Synthesis of xylan carbonates - An approach towards reactive polysaccharide derivatives showing self-assembling into nanoparticles

Martin Gericke; Lars Gabriel; Katja Geitel; Stefan Benndorf; Poonam Trivedi; Pedro Fardim; Thomas Heinze

doi:10.1016/j.carbpol.2018.03.083

Synthesis of xylan carbonates - An approach towards reactive polysaccharide derivatives showing self-assembling into nanoparticles

Carbohydr Polym. 2018 Aug 1:193:45-53. doi: 10.1016/j.carbpol.2018.03.083. Epub 2018 Mar 26.

Authors

Martin Gericke¹, Lars Gabriel¹, Katja Geitel¹, Stefan Benndorf¹, Poonam Trivedi², Pedro Fardim³, Thomas Heinze⁴

Affiliations

¹ Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Centre of Excellence for Polysaccharide Research, Humboldtstraße 10, D-07743, Jena, Germany.
² Laboratory of Fibre and Cellulose Technology, Åbo Akademi University, Porthansgatan 3, FI-20500, Turku, Finland.
³ Laboratory of Fibre and Cellulose Technology, Åbo Akademi University, Porthansgatan 3, FI-20500, Turku, Finland; Department of Chemical Engineering, University of Leuven, Celestijnenlaan 200 F, 3001, Leuven, Heverlee, Belgium.
⁴ Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Centre of Excellence for Polysaccharide Research, Humboldtstraße 10, D-07743, Jena, Germany; Laboratory of Fibre and Cellulose Technology, Åbo Akademi University, Porthansgatan 3, FI-20500, Turku, Finland. Electronic address: thomas.heinze@uni-jena.de.

PMID: 29773396
DOI: 10.1016/j.carbpol.2018.03.083

Abstract

Xylan phenyl carbonate (XPC) derivatives were prepared and characterized comprehensively. By conversion of xylan with phenyl chloroformate either in dipolar aprotic solvents with LiCl or in an ionic liquid, XPC with degrees of substitution (DS) of up to 2.0, i.e., fully functionalized derivatives, could be obtained. The synthesis was studied with respect to the influence of different reaction parameters. It was found that the reaction medium as well as the type of starting xylan strongly affected the efficiency of the derivatization. The derivatives obtained were characterized by FT-IR- and NMR spectroscopy. Surprisingly, it was found that C-3 is the most reactive position in this particular reaction while substitution in position C-2 only occurred if the neighboring position C-3 already carried a phenyl carbonate group. XPC were found to form spherical nanoparticles (NP) of well-defined shape with diameters around 158 nm. These materials possess unique potential as activated NP for advanced applications.

Keywords: Ionic liquids; Nanoparticles; Polysaccharides; Substituent distribution pattern; Xylan carbonates; Xylan derivatization.