Electrosprays atomization technique

The dominating method of ion formation in metabolic flux analysis is electron impact. It might be supplemented in the future by novel methods, such as matrix assisted laser desorption and electrospray. Additional techniques such as chemical ionization, fast atom bombardment or inductively coupled plasma ionization are only of minor importance and not further discussed in this context. 

Electrospray, also called electrohydrodynamic or electrostatic spray, is an atomization technique in which liquids are dispersed solely by the application of high voltages. A simple electrospray setup is shown in Fig. 4. A liquid flows into a metal capillary tube charged to the kilovolt range and emerges from the tip as a conical meniscus, known as a Taylor cone, due to the intense electric field (Fig. 5). An unstable jet extends continuously from the apex of the cone and disperses into charged droplets further downstream. Electrosprays have been used in industrial... 

The concept or the basis of spray pyrolysis method assumes that one droplet forms one product particle. To date, submicrometer- to micrometer-sized particles are typically formed in a spray pyrolysis process. A variety of atomization techniques have been used ftn- solution aerosol formation, such as ultrasonic spray pyrolysis, electrospray pyrolysis, low pressure spray pyrolysis using a filter expansion aerosol generator (FEAG), salt-assisted spray pyrolysis, two-fluid pyrolysis method, etc. [15-18]. These atomization methods differ in droplet size, rate of atomization, and... 

Among other new monophosphines prepared by this route are some involving an additional, non-phosphorus donor atom or group. Included among these are the proton-sponge-functionalised phosphines (11), complexes of which are readily studied by electrospray-MS techniques, a series of ortAo-sulfonyl- and ortto-sulfonamido-arylphosphines, e.g., (12), the ort/jo-phosphazenylarylphosphines (13), and the phosphino(boranyl)thiaxanthene (14). ... 

Some mild methods of ionization (e.g., chemical ionization. Cl fast-atom bombardment, FAB electrospray, ES) provide molecular or quasi-molecular ions with so little excess of energy that little or no fragmentation takes place. Thus, there are few, if any, normal fragment ions, and metastable ions are virtually nonexistent. Although these mild ionization techniques are ideal for yielding molecular mass information, they are almost useless for providing details of molecular structure, a decided disadvantage. 

This method is still in use but is not described in this book because it has been superseded by more recent developments, such as particle beam and electrospray. These newer techniques have no moving parts, are quite robust, and can handle a wide variety of compound types. Chapters 8 through 13 describe these newer ionization techniques, including electrospray, atmospheric pressure ionization, plasmaspray, thermospray, dynamic fast-atom bombardment (FAB), and particle beam. 

To achieve sufficient vapor pressure for El and Cl, a nonvolatile liquid will have to be heated strongly, but this heating may lead to its thermal degradation. If thermal instability is a problem, then inlet/ionization systems need to be considered, since these do not require prevolatilization of the sample before mass spectrometric analysis. This problem has led to the development of inlet/ionization systems that can operate at atmospheric pressure and ambient temperatures. Successive developments have led to the introduction of techniques such as fast-atom bombardment (FAB), fast-ion bombardment (FIB), dynamic FAB, thermospray, plasmaspray, electrospray, and APCI. Only the last two techniques are in common use. Further aspects of liquids in their role as solvents for samples are considered below. 

Cl is not the only ionization technique where this aspect of interpretation must be considered carefully fast-atom bombardment, thermospray, electrospray and atmospheric-pressure chemical ionization, described below in Sections 3.2.3, 4.6, 4.7 and 4.8, respectively, all produce adducts in the molecular ion region of their spectra. 

Various forms of off- and on-line AES/AAS can achieve element specific detection in IC. The majority of atomic emission techniques for detection in IC are based on ICP. In the field of speciation analysis both IC-ICP-AES and IC-ICP-MS play an important role. Besides the availability of the ICP ion source for elemental MS analysis, structural information can be provided by interfaces and ion sources like particle beam or electrospray. 

Mass spectrometry (MS) in its various forms, and with various procedures for vaporization and ionization, contributes to the identification and characterization of complex species by their isotopomer pattern of the intact ions (usually cation) and by their fragmentation pattern. Upon ionization by the rough electron impact (El) the molecular peak often does not appear, in contrast to the more gentle field desorption (FD) or fast-atom bombardment (FAB) techniques. An even more gentle way is provided by the electrospray (ES) method, which allows all ionic species (optionally cationic or anionic) present in solution to be detected. Descriptions of ESMS and its application to selected problems are published 45-47 also a representative application of this method in a study of phosphine-mercury complexes in solution is reported.48... 

Over the years, a lot of desorption ionization techniques have been introduced to MS, such as plasma desorption, field desorption, laser desorption, secondary ion mass spectrometry, fast atom bombardment, matrix assisted laser desorption and desorption electrospray ionization. Most of them are actually no longer used. In the following paragraphs, both matrix assisted laser desorption (MALDI) and desorption electrospray ionization (DESI) will be discussed. 

In off-line coupling of LC and MS for the analysis of surfactants in water samples, the suitability of desorption techniques such as Fast Atom Bombardment (FAB) and Desorption Chemical Ionisation was well established early on. In rapid succession, new interfaces like Atmospheric Pressure Chemical Ionisation (APCI) and Electrospray Ionisation (ESI) were applied successfully to solve a large number of analytical problems with these substance classes. In order to perform structure analysis on the metabolites and to improve sensitivity for the detection of the various surfactants and their metabolites in the environment, the use of various MS-MS techniques has also proven very useful, if not necessary, and in some cases even high-resolution MS is required. 

Several years later, the next step in the application of MS-MS for mixture analysis was developed by Hunt et al. [3-5] who described a master scheme for the direct analysis of organic compounds in environmental samples using soft chemical ionisation (Cl) to perform product, parent and neutral loss MS-MS experiments for identification [6,7]. The breakthrough in LC-MS was the development of soft ionisation techniques, e.g. desorption ionisation (continuous flow-fast atom bombardment (CF-FAB), secondary ion mass spectrometry (SIMS) or laser desorption (LD)), and nebulisation ionisation techniques such as thermospray ionisation (TSI), and atmospheric pressure ionisation (API) techniques such as atmospheric pressure chemical ionisation (APCI), and electrospray ionisation (ESI). 

Electrospray ionization (ESI) is a soft ionization technique that accomplishes the transfer of ions from solution to the gas phase. The technique is extremely useful for the analysis of large, non-volatile, chargeable molecules such as proteins and nucleic acid polymers. [1] Different from fast atom bombardment (FAB, Chap. 9) the solution is composed of a volatile solvent and the ionic analyte at very low concentration, typically M. In addition, the transfer of ions... 

For the determination of organotin compounds (tributyltin, triphenyltin, triethyltin, and tetra-ethyltin) a MAE is proposed before the normal phase (NP) HPLC/UV analysis [35], In organotin and arsenic speciation studies, hydride generation is the most popular derivatization method, combined with atomic absorption and fluorescence spectroscopy or ICP techniques [25,36], Both atmospheric pressure chemical ionization (APCI)-MS and electrospray ionization ESI-MS are employed in the determination of butyltin, phenyltin, triphenyltin, and tributyltin in waters and sediments [37], A micro LC/ESI-ion trap MS method has been recently chosen as the official EPA (Environmental Protection Agency) method (8323) [38] it permits the determination of mono-, di-, and tri- butyltin, and mono-, di-, and tri-phenyltin at concentration levels of a subnanogram per liter and has been successfully applied in the analysis of freshwaters and fish [39], Tributyltin in waters has been also quantified through an automated sensitive SPME LC/ESI-MS method [40],... 

The progress of the mass spectrometry of organozinc compounds has paralleled the development of new MS techniques. The first complexes studied by MS should have been volatile. However, the development of ionization methods such as fast atom bombardment, electrospray ionization and laser ionization has allowed the analysis of non-volatile, high molecular weight and ionic complexes. The evolution of methods of studying unimolecular... 

There are many different ionization techniques available to produce charged molecules in the gas phase, ranging from simple electron (impact) ionization (El) and chemical ionization (Cl) to a variety of desorption ionization techniques with acronyms such as fast atom bombardment (FAB), plasma desorption (PD), electrospray (ES), and matrix-assisted laser desorption ionization (MALDI) (Mano and Goto 2003). 

Mass spectrometry has been revolutionalized by the advent of electrospray ionization, but, before we concentrate on this relatively recent addition to the array of ionization methods, we will first discuss two other techniques which are routinely used for the ionization of biomolecules matrix assisted laser desorption ionization (MALDI) and fast atom bombardment (FAB). These techniques share common features in that ... 

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