequently interrogated using various analytical tools, such as lasers and mass spectrometers, to indirectly deduce information about the initial surface. The relationships between sputtered material and the surface, however, are not always clear, and erroneous conclusions are easily made. Computer simulations have demonstrated that a fundamental understanding of the sputtering process is required to interpret experimental data fully ... 

Since the development of HPLC as a separation technique, considerable effort has been spent on the design and improvement of suitable detectors. The detector is perhaps the second-most important component of an HPLC system, after the column that performs the actual separation it would be pointless to perform any separation without some means of identifying the separated components. To this end, a number of analytical techniques have been employed to examine either samples taken from a fraction collector or the column effluent itself. Although many different physical principles have been examined for their potential as chromatography detectors, only four main types of detectors have obtained almost universal application, namely, ultraviolet (UV) absorbance, refractive index (RI), fluorescence, and conductivity detectors. Today, these detectors are used in about 80% of all separations. Newer varieties of detector such as the laser-induced fluorescence (LIE), electrochemical (EC), evaporative light scattering (ELS), and mass spectrometer (MS) detectors have been developed to meet the demands set by either specialized analyses or by miniaturization. 

In our laboratory, an on-flow LC-NMR-MS screening (Figure 5.1.1) was applied to both saponin fractions which were not separated into pure compounds by classical column chromatography and further to total asterosaponin fractions obtained by the micropreparative technique, matrix solid-phase dispersion (MSPD) extraction [45] (see Figure 5.1.2). The LC-NMR-MS hyphenation is set up in the widely used parallel configuration of NMR and mass spectrometer (Figure 5.1.3). Typically, absolute amounts of asterosaponin mixtures of about 500 xg - 1 mg are injected onto the column. 

Produced by the EW technique CNM were subjected to investigation using XRD analysis, electron microscopy, and mass-spectrometer analysis. The typical XRD patterns for the exploded materials in different conditions are shown in Fig. 1 and Fig. 2. It is immediately obvious that there is a presence of additional diffraction peaks at small angle values besides those typical for common graphite. This fact clearly demonstrates the appearance of new structural compositions in the synthesis products. A phase analysis performed shows that these diffraction peaks correspond to those for carbonic spatial materials with the fullerene-like structure of the C60-C70 types. 

Ions exiting the drift tube are mass analyzed in mass spectrometer MS2, an important feature if reactions are occurring in the drift cell. Ions are generally detected after MS2 by ion counting techniques. The mass spectrometers MSI and MS2 are typically quadrupole mass filters, and either one or the other can be run in RF-only mode for better signal but without mass selection, if desired. 

This section is devoted to the types of devices most frequently used for both liquid and solid sampling prior to introduction into atomic spectrometers [12-14]. Atomic techniques and mass spectrometry make massive use of electrothermal devices, the maturity of which has been endorsed by lUPAC, which has included it in its Nomenclature, Symbols, Units and their Usage in Spectrochemical Analysis. XII. Terms Related to Electrothermal Atomization , published in 1992 and subsequently reprinted in Spectro-chimica Acta [1]. 

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