TEMPO/NaClO2/NaOCl oxidation of arabinoxylans. (1st May 2021)

• Record Type: Journal Article
• Authors: Pandeirada, Carolina O.; Merkx, Donny W.H.; Janssen, Hans-Gerd; Westphal, Yvonne; Schols, Henk A.
• Is Part Of: Carbohydrate polymers. Volume 259(2021)
• Publication Date: 2021-05-01
• Subjects: AX arabinoxylan -- AraAf arabinuronic acid -- BAIB bis(acetoxy)iodobenzene -- COSY homonuclear 1H-1H correlation spectroscopy -- DB degree of branching -- DO degree of oxidation -- EI impact mode -- GC–MS gas chromatography coupled to mass spectrometry -- HILIC hydrophilic interaction chromatography -- HPAEC-PAD High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection -- HPSEC high performance size exclusion chromatography -- Hydr_ox-AX1.0:2.6:0.4_H2O water fraction collected by SPE of the hydrolysate ox-AX1.0:2.6:0.4 -- Hydr_ox-AX1.0:2.6:0.4_TFA acetronitrile:water 60:40, containing 0.05 % (v/v) TFA fraction collected by SPE of the hydrolysate ox-AX1.0:2.6:0.4 -- IS internal standard -- Isugar 1H-NMR signal integrals derived from each identified sugar -- MS mass spectrometry -- Mw molecular weight -- NaBD4 sodium borodeuteride -- NaClO2 sodium chlorite -- NaOCl sodium hypochlorite -- ox-AX oxidized-AX -- ox-AX1.0:2.6:1.5 oxidized-AX with a TEMPO:NaClO2:NaOCl ratio of 1.0:2.6:1.5 per mol of C5-OH of Ara -- ox-AX0.2:2.6:1.5 oxidized-AX with a TEMPO:NaClO2:NaOCl ratio of 0.2:2.6:1.5 per mol of C5-OH of Ara -- ox-AX1.0:2.6:0.4 oxidized-AX with a TEMPO:NaClO2:NaOCl ratio of 1.0:2.6:0.4 per mol of C5-OH of Ara -- ox-product oxidized-product -- PMAA partially methylated alditol acetate -- Red-ox-AX1.0:2.6:0.4 carboxyl-reduced ox-AX1.0:2.6:0.4 with carbodiimide/NaBD4 -- SG switchgrass -- SPE solid phase extraction -- TEMPO 2, 2, 6, 6-tetramethylpiperidine-1-oxyl radical; Arabinoxylan -- TEMPO-oxidation -- Arabinuronoxylan -- Arabinuronic acid; Polysaccharides -- Periodicals; Polysaccharides -- Periodicals; Polysaccharides -- Périodiques; Electronic journals; 547.78
• DOI: 10.1016/j.carbpol.2021.117781
• Languages: English
• ISSNs: 0144-8617

Abstract

Graphical abstract: Highlights: TEMPO-oxidation of arabinoxylan with various TEMPO:NaClO2 :NaOCl systems was studied. TEMPO:NaClO2 :NaOCl (1.0:2.6:0.4) creates an ox-AX with high molecular weight. Arabinuronoxylans with a xylan substitution pattern resembling the parental AX. Abstract: TEMPO-oxidation of neutral polysaccharides has been used to obtain polyuronides displaying improved functional properties. Although arabinoxylans (AX) from different sources may yield polyuronides with diverse properties due to their variable arabinose (Ara f ) substitution patterns, information of the TEMPO-oxidation of AX on its structure remains scarce. We oxidized AX using various TEMPO:NaClO2 :NaOCl ratios. A TEMPO:NaClO2 :NaOCl ratio of 1.0:2.6:0.4 per mol of Ara gave an oxidized-AX with high molecular weight, minimal effect on xylose appearance, and comprising charged side chains. Although NMR analyses unveiled arabinuronic acid (AraA f ) as the only oxidation product in the oxidized-AX, accurate AraA quantification is still challenging. Linkage analysis showed that > 75 % of the β-(1→4)-xylan backbone remained single-substituted at position O -3 of Xyl similarly to native AX. TEMPO-oxidation of AX can be considered a promising approach to obtain arabinuronoxylans with a substitution pattern resembling its parental AX.