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

{"title":"About the assessment of the degree of oxidation of cellulose during periodate reaction: Comparison of different characterization techniques and their discrepancies","authors":"Lorette Brault , Nathalie Marlin , Gérard Mortha , Jérémy Boucher , Dominique Lachenal","doi":"10.1016/j.carres.2025.109438","DOIUrl":null,"url":null,"abstract":"<div><div>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, <sup>13</sup>C 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.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"552 ","pages":"Article 109438"},"PeriodicalIF":2.4000,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Carbohydrate Research","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0008621525000643","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}

引用次数: 0

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.

Abstract Image

查看原文本刊更多论文

本研究着重于纤维素高碘酸盐-绿泥酸盐氧化序列效率低的副反应。系统地观察了不同常用的表征方法之间的差异，以评估纤维素的氧化程度（DO）。的确，对由Malaprade反应在纤维素上生成的二醛纤维素（DAC）中发现的醛基的不同滴定方法，通常不适用于DAC经亚氯酸盐氧化后生成的二醛纤维素（DCC）中发现的羧基的滴定。可能的副反应影响Malaprade和亚氯酸盐反应，或影响滴定的准确性，在这里提出和讨论。通过对DAC β-烷氧基消除反应中高碘酸盐消耗、碘酸盐生成、有机酸释放、纤维质量产率、氢氧化钠消耗、DAC和DCC的13C NMR谱、DCC的羧基滴定等方面的研究，可以得出结论：亚氯酸盐并没有完全氧化DAC中的醛基，只氧化了两个醛基中的一个。发现DAC中非氧化醛受到半缩醛型键的阻碍。当应用于温和条件下的反应时，本研究驳斥了文献中几个公认的假设。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

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".