Synthesis of <sup>13</sup>C-Perlabeled Cellulose with more than 99% Isotopic Enrichment by a Cationic Ring-Opening Polymerization Approach

Adelwöhrer, Christian; Takano, Toshiyuki; Nakatsubo, Fumiaki; Rosenau, Thomas

doi:10.1021/bm9006612

Cited by 22 publications

(13 citation statements)

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“…Similar to a puzzle where the arrangement of the individual pieces must fit to give the final picture, the number of furanoyl units per chromophore molecule and their linkage sites can be determined by this methodology, which was done for all five chromophores. The combination of isotopic labeling and NMR spectroscopy, as also used previously (Adelwöhrer et al 2009;Krainz et al 2010;Malz et al 2007), once more proved to be a powerful tool in chromophore research.…”

Section: Resultsmentioning

confidence: 93%

Chromophores from hexeneuronic acids: identification of HexA-derived chromophores

et al. 2017

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Hexeneuronic acids (HexA) have long been known as triggers for discoloration processes in glucuronoxylan-containing cellulosic pulps. They are formed under the conditions of pulping from 4-Omethylglucuronic acid residues, and are removed in an ''A stage'' along the bleaching sequences, which mainly comprises acidic washing treatments. The chemical structures of HexA-derived chromophoric compounds 4-8, which make up 90% of the HexAderived chromophores, are reported here for the first time. The compounds are ladder-type, mixed quinoidaromatic oligomers of the bis(furano)-[1,4]benzoquinone and bis(benzofurano)-[1,4]benzoquinone type. The same chromophoric compounds are generated independently of the starting material, which can be either a) HexA in pulp, b) the HexA model compound methyl 1-13 C-4-deoxy-b-L-threo-hex-4-enopyranosiduronic acid (1) or c) a mixture of the primary degradation intermediates of 1, namely 5-formyl-furancarboxylic acid (2) and 2-furancarboxylic acid (3). Isotopic labeling ( 13 C) in combination with NMR spectroscopy and mass spectrometry served for structure elucidation, and final confirmation was provided by X-ray structure analysis.13 C-Isotopic labeling was also used to establish the formation mechanisms, showing all the compounds to be composed of condensed, but otherwise largely intact, 2-carbonylfuran and 2-carbonylfuran-5-carboxylic acid moieties. These results disprove the frequent assumption that HexA-derived or furfural-derived chromophores are linear furanoid polymers, and might have a direct bearing on structure elucidation studies Chromophores in cellulosic materials. Part XVI.

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Section: Resultsmentioning

confidence: 93%

Chromophores from hexeneuronic acids: identification of HexA-derived chromophores

et al. 2017

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“…Cationic ring-opening copolymerization of glucose orthoester derivatives 2D and 2L Glucose orthoester derivatives 2D and 2L were synthesized from compounds 1D and 1L, respectively, according to previous reports (Adelwöhrer et al 2009, Yagura et al 2020). The ring-opening copolymerization of compounds 2D and 2L in a 1:1 ratio was conducted to give compound 3DL in quantitative yield.…”

Section: Resultsmentioning

confidence: 99%

“…Materials D-glucose (1D) and L-glucose (1L) were purchased from Nacalai Tesque Inc. (Kyoto, Japan) and Tokyo Chemical Industry Co. (Tokyo, Japan), respectively, and were dried in a vacuum desiccator under high vacuum (less than 1 hPa) at 70 C for 16 h before use. Compounds 2D and 2L were synthesized from compounds 1D and 1L, respectively, according to previous reports (Adelwöhrer et al 2009, Yagura et al 2020. Powdered 4 Å molecular sieves were activated in a GTO-2000 glass tube oven (Sibata Scientific Technology Ltd, Tokyo, Japan) Scheme 1.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of optically inactive cellulose via cationic ring-opening polymerization

et al. 2021

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Cellulose, which comprises D-glucose and L-glucose (D,L-cellulose), was synthesized from D-glucose (1D) and L-glucose (1L) via cationic ring-opening polymerization. Specifically, the ring-opening copolymerization of 3-O-benzyl-2,6-di-O-pivaloyl--D-glucopyranoside (2D) and 3-O-benzyl-2,6-di-O-pivaloyl-β-D-glucopyranoside (2L), synthesized from compounds 1D and 1L, respectively, in a 1:1 ratio, afforded 3-O-benzyl-2,6-di-O--D,L-glucopyranan (3DL) with a degree of polymerization (DPn) of 28.5 (Mw/Mn = 1.90) in quantitative yield.The deprotection of compound 3DL and subsequent acetylation proceeded smoothly to afford acetylated compound 4DL with a DPn of 18.6 (Mw/Mn = 2.08). The specific rotation of acetylated compound 4DL was +0.01, suggesting that acetylated compound 4DL was optically inactive cellulose triacetate. Furthermore, before acetylation, compound 4DL was an optically inactive cellulose comprising an almost racemic mixture of D-glucose and Lglucose. Compound 4DL was an amorphous polymer. This is the first reported synthesis of optically inactive D,L-cellulose.

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“…In 2009, Adelw€ ohrer et al [41] reported the successful synthesis of 13 Cperlabeled cellulose through an approach involving cationic ring-opening polymerization. As precursor, the authors used 3-O-benzyl-13 C 6 -glucopyranose 1,2,4-orthopivalate and obtained fully labeled 13 C-cellulose as the cellulose II allomorph, with a DP of 40 and an overall yield of 28%.…”

Section: Chemical Synthesismentioning

confidence: 99%

Preparation and Analysis of Cello- and Xylooligosaccharides

Vejdovszky

Oberlerchner

Zweckmair

et al. 2015

Advances in Polymer Science

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This review provides a general overview of preparation, separation, and analytical methods for cello-and xylooligosaccharides. Arising as side-stream products of different biorefinery processes, these compounds have increasingly gained the interest of researchers and engineers in the last few decades. Beside their application as additives in the food, feed, and pharmaceutical industries, these oligomeric carbohydrates are of key importance as model compounds for studying the dependence of physicochemical properties on the degree of polymerization (DP). First, different preparation methods for mixtures of oligosaccharides with DPs between 1 and 30 are discussed. These methods include acetolysis, acid and enzymatic hydrolysis, and glycoside synthesis. Then, separation techniques, including size exclusion chromatography, normal phase and hydrophilic interaction chromatography, and chromatography on cation exchange resins, are presented. Analysis of oligosaccharides by different techniques is described.

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Synthesis of ¹³C-Perlabeled Cellulose with more than 99% Isotopic Enrichment by a Cationic Ring-Opening Polymerization Approach

Cited by 22 publications

References 13 publications

Chromophores from hexeneuronic acids: identification of HexA-derived chromophores

Chromophores from hexeneuronic acids: identification of HexA-derived chromophores

Synthesis of optically inactive cellulose via cationic ring-opening polymerization

Preparation and Analysis of Cello- and Xylooligosaccharides

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Synthesis of 13C-Perlabeled Cellulose with more than 99% Isotopic Enrichment by a Cationic Ring-Opening Polymerization Approach

Cited by 22 publications

References 13 publications

Chromophores from hexeneuronic acids: identification of HexA-derived chromophores

Chromophores from hexeneuronic acids: identification of HexA-derived chromophores

Synthesis of optically inactive cellulose via cationic ring-opening polymerization

Preparation and Analysis of Cello- and Xylooligosaccharides

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Product

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Synthesis of ¹³C-Perlabeled Cellulose with more than 99% Isotopic Enrichment by a Cationic Ring-Opening Polymerization Approach