MS technique

The vacuum residua or vacuum bottoms is the most complex fraction. Vacuum residua are used as asphalt and coker feed. In the bottoms, few molecules are free of heteroatoms molecular weights range from 400 to >2000, so high that characteri2ation of individual species is virtually impossible. Separations by group type become blurred by the sheer mass of substitution around a core stmcture and by the presence of multiple functionahties in a single molecules. Simultaneously, the traditional gc and ms techniques require the very volatiUty that this fraction lacks. 

The development of methods of analysis of tria2ines and thek hydroxy metabohtes in humic soil samples with combined chromatographic and ms techniques has been described (78). A two-way approach was used for separating interfering humic substances and for performing stmctural elucidation of the herbicide traces. Humic samples were extracted by supercritical fluid extraction and analy2ed by both hplc/particle beam ms and a new ms/ms method. The new ms /ms unit was of the tandem sector field-time-of-flight/ms type. 

It was found, that at standard gas-chromatograph sampling of 1 pL of analyte solution the limit of detection for different amines was measured as 0.1-3 ng/ml, or of about 1 femtomole of analyte in the probe. This detection limit is better of published data, obtained by conventional GC-MS technique. Evidently, that both the increasing of the laser spot size and the optimization of GC-capillary position can strongly improve the detection limit. 

The liquid chromatography - tandem mass spectrometry (LC/MS/MS) technique was proposed for the determination of corticosteroids in plasma and cerebrospinal fluid (CSF, liquor) of children with leucosis. Preliminai y sample prepai ation included the sedimentation of proteins, spinning and solid-phase extraction. MS detection was performed by scanning selected ions, with three chai acteristic ions for every corticosteroids. The limit of detection was found 80 pg/ml of plasma. 

What is common to all of these areas is that the relevant number of published GC-GC papers is very small when compared to those concerning single-column and GC-MS methods. While approximately 1000 papers per year are currently published on single-column GC methods and, in recent years, nearly 750 per year on GC-MS techniques, only around 50 per annum have been produced on two-dimensional GC. Of course, this may not be a true reflection of the extent to which two-dimensional GC is utilized, but it is certainly the case that research interest in its application is very much secondary to that of mass spectrometric couplings. A number of the subject areas where two-dimensional methods have been applied do highlight the limitations that exist in single-column and MS-separation analysis. 

Azepine (m/z 93) was first detected and characterized by application of GC/MS techniques to the thermolysis products of 3-[hydroxy(diphenyl)methyl]-3//-azepine.91... 

Acridine-9-carbaldehyde (24%) is one of several products formed from the oxidation of 5//-dibenz[A/]azepine with tert-butyl hypochlorite in dichloromethane at — 70 C.229 The reaction is even more complex in the presence of silver(I) trifluoroacetate, and an analysis of the reaction mixture by GC-MS techniques reveals the presence of eleven products, the major ones being acridine (37%), an unidentified 5//-dibenz[/ ,/]azepinecarbaldehyde (23%) and acridine-9-carbaldehyde (9 %). 

Interpretation Active component A is so stable that a shelf-life in excess of 60 months could be assigned (it is unusual for a pharmaceutical to be approved for more than 5 years). Component B, however, undergoes hydrolysis (this fact has to be independently established, i.e., by GC/MS techniques, or equivalents). (See Fig. 4.26.) The data points cover an incomplete 24-month stability program T - 0, 3, 7, 24). The intercept is at 104.3%, an indication for over-dosing, and the slope is = 0.49 [%/month]. The... 

An important breakthrough in HTS ee assays came from the group of Reetz in late 1990, with the introduction of mass spectroscopy (MS)-based procedures [90]. These methods use special asymmetrically isotope-labeled compounds. Enzymatic transformations of these compounds usually lead to two pseudoenantiomeric compounds whose relative concentration can be estimated using MS techniques. 

Due to the high mass, low volatility, and thermal instability of chlorophylls and derivatives, molecular weight determination by electron impact (El) MS is not recommended. Desorption-ionization MS techniques such as chemical ionization, secondary ion MS, fast-atom bombardment (FAB), field, plasma- and matrix-assisted laser desorption have been very effective for molecular ion detection in the characterization of tetrapyrroles. These techniques do not require sample vaporization prior to ionization and they are effective tools for allomerization studies. 

Common additives in food are sulfur S(IV) oxospecies. Quinoline Yellow and Tartrazine show excellent stability toward S(IV) oxospecies while erythrosine. Red 2G, and Green S show good stability. - All other colorants show fair stability, except indigotine, which fades. In the presence of metabisulflte. Sunset Yellow FCF is degraded to a lemon yellow compound identified as l-(4 -sulfo-l-phenylhydrazo)-keto-3,3,4-trihydronaphtalene-4,6-disulfonic acid by NMR and FAB-MS techniques. ... 

M. V. Juskelis, an unpublished study done using the same TPR/MS technique. 

The GC-MS techniques give much more chemical information than does measurement of only 8-OH-dGua. However, the hydrolysis and derivatization procedures are lengthy and tedious, and may destroy some modified bases, e.g. hydroxymethyluracil (Djuric etal., 1991). It has also been speculated that they might create artefacts, e.g. if the amounts of modified bases increase during the preparation procedures. Data surest that formic acid hydrolysis does not create additional 8-OH-Gua in DNA (Halliwell and Dizdaroglu, 1992) but the question is currently open as to whether the derivatization procedures might do so. 

Once several target methods employing, e.g., LC/MS/MS techniques have been combined, a multi-residue method will evolve which includes the DEC S19 extraction procedures in combination with the generally applicable GPC cleanup and requires automatic multiple injections to circumvent the limitations of the limited HPLC peak capacity and the target-specific MS/MS methods. 

LC/MS/MS. LC/MS/MS is used for separation and quantitation of the metabolites. Using multiple reaction monitoring (MRM) in the negative ion electrospray ionization (ESI) mode, LC/MS/MS gives superior specificity and sensitivity to conventional liquid chromatography/mass spectrometry (LC/MS) techniques. The improved specificity eliminates interferences typically found in LC/MS or liquid chro-matography/ultraviolet (LC/UV) analyses. Data acquisition is accomplished with a data system that provides complete instmment control of the mass spectrometer. 

The use of collision-induced dissociation (CID) and MS/MS techniques in conjunction with the API interfaces has dramatically impacted the fleld of environmental analysis. These techniques are now preferred for the determination of triazine compounds in water, soil, crops, etc., owing to the significant improvements in selectivity obtained via the monitoring of precursor-product ion pairs and increased sensitivity due to the reduction of chemical noise. 

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