Solvent suppression techniques for coupling of size exclusion chromatography and 1H NMR using benchtop spectrometers at 43 and 62 MHz

J Höpfner; B Mayerhöfer; C Botha; D Bouillaud; J Farjon; P Giraudeau; M Wilhelm

doi:10.1016/j.jmr.2020.106889

Solvent suppression techniques for coupling of size exclusion chromatography and ¹H NMR using benchtop spectrometers at 43 and 62 MHz

J Magn Reson. 2021 Feb:323:106889. doi: 10.1016/j.jmr.2020.106889.

Authors

J Höpfner¹, B Mayerhöfer¹, C Botha¹, D Bouillaud², J Farjon², P Giraudeau³, M Wilhelm⁴

Affiliations

¹ Karlsruhe Institute of Technology (KIT), Institute for Chemical Technology and Polymer Chemistry, Engesserstr. 18, 76131 Karlsruhe, Germany.
² Université de Nantes, CNRS, CEISAM UMR 6230, F-44000 Nantes, France.
³ Université de Nantes, CNRS, CEISAM UMR 6230, F-44000 Nantes, France. Electronic address: patrick.giraudeau@univ-nantes.fr.
⁴ Karlsruhe Institute of Technology (KIT), Institute for Chemical Technology and Polymer Chemistry, Engesserstr. 18, 76131 Karlsruhe, Germany. Electronic address: manfred.wilhelm@kit.edu.

PMID: 33518176
DOI: 10.1016/j.jmr.2020.106889

Abstract

The characterisation of polymeric materials in their full complexity of chain length, monomeric composition, branching and functionalization is a tremendous challenge and is best tackled by tailored multi-dimensional coupled analytical and detection techniques. Herein, we focus on the improvement of an affordable but information rich 2D-method for polymer analysis: the online hyphenation of benchtop ¹H NMR spectroscopy with size exclusion chromatography (SEC). The main benefit of this approach is correlated information of chain length (SEC) to chemical composition (¹H NMR). Our setup combines SEC onflow with a benchtop NMR spectrometer at 43 or 62 MHz with chemical shift resolution as a robust detector. A detailed comparison of the two instruments is included considering, that only the 43 MHz instrument is equipped with a dedicated z-gradient enabling pulse sequences such as WET. The main challenge of this method is the very low concentration of species of interest after chromatographic separation. At typical SEC conditions, the analyte dilution is typically more than a factor of 1000:1 in a protonated solvent. Therefore, an efficient solvent signal suppression is needed. In this article, several suppression pulse sequences are explored like WET, WEFT, JNR and a simple one-pulse approach - some for the first time on this hardware. By choosing an optimal method, signal strength ratios of solvent to analyte of 1:1 or better are achievable on flow. To illustrate the broad range of possible applications, three typical cases of analyte to solvent signal proximity (no overlap, partial and full overlap) are discussed using typical polymers (PS, PMMA, PEMA) and solvents (chloroform and THF). For each case, several suppression methods are compared and evaluated using a set of numerical criteria (analyte signal suppression and broadening, solvent signal suppression, remaining solvent signal width).

Keywords: Benchtop NMR; Chromatography; Combined method; Polymer analysis; SEC-NMR; Solvent suppression.

Publication types

Research Support, Non-U.S. Gov't