Abstract

Hemicelluloses, the second most abundant polysaccharides right after cellulose, represent complex biopolymers whose structural features are not yet fully understood. Hence, the applicability of functionalized hemicellulose derivatives is still limited. Thus, the development of practical methods to reveal their structure is essential. Anionic, carboxylated GGM was prepared as the substrate, and their corresponding oligomers have been isolated and fully characterized for the first time in the present work. In order to accomplish this, each step has been optimized sequentially. Oxidized GGM was enzymatically digested, and the corresponding oligomers were isolated by preparative GPC. A toolset of wet chemistry and instrumental methods was used to characterize the isolated compounds in detail. Moreover, quantitative 13C-NMR combined with MALDI was demonstrated to deliver accurate analytical data compared to standard but time-consuming wet chemistry methods. The developed toolset is expected to be applicable to other plant polysaccharides and their derivatives as well.

Highlights

  • In order to enhance the sustainability of lignocellulosic biorefinery concepts, new approaches for utilizing side streams must be found

  • Large quantities are available as a side product of papermaking as it can be recovered from the process water or thermomechanical pulp (Willför et al 2003a) or directly from softwood by pressurized hot water extraction (Leppänen et al 2011; Song et al 2008)

  • GGM was TEMPO-oxidized at 5 °C on a minute timescale followed by enzymatic hydrolysis

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Summary

Introduction

In order to enhance the sustainability of lignocellulosic biorefinery concepts, new approaches for utilizing side streams must be found. Large quantities are available as a side product of papermaking as it can be recovered from the process water or thermomechanical pulp (Willför et al 2003a) or directly from softwood by pressurized hot water extraction (Leppänen et al 2011; Song et al 2008) This compound family corresponding to a monomeric sugar ratio of 3.5–4.5:1:0.5–1 (Man/Glc/Gal) (Hannuksela and Du Penhoat 2004; Willför et al 2003b, 2005) consists of a linear backbone of randomly distributed (1 → 4)-linked β-d-mannopyranosyl and (1 → 4)-linked β-d-glucopyranosyl units, with (1 → 6)-linked α-d-galactopyranosyl units coupled to the mannosyl units as shown in Fig. 1 (Hannuksela and Du Penhoat 2004; Willför et al 2003b).

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