Abstract

Metabolic products of biological systems in most cases are polyatomic molecular structures containing polyisotopic elements (hydrogen, carbon, nitrogen, oxygen, sulfur, chorine, etc.) that are different in genesis and biosynthetic pathways. In the molecules carrying two and more atoms of polyisotopic element in different positions (sites), the probability of detection of isotopes by sites in the pool (array) of analyzed molecules may be different, i.e., there is intramolecular isotopic heterogeneity by the specified element. Detection and quantitative estimation of isotopic heterogeneity of polyisotopic elements in molecules by the methods of isotopic mass spectrometry is a novel source of information about the processes involving the respective polyisotopic element. An isotopic equation has been proposed, the coefficients of which are normalized peak intensities of isotopically different molecular ions in the mass spectrum of the analyte. Solutions of this equation reflect the abundance ratios of isotopic atoms of polyisotopic element by its positions in molecules comprising the analyzed pool. During homogenous (equally probable) distribution of isotopic atoms of the element by all of its sites in molecules of the analyzed pool, solutions of the isotopic equation are equal to each other. In the case of non-homogenous isotope distribution of the polyisotopic element in the pool of molecules, solutions of the isotopic equation take on different values and may be presented by both real and complex numbers. Solutions of the isotopic equation reflect the peculiarities of distribution of element isotopes in a molecule and possible pathways of formation of a pool of analyzed molecules under laboratory and natural conditions.

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