This study presents, for the first time, the successful application of analyzing a whole gas chromatography (GC) chromatogram by nuclear magnetic resonance (NMR) spectroscopy using a continuous repeatable and stable (n = 280) high-resolution (HR) GC fractionation platform with a 96-well plate. Typically with GC- or liquid chromatography-mass spectrometry analysis, (isomer) standards and/or additional NMR analysis are needed to confirm the identification and/or structure of the analyte of interest. In the case of complex substances (e.g., UVCBs), isomer standards are often unavailable and NMR spectra too complex to achieve this. This proof of concept study shows that a HR GC fractionation collection platform was successfully applied to separate, purify, and enrich isomers in complex substances from a whole GC chromatogram, which would facilitate NMR analysis. As a model substance, a chlorinated paraffin (CP) mixture (>8,000 isomers) was chosen. NMR spectra were obtained from all 96 collected fractions, which provides important information for unravelling their full structure. As a proof of concept, a spectral interpretation of a few NMR spectra was made to assign sub-structures. More research is ongoing for the full characterization of CP isomers using multivariate statistical analysis. For the first time, up to only a few CP isomers per fraction were isolated from a highly complex mixture. These may be further purified and certified as standards, which are urgently needed, and can also be used for persistency, bioaccumulation, or toxicity studies.
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Da Vinci Laboratory Solutions is thanked for providing the GC-fractionation platform and Jaap Schaap from Da Vinci is acknowledged for his advice and support concerning the GC fractionation platform. Quimica del Cinca is acknowledged for synthesizing the CP-14 50% mixture and Andrew Jaques of the Chlorinated Paraffins Industry Association is thanked for arranging the provision of the samples. Dr. Eelco Ruijter is acknowledged for his input and expertise on the interpretation of the NMR Spectra. L.M.v.M. and P.E.G.L. were financially supported by CEFIC LRI (ECO 38, ECO 42). L.M.v.M. was also financially supported by Eurostars (E!113388—CHLOFFIN).
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