Mass spectrometry for stable isotopic

Taylor SR, McLennan SM (1985) The Continental Crust Its Composition and Evolution. Blackwell, Boston Tuit CB, Ravizza G (2003) The marine distribution of molybdenum. Geochim Cosmochim Acta 67 A4950 Tumlund JR, Keyes WR, Peiffer GL (1993) Isotope ratios of molybdenum determined by thermal ionization mass spectrometry for stable isotope studies of molybdenum metabolism in humans. Anal Chem 65 1717-1722... 

FIGURE 40.19 Schematic of an accelerator mass spectrometer. Reprinted from Matteson, S. (2008) Issues and opportunities in accelerator mass spectrometry for stable isotopes. Mass Spectrometry Revieu s, 27(5), 470-484. Copyright (2008), with permission from Wiley Periodicals. 

Matteson, S. (2008) Issues and opportunities in accelerator mass spectrometry for stable isotopes. Mass Spectrometry Reviews, 27,470-484. 

Luong, E.T. (1999). Inductively coupled plasma mass spectrometry for stable isotope metabolic tracer studies of living systems. Unpublished Ph.D. Thesis, Iowa State University, Ames. 

Keshishian H, Addona T, Burgess M, Kuhn E, Carr SA (2007) Quantitative, multiplexed assays for low abundance proteins in plasma by targeted mass spectrometry and stable isotope dilution. Mol Cell Proteomics 6 2212-2229... 

Huang, M.C., Muddana, S., Horowitz, E.N., McCormick, C.C., Infante, J.P., and Brenna, J.T. (2000) High-Precision Isotope Ratio Mass Spectrometry and Stable Isotope Precursors for Tracer Studies in Cell Culture, Anal. Biochem. 287, 80-86. 

Raymond M W., Howard C P, Miles J. M., and Gensh J E (1980) Determination of leucine flux in vivo by gas chromatography-mass spectrometry utilizing stable isotopes for trace and internal standard / Chromatogr 183, 403 09. 

Dahmen, L, Pfluger, M., Martin, M., Rottmann, L., Weichbrodt, G. (1997) Trace element determination of high-purity chemicals for the processing of semiconductors with high-resolution ICP-mass spectrometry using stable isotope dilution analysis (IDA). Fresenius Journal of Analytical Chemistry, 359,410-413. 

Aranda, M., Morlock, G. (2007) New method for caffeine quantification by planar chromatography coupled with electrospray ionization mass spectrometry using stable isotope dilution analysis. Rapid Communications in Mass Spectrometry RCM, 21,1297-1303. 

Layne GD (2003) Advantages of secondary ion mass spectrometry (SIMS) for stable isotope microanalysis of the trace light elements. EOS Trans, Am Geophys Union 84 F1635 Lundstrom CC, Chaussidon M, Kelemen P (2001) A Li isotope profile in a dunite to Iherzolite transed within the Trinity Ophiolite evidence for isotopic fractionation by diffusion. EOS Trans, Am Geophys Union 82 991... 

Pickup JF, McPherson K. 1976. Theoretical considerations in stable isotope dilution mass spectrometry for organic analysis. Anal Chem 48 1885-1890. 

System (3) described the use of stable-isotope-dilution mass spectrometry for the simultaneous determination of cortisol, cortisone, prednisolone, and prednisone in plasma [177]. Cortisol, cortisone, prednisolone, and prednisone were simultaneously extracted from acidified plasma on a Sep-Pak Ci8 cartridge. The column was eluted with methanol, the eluent evaporated, and the residue compounds reacted to their bismethylenedioxy-3-heptafluoro-n-butyryl derivatives by treatment with formaldehyde and heptafluoro-n-butyric anhydride. The derivatives were... 

Perhaps no reagent is more important than the stable-isotope-labeled internal standard in any clinical assay utilizing mass spectrometry for quantification. Internal standards are important in many aspects of the analysis and are somewhat different than standards utilized in other clinical, non-mass-spectrometric assays. The ideal internal standard is an enriched isotopic version of the analyte being measure. For example, in the case of phenylalanine, a standard available may contain six 13C molecules rather than 12C in the aromatic ring. This has the net effect of shifting the mass of phenylalanine by six units while also maintaining nearly identical chemical... 

In addition, one of the main features of mass spectrometry is, and this is the major advantage in comparison to other atomic and molecular non-mass spectrometric techniques, that it offers the possibility of determining isotope ratios and abundances of isotopes with high precision and accuracy in all types of samples (in solid, liquid and gaseous materials as well). Isotope ratio measurements have applied increasingly for stable isotopes in nature, especially for investigating... 

Measurement of the isotope abundances of a chemical element is based on the fact that the sum of all abundances of isotopes with the same Z is 100 %. For example, copper possesses two stable isotopes with m/z = 63 and 65. If the isotope ratio 63Cu/65Cu has been determined, e.g., by mass spectrometry, then the isotope abundance of 65Cu ( ) can be obtained by ... 

The most famous cosmogenic radionuclide is 14C (t1/2 = 5730 a), which is produced by the interaction of cosmic ray neutrons via an (n,p) reaction with nitrogen [14N(n, p)14C], whereas the radioactive decay of 14C takes place by (3 decay to form the stable 14N isotope. 14C is the most important cosmogenic radionuclide for dating (see Section 9.7.5) in archaeology and can be analyzed using isotope sensitive accelerator mass spectrometry. Extremely small isotope ratios 14C/12C = 12 in nature can be measured by means of AMS.28... 

In quantitative proteomics, two alternative strategies have been developed. The first one is based on 2-D PAGE combined with mass spectrometry for protein identification (Haynes and Yates, 2000). This method and current advances in the differential display of proteins by 2-D PAGE are discussed at length in another chapter of this book. The second approach exploits mass spectrometry in combination with stable isotope labeling for gaining accurate quantitative information on proteins. Quantitative MS via stable isotope labeling of proteins... 

Thermal ionization mass spectrometry has been used extensively in the geological nuclear and analytical sciences for stable isotope measurements A new technique resonance ionization mass spectrometry offers a comprehensive approach to sensitive and selective elemental and isotopic analysis Recent developments in thermal and resonance ionization mass spectrometry are reviewed) and specific applications of the technology to zinc and calcium metabolism studies and to trace element analysis of foodstuffs are summarized ... 

The use of carbon isotopes to study DOC is becoming more prevalent due to technological advances in mass spectrometry. DOC generally occurs in natural waters in low concentrations, typically ranging between 0.5 ppm and 10 ppm carbon (Thurman, 1985 see Chapter 5.10). Thus, several liters to tens of liters of water were once necessary to extract enough DOC for conventional dual gas-inlet isotopic analysis. Today, automated total organic carbon analyzers (TOCs) are commercially available, and have been successfully interfaced with continuous flow isotope ratio mass spectrometers (CF-IRMS) for stable isotopic measurements of samples containing ppb concentrations of DOC (e.g., St-Jean, 2003). 

Following the classification of the analytical methods given by ISO 32 [3] two major type of calibration materials can be certified. For relative methods such as all spectrometric ones, pure substances are necessary. They can be certified for the stoichiometry and degree of purity but also for isotopic composition. The latter case is a prerequisite for measurements of radioactive materials and for stable isotope mass spectrometry (isotope dilution TIMS or ICP-MS). For comparative methods, pure substances and mixtures of substances are necessary, as well as matrix materials for which the element to be determined is perfectly known and also the major compounds that produce a matrix influence on the signal (e.g. alloys, gases). 

Analysis at the appropriate scale for thermometry often requires very small samples, either as mineral separates, chips, or in situ. Table 1 reviews techniques for stable isotope microanalysis and Figure 1 shows the analytical trade-offs for different systems of microanalysis as they are generally applied in 2001 ion microprobe analysis IR-wavelength laser fluorination of chips or powder UV-wavelength laser analysis in situ, and continuous flow mass-spectrometry (CFMS) which can be coupled to pyrolysis or laser systems. 

Esteban, N.V. Yergey, A.L. Liberate, D.J. Lougfalin, T. Loriaux, D.L. Stable isotope dilution method using thermospray liquid chromatography/mass spectrometry for quantification of daily cortisol production in humans. Biomed.Environ.Mass.Spectrom., 1988, 15, 603-608 [thermospray LC-MS] Sheikh, S.U. Touchstone, J. HPLC of steroids in non-aqueous mobfle phase at subambient temperature. J.Liq.Chromatogr., 1987, 10, 2489-2496 [column temp -50 simultaneous cortisone, desoxycorticos-terone, estradiol, estrone]... 

Mass spectrometric approaches are also very useful for the measurement of stable isotopes in drug metabolism studies. The application of MS to the quantitative measurement of stable isotope has been limited due to the high cost and sophistication of the instruments necessary for stable isotope enrichment studies. Nonetheless, recent improvements in instrument design and performance, as well as computer software for instrument control, data acquisition, and analysis, have increased the sensitivity and reliability of stable isotopic enrichment studies. These new MS instruments, including continuous-flow isotope ratio mass spectrometry (CF-IRMS) and HPLC-chemical reaction interface mass spectrometry (HPLC-CRIMS) are increasingly less expensive, easier to operate, and accessible for mass balance/ metabolite identification studies with stable isotopes. 

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