About the assessment of the degree of oxidation of cellulose during periodate reaction: Comparison of different characterization techniques and their discrepancies

IF 2.4 3区化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY

Carbohydrate Research Pub Date : 2025-02-25 DOI:10.1016/j.carres.2025.109438

Lorette Brault , Nathalie Marlin , Gérard Mortha , Jérémy Boucher , Dominique Lachenal

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Abstract

This study focuses on the side reactions responsible for the low efficiency of the periodate-chlorite oxidation sequence of cellulose. Discrepancies are systematically observed between different commonly-used characterization methods for assessing the degree of oxidation (DO) of cellulose. Indeed, the different titration methods of the aldehyde groups found in the dialdehyde cellulose (DAC) generated by the Malaprade reaction on cellulose, do not generally fit the titration of the carboxyl groups found in the dicarboxycellulose (DCC), generated after chlorite oxidation of the DAC. Possible side reactions affecting the Malaprade and chlorite reactions, or affecting the accuracy of the titrations, are presented here and discussed. Studying periodate consumption, iodate generation, organic acids release during the reactions, fiber mass yield, sodium hydroxide consumption during the β-alkoxy-elimination reaction of DAC, ¹³C NMR spectra of DAC and DCC, and carboxyl titration of DCC, allowed to conclude that chlorite did not fully oxidize the aldehyde groups in the DAC, but only about one aldehyde out of two. It was found that the non-oxidized aldehydes in the DAC were hindered by hemiacetal-type linkages. This study refutes several well-established hypotheses from the literature when applied to reactions under mild conditions.

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来源期刊

Carbohydrate Research 化学-生化与分子生物学

CiteScore

5.00

自引率

3.20%

发文量

183

审稿时长

3.6 weeks

期刊介绍： Carbohydrate Research publishes reports of original research in the following areas of carbohydrate science: action of enzymes, analytical chemistry, biochemistry (biosynthesis, degradation, structural and functional biochemistry, conformation, molecular recognition, enzyme mechanisms, carbohydrate-processing enzymes, including glycosidases and glycosyltransferases), chemical synthesis, isolation of natural products, physicochemical studies, reactions and their mechanisms, the study of structures and stereochemistry, and technological aspects. Papers on polysaccharides should have a "molecular" component; that is a paper on new or modified polysaccharides should include structural information and characterization in addition to the usual studies of rheological properties and the like. A paper on a new, naturally occurring polysaccharide should include structural information, defining monosaccharide components and linkage sequence. Papers devoted wholly or partly to X-ray crystallographic studies, or to computational aspects (molecular mechanics or molecular orbital calculations, simulations via molecular dynamics), will be considered if they meet certain criteria. For computational papers the requirements are that the methods used be specified in sufficient detail to permit replication of the results, and that the conclusions be shown to have relevance to experimental observations - the authors'' own data or data from the literature. Specific directions for the presentation of X-ray data are given below under Results and "discussion".