Full Spectrum Isotopic 13 C NMR Using Polarization Transfer for Position-Specific Isotope Analysis.

For the last ten years, quantitative isotope ratio monitoring 13C NMR (irm-13C NMR) has been successfully tested and proved as an efficient tool for the determination of the position-specific determination of 13C/12C ratios. Several applications in different domains have shown its interest. In the context of origin assignment, the possibility to track the distribution network of illicit drugs or cutting agents is of prime importance. However irm-13C NMR still suffers from a relative lack of sensitivity limiting its dissemination among control laboratories. Improvements were proposed to reduce experiment time by using the INEPT sequence ("Insensitive Nuclei Enhanced by Polarization Transfer") based on polarization transfer from highly sensitive 1H to less sensitive 13C. Several applications based on the use of the one bond scalar coupling between 1H and 13C (1JCH) have shown the potential of this methodology in terms of short experimental duration. However, the isotopic information given by quaternary carbons was lost. The aim of this study is to extend this approach by using short and long range coupling (1JCH, 2JCH and 3JCH) in order to have access to all 13C/12C position-specific ratios, i.e. acquisition of the full spectrum (FS-INEPT). It is shown that this innovative tool provides both sensitivity gain -thanks to the long-range polarization transfer- and appropriate repeatability. The relative isotopic profiles allowed the classification of two cutting agents, caffeine and paracetamol (acetaminophen), according to their origin, as it was previously observed with "classical" irm-13C NMR but consuming much less sample and/or reducing the experimental time.