title: Evidence of 13C non-covalent isotope effects obtained by quantitative 13C nuclear magnetic resonance spectroscopy at natural abundance during normal phase liquid chromatography.
abstract: Quantitative isotopic (13)C NMR at natural abundance has been used to determine the site-by-site (13)C/(12)C ratios in vanillin and a number of related compounds eluted from silica gel chromatography columns under similar conditions. Head-to-tail isotope fractionation is observed in all compounds at the majority of carbon positions. Furthermore, the site-specific isotope deviations show signatures characteristic of the position and functionality of the substituents present. The observed effects are more complex than would be obtained by simply summing the individual effects. Such detail is hidden when only the global (13)C content is measured by mass spectrometry. In particular, carbon positions within the aromatic ring are found to show site-specific isotope fractionation between the solute and the stationary phase. These interactions, defined as non-covalent isotope effects, can be normal or inverse and vary with the substitution pattern present.
authors.affiliation: Elucidation of Biosynthesis by Isotopic Spectrometry Group, CNRS-University of Nantes Unit for Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), UMR CNRS6230, 2 rue de la Houssinière, BP 92208, Nantes 44322, France.
authors.forename: Eliot P
authors.initials: EP
authors.lastname: Botosoa
authors.forename: Virginie
authors.initials: V
authors.lastname: Silvestre
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Robins
authors.forename: Jose Manuel Moreno
authors.initials: JM
authors.lastname: Rojas
authors.forename: Claude
authors.initials: C
authors.lastname: Guillou
authors.forename: Gérald S
authors.initials: GS
authors.lastname: Remaud
mesh_terms: D001547:Benzaldehydes / Q000737:chemistry; D002247:Carbon Isotopes / Q000737:chemistry*; D002853:Chromatography, Liquid / Q000379:methods*; D003373:Coumaric Acids / Q000737:chemistry; D003903:Deuterium / Q000737:chemistry; D008956:Models, Chemical; D019906:Nuclear Magnetic Resonance, Biomolecular / Q000379:methods*; D010103:Oxygen Isotopes / Q000737:chemistry; D058428:Silica Gel; D012822:Silicon Dioxide / Q000737:chemistry
chemical_list: D001547:Benzaldehydes; D002247:Carbon Isotopes; D003373:Coumaric Acids; D010103:Oxygen Isotopes; D058428:Silica Gel; D012822:Silicon Dioxide; C024896:4-anisaldehyde; D003903:Deuterium; C004999:ferulic acid; C100058:vanillin