Electron ionization 740 Subject

Molecules can lose an electron when subjected to a high electric potential resulting in field ionization (FI) [366,534,535]. High fields can be created in an ion source by applying a high voltage between a cathode and an anode called a field emitter. A field emitter consists of a wire covered with microscopic carbon dendrites, which greatly amplify the effective field at the carbon points. 

To summarize, mass spectrometry has successfully been used for the identification of compounds containing a Zn—C bond, which have a large diversity of structures and complexity. These complexes have been subjected to different ionization methods (such as El, Cl, EAB and ESI) and in many cases they generated numerous Zn-containing fragment ions. Under soft (Cl or FAB) experimental conditions, some of these compounds produced protonated molecules [M-t-H]" " or even protonated dimerlike species [M2H — R]+. Electron ionization was successful for the characterization of many volatile Zn-containing compounds. Peaks of molecular ions M+ were frequently observed, but the majority of the mass spectra were dominated by Zn—C bond dissociation products. 

Using conventional electron ionization mass spectrometry, everything occurs in a vacuum such that any collision is highly unlikely. The molecule receives energy from an electron beam and is ionized into a radical cation. The ion that is thus formed is subjected to an electric field that directs it towards the analyser. For instance, suppose a singly charged 100 u mass ion is accelerated by a 1000 V potential difference in the source. This ion has a mass of... 

At that time the mass spectrometric ionization techniques of electron ionization (El) [1] and chemical ionization (Cl) [2] required the analyte molecules to be present in the gas phase and were thus suitable only for volatile compounds or for samples subjected to derivatization to make them volatile. Moreover, the field desorption (FD) ionization method [3], which allows the ionization of non-volatile molecules with masses up to 5000 Da, was a delicate technique that required an experienced operator [4], This limited considerably the field of application of mass spectrometry of large non-volatile biological molecules that are often thermolabile. 

Cationic radicals are much less stable and noticed prominently in mass spectroscopy. When a molecule in gas phase is subjected to electron ionization, one electron is abstracted by the electron beam to create a radical cation. This species represents the molecular ion or parent ion, which on fragmentation gives a complex mixture of ions and uncharged radical species. For example, the methanol radical cation fragments into a methyl cation CFl and a hydroxyl radical. Secondary species are also generated by proton gain (M -F 1) and proton loss (M — 1). 

One-electron atoms subjected to a time-dependent external field provide physically realistic examples of scattering systems with chaotic classical dynamics. Recent work on atoms subjected to a sinusoidal external field or to a periodic sequence of instantaneous kicks is reviewed with the aim of exposing similarities and differences to frequently studied abstract model systems. Particular attention is paid to the fractal structure of the set of trapped unstable trajectories and to the long time behavior of survival probabilities which determine the ionization rates of the atoms. Corresponding results for unperturbed two-electron atoms are discussed. 

The distinguishing feature of LFCM is low activation energy for electron ionization, which can provide a high spatial density of electron excitations in Q-particlcs tracks and can lead to the group of phenomena, connected with the so-called Coulomb explosion. The latter item is a subject of a special interest [14,15],... 

Biological specimen extraction can be accomplished by liquid-liquid, solid-phase or solid-phase microextraction with subsequent detection of GHB or GBL by gas chromatography-mass spectrometry (GC-MS) using electron ionization (El), positive or negative chemical ionization (CI) or gas chromatography with flame ionization detection (GC-FID). LeBeau et al. (1999) describes a method that employs two ahquots of specimen. The first is converted to GBL with concentrated sulfuric acid while the second is extracted without conversion. A simple liquid-liquid methylene chloride extraction was utilized, and the ahquots were then screened by GC-FID without derivatization. Specimens that screened positive by this method were then re-aliquoted and subjected to the same extraction with the addition of the deuterated analog of GBL. The extract was then analyzed by headspace GC-MS in the full-scan mode. Quantitation was performed by comparison of the area of the... 

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... 

GC-MS is conducted with the same types of capillary columns using He carrier gas. Gas chromatographic conditions are usually similar to GC-ECD. There are a range of possible detection modes for POPs by GCMS and the reader is referred to recent texts on the subject (Chapman, 1995, Oehme, 1999). Electron ionization (El) mode is used for... 

The oldest and most frequently applied ionization technique is electron ionization (El). In El, the analyte vapor is subjected to bombardment by energetic electrons (typically 70 eV). Most electrons are elastically scattered, others cause electron excitation of the analyte molecules upon interaction, while a few excitations cause the complete removal of an electron from the molecule. The last type of interaction generates a radical cation, generally denoted as M", and two electrons ... 

In electron ionization, internal energy distribution is very important This means that ions possess very different internal energies among the formed M+- ion population. This phenomenon occurs because (1) all the molecules M do not arrive in the source with the same energy because they clash and collide with the omnipresent helium atoms and residual atmospheric molecules, and (2) all the electrons emitted by the filament do not collide with the molecules with the same kinetic energy (70 eV is the average value). These electrons have different speed characteristics according to the part of the filament that emits them they are also subject to collisions with helium atoms and HjO, Nj, and O2 molecules present in the source. 

The spectra are therefore often dominated by a molecular ion of m/z ratio M, which by the way constitutes the main objective of electron attachment users. This is why the dissociation of M ions has been the subject of very few studies compared to M+ and MH+ ions. Figure 9.57 compares the electron ionization and electron... 

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