Direct Mass Spectrometry Method

T-MS). The main direct mass-spectral methods are thermal desorption and pyrolysis mass spectrometry. Several factors favour the efficiency at which volatiles can be removed from a polymeric matrix ... 

Mass spectrometry combines exquisite sensitivity with a precision that often depends more on the uncertainties of sampling and sample preparation than on those of the method itself. Mass spectrometry is a supreme identification and recognition method in polymer/additive analysis through highly accurate masses and fragmentation patterns quantitation is its weakness. Direct mass spectrometry of complex polymeric matrices is feasible, yet not often pursued. Solid probe ToF-MS (DI-HRMS) is a breakthrough. Where used routinely, mass spectrometrists are usually still in charge. At the same time, however, costs need to be watched. 

In contrast to direct mass spectrometry used in the El mode, ESI often requires specific pretreatments of the samples to purify the components of interest, to increase their yield of ionisation and consequently to improve selectivity and sensitivity. It is thus not a preliminary step of analysis but a method that forms part of an analytical strategy that allows the presence of well preserved high molecular long chain compounds to be shown before their fine characterisation by ESI techniques (Regert et al., 2003a Mirabaud, 2007 Mirabaud et al., 2007). 

Conductometric transducers, as the oldest electrochemical devices, seem not to enjoy wide applications due to their poor selectivity. For example, Yagiuda et al. proposed a conductometric immunosensor for the determination of methamphetamine (MA) in urine [89], The decrease in the conductivity between a pair of platinum electrodes might result from the direct attachment of MA onto the anti-MA antibodies immobilized on the electrode surface. The system was claimed to be a useful detection technique of MA in comparison with a gas chromatography-mass spectrometry method. 

Recently, a quantitative electrospray ionization/mass spectrometry method (ESI/MS) has been developed to analyze the molecular profile, or hpidome of different lipid classes in very small samples. In this method, total lipid extracts from tissues or cultured cells can be directly analyzed. By manipulating the ionization method, the mass spectrographs of polar or even non-polar lipids can be obtained [8]. This method and the use of lipid arrays allow precise and quantitative identification of the lipid profile of a given tissue, and map functional changes that occur. 

Zeng W. et al., 2003b. A direct injection high-throughput liquid chromatography tandem mass spectrometry method for the determination of orally active ajSj antagonist in huma urine and dialysatc. Rapid Commun Mass Spectrom 17 2475. 

A number of methods have been described for determination of tetracycline (chlortetracycline, tetracycline, and oxytetracycline) residues in tissues of food-producing animals (53-62), fish (63), eggs (64), and honey (65,66). Most of these methods use reversed-phase HPLC for determination. However, one uses TLC with UV densitometry ( ) and one uses GLC ( ), and one uses a direct mass spectrometric method CAD MIKE spectrometry (collisionally activated decomposition mass-analyzed ion kinetic spectrometry) for oxytetracycline in milk and meat (62). Several use solid-phase extraction in the cleanup procedure using XAD-2 resin (56,58) or Cj g cartridges... 

Mass spectrometry methods based on soft ionization techniques, 59,61,88,89 matrix-assisted laser desorption ionization/time-of-flight (MALDI-TOF), have been successfully applied for the direct analysis of grape and wine extracts and for monitoring flavonoid reactions in model solution studies. They give access to the molecular weights of the different species present in a fraction or extract and, through fragmentation patterns, provide important information on their constitutive units. Description of the various MS techniques can be found in Chapters 1 and 2. 

A brief informal intercomparison study of the mass spectrometry methods with a nylon filter pack method near Boulder, Colorado, gave average levels of 0.38-1.6 ppb when the wind carried air from the direction of the greater metropolitan Denver urban area and 0.14-0.56 ppb when the wind was downslope and westerly, where there are fewer emissions sources previous filter pack... 

Several methods are available in the literature for the measurement of aliphatic amines in biological samples [28]. Problems with specificity and separation and cumbersome derivatisation and/or extraction procedures have limited the use of these techniques on a larger scale in clinical practice. The lack of a simple analytical method may have led to an underestimation of the incidence of the fish odour syndrome. For diagnosing the syndrome, an analytical technique should be used that is able to simultaneously and quantitatively measure TMA and its N-oxide in the complex matrix of human urine. Two such methods are currently available for this purpose proton nuclear magnetic resonance (NMR) spectroscopy and head-space gas analysis with gas chromatography or direct mass spectrometry (see below). 

For the isotope dilution, mass spectrometry method samples are injected directly into the gas sample injection port of the mass spectrometer [27]. These techniques do not allow concurrent analysis of TMA and TMA N-oxide in the sample. TMA N-oxide is quantified indirectly by measuring the increase in TMA after chemical reduction. 

Smalley, J., Kadiyala, P., Xin, B., Balimane, P., and Olah, T. (2006). Development of an online extraction turbulent-flow chromatography tandem mass spectrometry method for cassette analysis of Caco-2 cell based bi-directional assay samples. J. Chromatogr. B Ana. Technol. Biomed. Life Sci. 830 270-277. 

Frequently industrial hygiene analyses require the identification of unknown sample components. One of the most widely employed methods for this purpose is coupled gas chromatography/ mass spectrometry (GC/MS). With respect to interface with mass spectrometry, HPLC presently suffers a disadvantage in comparison to GC because instrumentation for routine application of HPLC/MS techniques is not available in many analytical chemistry laboratories (3). It is, however, anticipated that HPLC/MS systems will be more readily available in the future ( 5, 6, 1, 8). HPLC will then become an even more powerful analytical tool for use in occupational health chemistry. It is also important to note that conventional HPLC is presently adaptable to effective compound identification procedures other than direct mass spectrometry interface. These include relatively simple procedures for the recovery of sample components from column eluate as well as stop-flow techniques. Following recovery, a separated sample component may be subjected to, for example, direct probe mass spectrometry infra-red (IR), ultraviolet (UV), and visible spectrophotometry and fluorescence spectroscopy. The stopped flow technique may be used to obtain a fluorescence or a UV absorbance spectrum of a particular component as it elutes from the column. Such spectra can frequently be used to determine specific properties of the component for assistance in compound identification (9). 

Neither of the mass-spectrometry methods commonly used for measuring gas-phase basicities is capable of directly identifying the site of protonation in the base molecule, and those methods traditionally employed to deduce this information (e.g., NMR spectroscopy) are carried out in solution, in which the... 

The vahdity of assay results is best proved by tests for parallelism of the response curves for both calibrators and randomly selected samples from male and female subjects of various ages. In addition, comparison of extraction/ chromatography immunoassays should be validated by comparison with mass spectrometry methods. Direct immunoassays should not be used for female and prepubertal subjects, especially infants. These groups should be tested using an extraction immunoassay or an LC-MS/MS assay. It is important to note that both types of direct immunoassay demonstrate problems with functional sensitivity for low concentrations. Each lab should determine the low-end detection limit of their assay despite manufacturer claims. 

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