Mass spectrometry pure samples

Spark source mass spectrometry is used for the examination of non-volatile inorganic samples and residues to determine elemental composition. An RF spark of about 30 kV is passed between two electrodes, one of which may be the sample itself, causing vaporization and ionization. Powdered samples or residues from ashed organic materials can be formed into an electrode after mixing with pure graphite powder. 

Using the three measured ratios, Ca/ Ca, Ca/ " Ca and Ca/ " Ca, three unknowns can be solved for the tracer/sample ratio, the mass discrimination, and the sample Ca/ Ca ratio (see also Johnson and Beard 1999 Heuser et al. 2002). Solution of the equations is done iteratively. It is assumed that the isotopic composition of the Ca- Ca tracer is known perfectly, based on a separate measurement of the pure spike solution. Initially it is also assumed that the sample calcium has a normal Ca isotopic composition (equivalent to the isotope ratios listed in Table 1). The Ca/ Ca ratio of the tracer is determined based on the results of the mass spectrometry on the tracer-sample mixture, by calculating the effect of removing the sample Ca. This yields a Ca/ Ca ratio for the tracer, which is in general different from that previously determined for the tracer. This difference is attributed to mass discrimination in the spectrometer ion source and is used to calculate a first approximation to the parameter p which describes the instrumental mass discrimination (see below). The first-approximation p is used to correct the measured isotope ratios for mass discrimination, and then a first-approximation tracer/sample ratio and a first-approximation sample CeJ Ca... 

Very few, if any, recent biomedical publications describe the use of ion-impact mass spectrometry without the use of GC or some other separation method because most biological samples are chemically complex. The production of clean and useful El mass spectrometric signals requires the substance of interest to be very pure, and thus direct El experiments are usually confined to preliminary studies of highly purified biomolecules or to studies on the metabolism of pure materials. Two publications that describe direct El methods applicable to biochemical analysis and neuropharmaceutical studies are those of Costa et al. (1992) and Karminski-Zamola et al. (1995). 

Hyphenated analytical techniques such as LC-MS, which combines liquid chromatography and mass spectrometry, are well-developed laboratory tools that are widely used in the pharmaceutical industry. Eor some compounds, mass spectrometry alone is insufficient for complete structural elucidation of unknown compounds nuclear magnetic resonance spectroscopy (NMR) can help elucidate the structure of these compounds (see Chapter 20). Traditionally, NMR experiments are performed on more or less pure samples, in which the signals of a single component dominate. Therefore, the structural analysis of individual components of complex mixtures is normally time-consuming and less cost-effective. The... 

Temperature programmed reaction (TPR) experiments were carried out by adsorbing allyl alcohol and allyl iodide on a 9.0 wt% Mo03/Si02 sample and monitoring the evolved products by mass spectrometry. The Raman spectra of the pure liquid reference compounds are shown in Fig. 2. They agree well with those reported earlier (18-20). 

Chemical and instrumental (e.g., chromatography and mass spectrometry) methods have provided valuable information that lead to the advancement of cheese science. However, these techniques suffer from one or more of the following problems (1) the extensive use of solvents and gases that are expensive and hazardous, (2) high costs, (3) the requirement of specific accessories for different analytes, (4) the requirement of extensive sample preparation to obtain pure and clean samples, and (5) labor-intensive operation. These disadvantages have prompted for the evaluation and adoption of new, rapid, and simple methods such as Fourier-transform infrared (FTIR) spectroscopy. Many books are available on the basics of FTIR spectroscopy and its applications (Burns and Ciurczak, 2001 Sun, 2009). FTIR spectroscopy monitors the vibrations... 

Both the liquid and gas products were analyzed by gas chromatography. The column for the liquid analysis was 20% Apiezon L on 60-80 mesh Chromosorb P. The column measured 1/4 inch by 7 feet. The gas analysis utilized a 1/4 inch by 10 foot column of 60-80 mesh Chromosorb 102. Temperature programming was required in both analyses. Identification of the GC peaks was based on retention time of pure compounds when these were available. In addition, two of the samples were analyzed by combined gas chromatography-mass spectrometry. By comparing the observed mass spectrometer fragmentation patterns with tabulated patterns it was possible to identify virtually every component in the product. Further details are available in the theses by Wu (23) and Early (J+). 

Variable recovery is a principal cause of non-equivalence of data and there is no straightforward solution to this problem [26], Artificially made reference samples or pure compounds added to test material cannot be used for estimations of recovery of analytes. Direct speciation analysis from the solid sample [27] is not feasible at present, although analytical methods are appearing that could be useful in the future (X-ray absorption spectrometry, laser mass spectrometry, static secondary ion mass spectrometry). 

Liquid chromatography/mass spectrometry (LC/MS)-based techniques provide unique capabilities for pharmaceutical analysis. LC/MS methods are applicable to a wide range of compounds of pharmaceutical interest, and they feature powerful analytical figures of merit (sensitivity, selectivity, speed of analysis, and cost-effectiveness). These analytical features have continually improved, resulting in easier-to-use and more reliable instruments. These developments coincided with the pharmaceutical industry s focus on describing the collective properties of novel compounds in a rapid, precise, and quantitative way. As a result, the predominant pharmaceutical sample type shifted from nontrace/pure samples to trace mixtures (i.e., protein digests, natural products, automated synthesis, bile, plasma, urine). The results of these developments have been sig-... 

With the exception of stilbene, all organic compounds listed in Table I (samples 14 to 28) were either obtained commercially or prepared by scientists at the USDA Forest Service, Forest Products Laboratory using well-established methods. Purchased chemicals were from both Aldrich Chemical Co., Milwaukee, Wisconsin, and Fluka Chemical Corporation, Ronkonkoma, New York. The Raman data for stilbene were taken from the literature [17]. Whenever the purity of a compound was in doubt, it was checked by gas chromatography-mass spectrometry. The Raman spectra reported here are from compounds that were more than 99% pure. 

Mass spectrometry on its own is not suitable for FDR work because generally speaking pure compounds must be analyzed. Samples for FDR examination taken from skin and clothing surfaces are complex mixtures containing many unpredictable contaminants from occupational and... 

When analyzing any compound obtained as a result of subsequent chemical reactions, chemists always address three major issues identity (Did we synthesize what we intended ), quality (How pure is our compound What side product(s) do we have in our sample ), and quantity (How much did we synthesize What is the yield of the reactions ). In the process of analysis of organic compounds, the focus has always been on obtaining comprehensive information with a variety of analytical methods. The traditional scheme of analysis includes structure identification by NMR ( 11 and 13C) and MS (including high-resolution mass spectrometry), with additional confirmation of structure provided by IR spectroscopy, X-ray, etc. [5]. 

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