Improving quantitative 13C NMR performance by an adiabatic scheme

Abstract NMR is a primary method of measurement that provides quantitative traceable results without the need for a standard of the same measurand. Despite the advantages of the 1 H nucleus, such as high sensitivity, short relaxation times and widespread distribution in organic compounds, some molecules present only labile H atoms, or the 1 H peaks of a sample may overlap with impurities. With the CHORAD scheme – a combination of the pulse sequence CHORUS and adiabatic modulation for 1 H decoupling – this study has shown that 13 C NMR can be used for quantitative analyses with a bias smaller than 2% and expanded uncertainty of 0.7% (for a confidence level of 95%). Since 13 C is found with significant non-statistic isotope fractionation, all the peaks of the sample and internal standard should be integrated and their bulk 13 C abundances obtained by isotope ratio mass spectrometry (IRMS) must be considered to meet quantitative requirements. Future experimental work may be performed to test this procedure for complex matrix samples. This approach also proved to be suitable for studies of site-specific 13 C distribution and led to better heteronuclear decoupling when compared with the use of adiabatic decoupling with ordinary hard 90° pulses, a combination extensively reported in the literature over the last decade. An examination of the molecules studied in this work and others from the literature revealed an overall trend in the 13 C intramolecular profile – hydrogen-containing positions are often 13 C-depleted. A potential contribution of 1 J CH coupling to these results is discussed.