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ChemSusChem. 2018 Sep 21;11(18):3259-3268. doi: 10.1002/cssc.201801177. Epub 2018 Aug 21.

Getting Closer to Absolute Molar Masses of Technical Lignins.

ChemSusChem

Grigory Zinovyev, Irina Sulaeva, Stepan Podzimek, Dierk Rössner, Ilkka Kilpeläinen, Ivan Sumerskii, Thomas Rosenau, Antje Potthast

Affiliations

  1. Department of Chemistry, Division of Chemistry of Renewable Resources, University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz-Strasse 24, A-3430, Tulln, Austria.
  2. Wyatt Technology Europe GmbH, Hochstrasse 12a, 56307, Dernbach, Germany.
  3. Institute of Chemistry and Technology of Macromolecular Materials, University of Pardubice, Studentska 573, Pardubice, 532 10, Czech Republic.
  4. Department of Chemistry, University of Helsinki, A.I. Virtasen Aukio 1, 00014, Helsinki, Finland.

PMID: 29989331 PMCID: PMC6175078 DOI: 10.1002/cssc.201801177

Abstract

Determination of molecular weight parameters of native and, in particular, technical lignins are based on size exclusion chromatography (SEC) approaches. However, no matter which approach is used, either conventional SEC with a refractive index detector and calibration with standards or multi-angle light scattering (MALS) detection at 488 nm, 633 nm, 658 nm, or 690 nm, all variants can be severely erroneous. The lack of calibration standards with high structural similarity to lignin impairs the quality of the molar masses determined by conventional SEC, and the typical fluorescence of (technical) lignins renders the corresponding MALS data rather questionable. Application of MALS detection at 785 nm by using an infrared laser largely overcomes those problems and allows for a reliable and reproducible determination of the molar mass distributions of all types of lignins, which has been demonstrated in this study for various and structurally different analytes, such as kraft lignins, milled-wood lignin, lignosulfonates, and biorefinery lignins. The topics of calibration, lignin fluorescence, and lignin UV absorption in connection with MALS detection are critically discussed in detail, and a reliable protocol is presented. Correction factors based on MALS measurements have been determined for commercially available calibration standards, such as pullulan and polystyrene sulfonate, so that now more reliable mass data can be obtained also if no MALS system is available and these conventional calibration standards have to be resorted to.

© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Keywords: infrared laser; kraft lignin; lignosulfonate; multi-angle light scattering; size exclusion chromatography

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