Chemical ionization electrospray

See footnote cto Table3 LC/PB/MS = hquid chromatography/particle beam mass spectrometry LC/APcl/ESl-MS/MS = liquid chromtography/atmospheric pressure chemical ionization/electrospray ionization tandem mass spectrometry LC/FTIR = Fourier transform infrared LC/TSP-MS/MS = liquid chromatography/thermospray tandem mass spectrometry LC/TSP-MS = liquid chromatography/thermospray mass spectrometry. 

Ding, J., Desai, M., and Armstrong, D.W., Evaluation of ethoxynonafluorobu-tane as a safe and environmentally friendly solvent for chiral normal-phase LC-atmospheric pressure chemical ionization/electrospray ionization-mass spectrometry, J. Chromatogr. A, 1076, 34, 2005. 

W. A. Comparison of atmospheric pressure chemical ionization, electrospray ionization, and atmospheric pressure photoionization for the determination of cyclosporin a in rat plasma. Anal Chem 2005, 77, 541-548. 

Mass spectrometry by chemical ionization, electrospray, or other methods... 

Amide herbicides - preconcentration using SPMDs then bioassay. (2) Diethanol amides by solid-phase extraction-liquid chromatography-atmospheric pressure chemical ionization/electrospray ionization mass spectrometry (SPE-LC-APCI/ESI-MS) o-Phthaldialdehyde derivatization then reversed-phase LC with fluorescence defecfion. Chiral derivafizafion permifs separation of optical isomers on standard LC columns Anion exchange LC Ion-pair liquid chromatography... 

One of the first successful techniques for selectively removing solvent from a solution without losing the dissolved solute was to add the solution dropwise to a moving continuous belt. The drops of solution on the belt were heated sufficiently to evaporate the solvent, and the residual solute on the belt was carried into a normal El (electron ionization) or Cl (chemical ionization) ion source, where it was heated more strongly so that it in turn volatilized and could be ionized. However, the moving-belt system had some mechanical problems and could be temperamental. The more recent, less-mechanical inlets such as electrospray have displaced it. The electrospray inlet should be compared with the atmospheric-pressure chemical ionization (APCI) inlet, which is described in Chapter 9. 

The term nebulizer is used generally as a description for any spraying device, such as the hair spray mentioned above. It is normally applied to any means of forming an aerosol spray in which a volume of liquid is broken into a mist of vapor and small droplets and possibly even solid matter. There is a variety of nebulizer designs for transporting a solution of analyte in droplet form to a plasma torch in ICP/MS and to the inlet/ionization sources used in electrospray and mass spectrometry (ES/MS) and atmospheric-pressure chemical ionization and mass spectrometry (APCI/MS). 

The LC/TOF instmment was designed specifically for use with the effluent flowing from LC columns, but it can be used also with static solutions. The initial problem with either of these inlets revolves around how to remove the solvent without affecting the substrate (solute) dissolved in it. Without this step, upon ionization, the large excess of ionized solvent molecules would make it difficult if not impossible to observe ions due only to the substrate. Combined inlet/ionization systems are ideal for this purpose. For example, dynamic fast-atom bombardment (FAB), plas-maspray, thermospray, atmospheric-pressure chemical ionization (APCI), and electrospray (ES)... 

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. 

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). 

Electrospray Ionization (ES) and Atmospheric Pressure Chemical Ionization (APCI)... 

Samples containing mixtures of peptides can be analyzed directly by electrospray. Alternatively, the peptides can be separated and analyzed by LC/MS coupling techniques such as electrospray or atmospheric pressure chemical ionization (APCI). 

The ion guides are frequently used to transmit ions from an atmospheric-pressure inlet/source system (electrospray ionization, atmospheric-pressure chemical ionization) into the vacuum region of an m/z analyzer. 

An abundant molecular ion may indicate that an aromatic compound or highly unsaturated ring compound is present. If no molecular ion is observed and one cannot be deduced, the use of chemical ionization (ci), negative chemical ionization (nci), fast atom bombardment (FAB), or electrospray ionization (ESI) should provide a molecular ion. 

In the following chapters, the basic principles of HPLC and MS, in as far as they relate to the LC-MS combination, will be discussed and seven of the most important types of interface which have been made available commercially will be considered. Particular attention will be paid to the electrospray and atmospheric-pressure chemical ionization interfaces as these are the ones most widely used today. The use of LC-MS for identification and quantitation will be described and appropriate applications will be discussed. 

The pump must provide stable flow rates from between 10 ttlmin and 2 mlmin with the LC-MS requirement dependent upon the interface being used and the diameter of the HPLC column. For example, the electrospray interface, when used with a microbore HPLC column, operates at the bottom end of this range, while with a conventional 4.6 mm column such an interface usually operates towards the top end of the range, as does the atmospheric-pressure chemical ionization (APCI) interface. The flow rate requirements of the different interfaces are discussed in the appropriate section of Chapter 4. 

Ionization methods that may be utihzed in LC-MS include electron ionization (El), chemical ionization (Cl), fast-atom bombardment (FAB), thermospray (TSP), electrospray (ESI) and atmospheric-pressure chemical ionization (APCI). 

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. 

It was also the first of a number of interfaces, with the others being electrospray and atmospheric-pressure chemical ionization, in which ionization is effected directly from solution within the interface itself, i.e. the mass spectrometer was not nsed to prodnce ions from the analyte simply to separate them according to their m/z ratios. 

Particular emphasis has been placed upon electrospray and atmospheric-pressure chemical ionization (APCI) which, in addition to being the currently most widely used interfaces, are ionization techniques in their own right. 

Figure 5.1 Pesticides included in the systematic investigations on APCI-MS signal response dependence on eluent flow rate the parameter IsTow represents the distribution coefficient of the pesticide between n-octanol and water. Reprinted from J. Chromatogr, A, 937, Asperger, A., Efer, 1., Koal, T. and Engewald, W., On the signal response of various pesticides in electrospray and atmospheric pressure chemical ionization depending on the flow rate of eluent applied in liquid chromatography-mass spectrometry , 65-72, Copyright (2001), with permission from Elsevier Science.

Atmospheric-pressure chemical ionization (APCI) and electrospray ionization are both soft ionization techniques which give rise, almost exclusively, to the production of molecular species. Structural information. 

If a high -molecular-weight compound is being studied by LC-MS, the analyst has little choice in the ionization method to use, with atmospheric-pressure chemical ionization (APCl) being wholly inappropriate. However, when low -molecular-weight componnds are involved, both electrospray ionization and APCl are potentially of value. 

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