Issue 10, 2023

Formation of substituted dioxanes in the oxidation of gum arabic with periodate


Renewable polysaccharide feedstocks are of interest in bio-based food packaging, coatings and hydrogels. Their physical properties often need to be tuned by chemical modification, e.g. by oxidation using periodate, to introduce carboxylic acid, ketone or aldehyde functional groups. The reproducibility required for application on an industrial scale, however, is challenged by uncertainty about the composition of product mixtures obtained and of the precise structural changes that the reaction with periodate induces. Here, we show that despite the structural diversity of gum arabic, primarily rhamnose and arabinose subunits undergo oxidation, whereas (in-chain) galacturonic acids are unreactive towards periodate. Using model sugars, we show that periodate preferentially oxidises the anti 1,2-diols in the rhamnopyranoside monosaccharides present as terminal groups in the biopolymer. While formally oxidation of vicinal diols results in the formation of two aldehyde groups, only traces of aldehydes are observed in solution, with the main final products obtained being substituted dioxanes, both in solution and in the solid state. The substituted dioxanes form most likely by the intramolecular reaction of one aldehyde with a nearby hydroxyl group, followed by hydration of the remaining aldehyde to form a geminal diol. The absence of significant amounts of aldehyde functional groups in the modified polymer impacts crosslinking strategies currently attempted in the preparation of renewable polysaccharide-based materials.

Graphical abstract: Formation of substituted dioxanes in the oxidation of gum arabic with periodate

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Article information

Article type
03 Jan 2023
24 Apr 2023
First published
26 Apr 2023
This article is Open Access
Creative Commons BY license

Green Chem., 2023,25, 4058-4066

Formation of substituted dioxanes in the oxidation of gum arabic with periodate

H. S. Siebe, A. S. Sardjan, S. C. Maßmann, J. Flapper, K. J. van den Berg, N. N. H. M. Eisink, A. P. M. Kentgens, B. L. Feringa, A. Kumar and W. R. Browne, Green Chem., 2023, 25, 4058 DOI: 10.1039/D2GC04923F

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