Isotope ratio analysis mixture

Most flavourings are complex mixtures of many compounds. As IRMS makes only sense with pure analytes, a strict purification of individual substances is indispensable. Therefore GC-IRMS has been further developed and optimised to multi-compound isotope ratio analysis by its coupling IRMS to capillary (c) and multidimensional (MD) gas chromatography (see 6.2.2.2.2). This methodology demands a strict intrinsic control and standardisation [340] apart from the international standards (see Table 6.3) also secondary standards like the polyethylene foil IAEA-CH7 or the NBS22 oil are available from the IAEA in Vieima. However, as these substances are also not suitable for the direct standardisation of data from a coupled GC system for flavour isotope analysis, certificated tertiary laboratory standards for hydrogen have been developed by parallel analysis of flavour compounds by TC/EA-IRMS and MDGC-P-IRMS [210]. 

The isotopic distribution found in natural F F compounds serves as a signature that analysts can use to differentiate natural compounds from synthetic analogs. The metabolic pathways that plants use to create carbon compounds discriminate between C and C. The C/ C ratio of the carbon dioxide the plant uses as a reactant differs from the C/ C ratio of the compounds the plant produces. Stable carbon isotope ratio analysis (SIRA) measures the C/ C ratio and can authenticate the natural or synthetic origins of some F F materials. SIRA applied to isotopes of hydrogen, or D and H can also serve to authenticate natural F F materials. When combined with GC the on-line or D/ H SIRA analysis can authenticate each component in a complex mixture such as a cinnamon bark oil (19). 

Authenticity evaluation has recently received increased attention in a number of industries. The complex mixtures involved often require very high resolution analyses and, in the case of determining the authenticity of natural products, very accurate determination of enantiomeric purity. Juchelka et al. have described a method for the authenticity determination of natural products which uses a combination of enantioselective multidimensional gas chromatography with isotope ratio mass spectrometry (28). In isotope ratio mass spectrometry, combustion analysis is combined with mass spectrometry, and the ratio of the analyte is measured versus a... 

Both absolute quantitation and relative quantitation of species in mixtures is of interest in some circumstances. Quantitation in a 5-minute analysis can be achieved by addition of an internal standard, ideally the target microorganism grown in special media to incorporate heavy isotopes92-95 and determination of the relative peak heights of pairs of proteins from the analyte and the standard. Isotope-labeled proteins or peptides, selected to match proteins or peptides characteristic of target microorganisms, can also serve as internal standards for isotope ratio measurement. The addition of unmatched proteins or peptides is less reliable for either ESI or MALDI measurements because of unpredictable suppression in the variable mixture. 

Samples were prepared for Cu isotope analysis on the Multicollector Inductively-Coupled Plasma Mass Spectrometer (MC-ICPMS) at University of Arizona. The Cu-rich samples were loaded and dissolved in pure HNO3 and the Cu-poor samples were loaded and dissolved in a mixture of HCI and HNO3, Chromatographic separation of the Fe and Cu ions was deemed necessary for the Cu-rich samples. The diluted solutions were injected into the MC-ICPMS using a microconcentric nebulizer. Samples were run numerous times to increase precision. The Cu isotope ratios are reported in conventional per mil notation, relative to the NIST 976 standard. Mass bias was also accounted for by bracketing methods with the NIST 976 standard. 

The fundamentals and several applications of isotope dilution mass spectrometry requiring accurate isotope ratio measurements are reviewed by Heumann.50,51 Today isotope dilution mass spectrometry (IDMS) is recognized as a primary measurement method, by means of which accurate results with sufficiently small uncertainties can be achieved and therefore it has been used in certifying the composition of reference materials. A requirement of isotope dilution analysis in mass spectrometry is to achieve equilibration of spike and sample so that very careful sample preparation steps, especially in solid mass spectrometry, are necessary when a homogeneous sample spike mixture is to be prepared. 

The results of the second interlaboratory study of PCN analytical methods using environmental matrices, undertaken by the US National Institute of Standards and Technology (NIST), should provide an indication of the comparability of published environmental PCN data and show where additional method enhancements are needed. Further method development efforts in the analysis of PCNs, and other complex mixtures are likely to focus on improving efficiencies by optimizing run times and separation. Examples may include time-of-flight mass spectrometry and multidimensional GC. New methods, such as isotope ratio mass spectrometry, may contribute to further source apportionment of complex mixtures [88]. 

Theoretical and experimental results by Blom (45) have focused on the precision requirements for the mass spectrometric analysis of combinatorial library mixtures. In his work, Blom has used discrete mass filters in combination with mass-MS/MS, M + 1/M, and M + 2/M isotope ratio filters to determine library components specifically from peptide libraries. As pointed out below, while nonpeptide libraries have mass distributions that are completely random, peptide library building blocks are limited in their diversity,... 

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