Negative ion chemical ionization

Negative Ion Chemical Ionization Negative ions are produced under ci conditions by electron capture. Under the higher pressure conditions of the ci ion source, electrons, both primary (those produced by the filament) and secondary (produced during an ionization event), undergo collisions until they reach near-thermal energies. Under these conditions, molecules... 

Fig. 6. Methane chemical ionization negative ion mass spectra of pentafluoro benzyl ABA upper with insert of unlabelled material) and dipentafluoro benzyl ODA lower). The compounds were isolated from tomato shoots supplied with 40% -H. >O for six days, then severely wilted. M/z-263 = molecular ion — 1 mass unit after the loss of the pentafluorobenzyl residue +H.M/Z 377 = molecular ion of dipentafluorobenzyl ODA-1 mass unit after the loss of one pentafluorobenzyl residue +H. Ordinate. relative intensity abscissa, mass numbers...

An ion containing unpaired electrons in its ground state Electron impact ionization Positive chemical ionization Negative chemical ionization... 

Hj-Lorazepam, 3-hydroxy-1,4-benzodiazepine, 45, a sedative hypnotic and antianxiety agent, has been synthesized in a seven-step procedure presented in equation 12 for use as an internal standard in GC-MS-NICI-SIM (NICl-SIM = negative ion chemical ionization-selective ion monitoring) quantitative analysis of this drug in complex matrices encountered in forensic work and for study of its complex kinetics. The procedure involved selective trideuteriation, protection of the amino group and... 

Techniques GC-MS, negative ion chemical ionization, selected ion monitoring. Reference D. L. Swackhamer, M. J. Charles, and R. A. Hites, Quantitation of toxaphene in environmental samples using negative ion chemical ionization mass spectrometry. Anal. Chem. 59 913-917 (1987). 

To perform chemical ionization, the ion volume of the spectrometer is usually different from the one used for El, the operating pressure is higher (partially due to the additional reagent gas), and the temperature is lower. Certain types of molecules also yield good negative ion spectra by NCI, providing another option for analysis. However, most bench-top GC-MS instruments are not capable of Cl operation. 

The voltage applied to the extraction system determines the polarity of the accelerated ions. A negative voltage is used to extract positive ions in electron ionization and in positive chemical ionization and a positive voltage to accelerate negative ions in negative chemical ionization. An ion beam of the same charge systematically... 

Most of the ions produced by either thermospray or plasmaspray (with or without the repeller electrode) tend to be very similar to those formed by straightforward chemical ionization with lots of protonated or cationated positive ions or negative ions lacking a hydrogen (see Chapter l).This is because, in the first part of the inlet, the ions continually collide with neutral molecules in the early part of their transit. During these collisions, the ions lose excess internal energy. 

PPNICI. pulsed positive ion/negative ion chemical ionization... 

S. Lacorte and D. Barcelo, Determination of parts per trillion levels of organophospho-rus pesticides in groundwater by automated on-line liquid- solid extraction followed by liquid chr omatography/atmospheric pressure chemical ionization mass spectrometry using positive and negative ion modes of operation . Anal. Chem. 68 2464- 2470 (1996). 

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. 

Chemical ionization (Cl) The formation of new ionized species when gaseous molecules interact with ions. This process may involve the transfer of an electron, proton, or other charged species between the reactants in an ion-molecule reaction. Cl refers to positive ions, and negative Cl is used for negative ions. 

A number of analytical techniques such as FTIR spectroscopy,65-66 13C NMR,67,68 solid-state 13 C NMR,69 GPC or size exclusion chromatography (SEC),67-72 HPLC,73 mass spectrometric analysis,74 differential scanning calorimetry (DSC),67 75 76 and dynamic mechanical analysis (DMA)77 78 have been utilized to characterize resole syntheses and crosslinking reactions. Packed-column supercritical fluid chromatography with a negative-ion atmospheric pressure chemical ionization mass spectrometric detector has also been used to separate and characterize resoles resins.79 This section provides some examples of how these techniques are used in practical applications. 

GC/MS has been employed by Demeter et al. (1978) to quantitatively detect low-ppb levels of a- and P-endosulfan in human serum, urine, and liver. This technique could not separate a- and P-isomers, and limited sensitivity confined its use to toxicological analysis following exposures to high levels of endosulfan. More recently, Le Bel and Williams (1986) and Williams et al. (1988) employed GC/MS to confirm qualitatively the presence of a-endosulfan in adipose tissue previously analyzed quantitatively by GC/ECD. These studies indicate that GC/MS is not as sensitive as GC/ECD. Mariani et al. (1995) have used GC in conjunction with negative ion chemical ionization mass spectrometry to determine alpha- and beta-endosulfan in plasma and brain samples with limits of detection reported to be 5 ppb in each matrix. Details of commonly used analytical methods for several types of biological media are presented in Table 6-1. 

ECD = electron capture detector GC = gas chromatography HPLC = high-performance liquid chromatography MC = microcoulometric detector MS = mass spectrometry NICI = negative ion chemical ionization RSD = relative standard deviation SPE = solid phase extraction... 

Mass Spectrometry. Mass spectrometry holds great promise for low-level toxin detection. Previous studies employed electron impact (El), desorption chemical ionization (DCI), fast atom bombardment (FAB), and cesium ion liquid secondary ion mass spectrometry (LSIMS) to generate positive or negative ion mass spectra (15-17, 21-23). Firm detection limits have yet to be reported for the brevetoxins. Preliminary results from our laboratory demonstrated that levels as low as 500 ng PbTx-2 or PbTx-3 were detected by using ammonia DCI and scans of 500-1000 amu (unpublished data). We expect significant improvement by manipulation of the DCI conditions and selected monitoring of the molecular ion or the ammonia adduction. 

Both positive and negative ions are produced during the sputtering process, and either can be recorded by an appropriate choice of instrumental parameters. Positive ions are the result of protonation, [M + H]", or cationiz-ation, [M +cation], whereas negative ions are preponderantly [M-H], but can also be formed by the addition of an anion, that is, [M+anion]". The type of pseudomolecular ion produced is governed by the chemical nature of the sample and by the composition of the matrix from which it is ionized. 

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