ACS Publications. Most Trusted. Most Cited. Most Read
Ultrastructural Characterization of the Core–Shell Structure of a Wide Range of Periodate-Oxidized Cellulose from Different Native Sources by Solid-State 13C CP-MAS NMR

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:ACS Sustainable Chem. Eng. 2019, 7, 1, 412-420
    Research Article

    Ultrastructural Characterization of the Core–Shell Structure of a Wide Range of Periodate-Oxidized Cellulose from Different Native Sources by Solid-State 13C CP-MAS NMR
    Click to copy article linkArticle link copied!

    Other Access OptionsSupporting Information (1)

    ACS Sustainable Chemistry & Engineering

    Cite this: ACS Sustainable Chem. Eng. 2019, 7, 1, 412–420
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acssuschemeng.8b03772
    Published November 3, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    The periodate oxidation of cellulose, which leads to the opening of the glucosyl rings to yield two aldehyde groups in the so-called dialdehyde cellulose, stands as one of the major and promising pathways for the derivatization of cellulose for the design of new biosourced materials. Despite the wide use of this method and the simplicity of its chemistry, the measurement of the degree of oxidation (DO) of the periodate-oxidized cellulose is not straightforward due to the concomitant side reactions and heterogeneity of the oxidized products. Here, we present a new simple method based on solid-state 13C CP-MAS NMR spectroscopy relying on the quantification of the intricate signals of the washed oxidized sample, using the sharp C1 signal of intact cellulose as an internal standard, allowing the determination of degrees of substitution from 0 to 2. This new NMR method, applied first to microfibrillated cellulose, is compared to the current conventional methods, namely, the UV absorbance monitoring of the periodate consumption and the oxime formation protocol. Agreement between the DONMR and DOUV values can be obtained if one assumes a full oxidation for the solubilized part of the product. Regarding the DO deduced from the oxime formation, it agrees with the present DONMR only if buffered conditions are used during the reaction to prevent hydrolysis. Solid-state NMR experiments also provided information on the heterogeneous character of the reaction in favor of a core–shell model of an oxidized cellulosic material skin surrounding an intact core of unmodified native cellulose. This method could be applied on a wide range of substrates with a different morphology and crystallinity.

    Copyright © 2018 American Chemical Society

    Subjects

    what are subjects

    Keywords

    what are keywords

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.8b03772.

    • Calibration curve of absorbance as a function of the periodate concentration, the NMR spectra superposition protocol for DO calculation by 13C CP-MAS NMR, the 13C CP-MAS NMR spectra of periodate-oxidized MFC series, reconstructed 13C CP-MAS NMR spectra of oxidized MFC, and the relationship between DONMR and the DOtitrations (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 35 publications.

    1. Dengkang Guo, Wenting Ren, Sisi Yao, Jingpeng Li, Yan Yu, Fuxiang Chu. Conversion of Bamboo into Strong, Waterproof, and Biodegradable Thermosetting Plastic through Cell Wall Structure Directed Manipulation. ACS Nano 2024, 18 (35) , 24414-24425. https://doi.org/10.1021/acsnano.4c07148
    2. Kelcilene B. R. Teodoro, Murilo H. M. Facure, Rodrigo Schneider, Augusto D. Alvarenga, Rafaela S. Andre, Daniel S. Correa. Self-Standing Thin Films of Cellulose Nanocrystals and Graphene Quantum Dots for Detection of Trace Iron(III). ACS Applied Nano Materials 2023, 6 (13) , 11561-11571. https://doi.org/10.1021/acsanm.3c01584
    3. Yihua Ren, Libo Zhang, Tao Sun, Yingwu Yin, Qian Wang. Enzyme Immobilization on a Delignified Bamboo Scaffold as a Green Hierarchical Bioreactor. ACS Sustainable Chemistry & Engineering 2022, 10 (19) , 6244-6254. https://doi.org/10.1021/acssuschemeng.2c00346
    4. Yunus Can Gorur, Michael S. Reid, Céline Montanari, Per Tomas Larsson, Per A. Larsson, Lars Wågberg. Advanced Characterization of Self-Fibrillating Cellulose Fibers and Their Use in Tunable Filters. ACS Applied Materials & Interfaces 2021, 13 (27) , 32467-32478. https://doi.org/10.1021/acsami.1c06452
    5. Dimitrios Georgouvelas, Blanca Jalvo, Luis Valencia, Wassilios Papawassiliou, Andrew J. Pell, Ulrica Edlund, Aji P. Mathew. Residual Lignin and Zwitterionic Polymer Grafts on Cellulose Nanocrystals for Antifouling and Antibacterial Applications. ACS Applied Polymer Materials 2020, 2 (8) , 3060-3071. https://doi.org/10.1021/acsapm.0c00212
    6. Julien Leguy, Aminatou Diallo, Jean-Luc Putaux, Yoshiharu Nishiyama, Laurent Heux, Bruno Jean. Periodate Oxidation Followed by NaBH4 Reduction Converts Microfibrillated Cellulose into Sterically Stabilized Neutral Cellulose Nanocrystal Suspensions. Langmuir 2018, 34 (37) , 11066-11075. https://doi.org/10.1021/acs.langmuir.8b02202
    7. Feiyu Tang, BinWang, Jinpeng Li, Jun Xu, Jinsong Zeng, Wenhua Gao, Kefu Chen. Reactive template method for synthesis of water-soluble fluorescent silver nanoclusters supported on the surface of cellulose nanofibers. Carbohydrate Polymers 2025, 352 , 123166. https://doi.org/10.1016/j.carbpol.2024.123166
    8. Emile R. Engel, Giada Lo Re, Per A. Larsson. Melt processing of chemically modified cellulosic fibres with only water as plasticiser: Effects of moisture content and processing temperature. Carbohydrate Polymers 2025, 348 , 122891. https://doi.org/10.1016/j.carbpol.2024.122891
    9. Hampus Karlsson, Leo Svenningsson, Robin Storm, Poppy Chaiyupatham, Anders Brolin, Anette Larsson, Arthur C. Pinon, Staffan Schantz, Leif Karlson, Per A. Larsson, Lars Evenäs. Dynamic nuclear polarization solid-state NMR spectroscopy as a tool to rapidly determine degree of modification in dialcohol cellulose. Cellulose 2024, 31 (18) , 10727-10744. https://doi.org/10.1007/s10570-024-06234-8
    10. Oussama Hamzah, Tom Vandenbrouck, Laurent Heux, Bruno Jean. Insight into the hydrophobic functionalization of cellulose microfibrils using the Passerini three-component reaction. Carbohydrate Polymers 2024, 341 , 122323. https://doi.org/10.1016/j.carbpol.2024.122323
    11. Quanbin Fu, Houshen Li, Mouzhen An, Xin Sun, Shikai Zhang, Tingting Zhang, Wenjing Yang, Yijing Li, Geoffrey I.N. Waterhouse, Xiaonan Liu, Shiyun Ai. Dialdehyde cellulose films covalently crosslinked with porphyrin-based covalent organic polymers for photodynamic sterilization. International Journal of Biological Macromolecules 2024, 272 , 132893. https://doi.org/10.1016/j.ijbiomac.2024.132893
    12. Hicham Aitbella, Larbi Belachemi, Nicolas Merle, Philippe Zinck, Hamid Kaddami. Schiff Base Functionalized Cellulose: Towards Strong Support-Cobalt Nanoparticles Interactions for High Catalytic Performances. Molecules 2024, 29 (8) , 1734. https://doi.org/10.3390/molecules29081734
    13. Laura M. Hillscher, Mark V. Höfler, Torsten Gutmann, Cassia Lux, K. Uta Clerkin, Gerhard Schwall, Klaus Villforth, Samuel Schabel, Markus Biesalski. Influence of TEMPO-oxidation on pulp fiber chemistry, morphology and mechanical paper sheet properties. Cellulose 2024, 31 (5) , 3067-3082. https://doi.org/10.1007/s10570-024-05748-5
    14. Xianqing Lv, Chengke Zhao, Xiwei Zhang, Zhuotong Wu, Li Shuai. Preparation of aldehyde-functionalized cellulose nanocrystals via aerobic oxidation of cellulose in a recyclable triisopropoxy vanadium oxidation system. Green Chemistry 2024, 26 (4) , 1876-1882. https://doi.org/10.1039/D3GC04583H
    15. Jonas Simon, Inge Schlapp‐Hackl, Janak Sapkota, Matti Ristolainen, Thomas Rosenau, Antje Potthast. Towards Tailored Dialdehyde Cellulose Derivatives: A Strategy for Tuning the Glass Transition Temperature. ChemSusChem 2023, 373 https://doi.org/10.1002/cssc.202300791
    16. Jonas Simon, Lukas Fliri, Flavia Fröhlich, Janak Sapkota, Matti Ristolainen, Michael Hummel, Thomas Rosenau, Antje Potthast. Insights into the borohydride reduction of dialdehyde cellulose: the dilemma of competing reduction and β-elimination reactions. Cellulose 2023, 30 (13) , 8205-8220. https://doi.org/10.1007/s10570-023-05350-1
    17. Lukas Fliri, Jonas Simon, Irina Sulaeva, Thomas Rosenau, Antje Potthast, Michael Hummel. Indirect determination of partial depolymerization reactions in dialdehyde celluloses (DAC) by gel permeation chromatography of their oxime derivatives. Cellulose 2023, 30 (14) , 8677-8690. https://doi.org/10.1007/s10570-023-05412-4
    18. Ioana-Georgeta Grosu, Augustin Moț, Xenia Filip, Claudiu Filip. What Is Wrong with Hyaluronic Acid Chemistry? A 15N/13C Solid-State NMR Re-Evaluation of Its Dopamine Conjugates. Polymers 2023, 15 (13) , 2825. https://doi.org/10.3390/polym15132825
    19. Mathieu Nicolas, Anatoli Serghei, Christine Lucas, Emmanuel Beyou, Matthieu Fumagalli. Grafting of polyamines onto periodate oxidized nanocellulose, and its application to the fabrication of ionic nanopapers. Polymer 2023, 270 , 125760. https://doi.org/10.1016/j.polymer.2023.125760
    20. Li Wen Wong, Pooria Pasbakhsh, Wai Teng Cheng, Calvin Bok Sun Goh, Joash Ban Lee Tan. One-pot synthesis of injectable self-healing thermoresponsive halloysite nanotube-reinforced nanocomposite hydrogels for tissue engineering. Applied Clay Science 2023, 232 , 106812. https://doi.org/10.1016/j.clay.2022.106812
    21. Elena Subbotina, Farsa Ram, Sergey V. Dvinskikh, Lars A. Berglund, Peter Olsén. Aqueous synthesis of highly functional, hydrophobic, and chemically recyclable cellulose nanomaterials through oxime ligation. Nature Communications 2022, 13 (1) https://doi.org/10.1038/s41467-022-34697-5
    22. Lili Deng, Baoxiu Wang, Wenying Li, Zhiliang Han, Shiyan Chen, Huaping Wang. Bacterial cellulose reinforced chitosan-based hydrogel with highly efficient self-healing and enhanced antibacterial activity for wound healing. International Journal of Biological Macromolecules 2022, 217 , 77-87. https://doi.org/10.1016/j.ijbiomac.2022.07.017
    23. Ganeswar Dalei, Subhraseema Das, Manoranjan Pradhan. Dialdehyde cellulose as a niche material for versatile applications: an overview. Cellulose 2022, 29 (10) , 5429-5461. https://doi.org/10.1007/s10570-022-04619-1
    24. Ioana A. Duceac, Fulga Tanasa, Sergiu Coseri. Selective Oxidation of Cellulose—A Multitask Platform with Significant Environmental Impact. Materials 2022, 15 (14) , 5076. https://doi.org/10.3390/ma15145076
    25. Abhilash Venkateshaiah, Elmar Sehl, Renee L. Timmins, Stanisław Wacławek, Miroslav Černík, Seema Agarwal, Vinod V. T. Padil. Dialdehyde Modified Tree Gum Karaya: A Sustainable Green Crosslinker for Gelatin‐Based Edible Films. Advanced Sustainable Systems 2022, 6 (6) https://doi.org/10.1002/adsu.202100423
    26. Faezeh Hajiali, Tony Jin, Galen Yang, Madison Santos, Edmond Lam, Audrey Moores. Mechanochemical Transformations of Biomass into Functional Materials. ChemSusChem 2022, 15 (7) https://doi.org/10.1002/cssc.202102535
    27. Shirou Tsuchida, Rina Takahashi, Kurumi Yabe, Naoya Hamaue, Takashi Aoki. A simple method for preparing a diamino cellulose disk from a dialdehyde cellulose disk by reductive amination using 2-picoline-borane. Cellulose 2022, 29 (6) , 3025-3033. https://doi.org/10.1007/s10570-022-04503-y
    28. Jonas Simon, Otgontuul Tsetsgee, Nohman Arshad Iqbal, Janak Sapkota, Matti Ristolainen, Thomas Rosenau, Antje Potthast. A fast method to measure the degree of oxidation of dialdehyde celluloses using multivariate calibration and infrared spectroscopy. Carbohydrate Polymers 2022, 278 , 118887. https://doi.org/10.1016/j.carbpol.2021.118887
    29. Saül Llàcer Navarro, Koyuru Nakayama, Alexander Idström, Lars Evenäs, Anna Ström, Tiina Nypelö. The effect of sulfate half-ester groups on cellulose nanocrystal periodate oxidation. Cellulose 2021, 28 (15) , 9633-9644. https://doi.org/10.1007/s10570-021-04115-y
    30. Mohamed Hasanin, Amr H. Hashem, Ahmed A. El-Rashedy, Samir Kamel. Synthesis of novel heterocyclic compounds based on dialdehyde cellulose: characterization, antimicrobial, antitumor activity, molecular dynamics simulation and target identification. Cellulose 2021, 28 (13) , 8355-8374. https://doi.org/10.1007/s10570-021-04063-7
    31. Hongying Su, Rong Zheng, Linrui Jiang, Ni Zeng, Kun Yu, Yunfei Zhi, Shaoyun Shan. Dextran hydrogels via disulfide-containing Schiff base formation: Synthesis, stimuli-sensitive degradation and release behaviors. Carbohydrate Polymers 2021, 265 , 118085. https://doi.org/10.1016/j.carbpol.2021.118085
    32. Jie Liu, Liru Zhang, Chang Liu, Xuejing Zheng, Keyong Tang. Tuning structure and properties of gelatin edible films through pullulan dialdehyde crosslinking. LWT 2021, 138 , 110607. https://doi.org/10.1016/j.lwt.2020.110607
    33. Abil E. Aliev. Solid state NMR spectroscopy. 2020, 139-187. https://doi.org/10.1039/9781788010665-00139
    34. Asja Pettignano, Julien Leguy, Laurent Heux, Bruno Jean, Aurélia Charlot, Etienne Fleury. Multifunctionalization of cellulose microfibrils through a cascade pathway entailing the sustainable Passerini multi-component reaction. Green Chemistry 2020, 22 (20) , 7059-7069. https://doi.org/10.1039/D0GC02532A
    35. Arianna Lucia, Hendrikus W.G. van Herwijnen, Josua T. Oberlerchner, Thomas Rosenau, Marco Beaumont. Resource‐Saving Production of Dialdehyde Cellulose: Optimization of the Process at High Pulp Consistency. ChemSusChem 2019, 12 (20) , 4679-4684. https://doi.org/10.1002/cssc.201901885
    Download PDF
    Go to ACS Sustainable Chemistry & Engineering
    Get e-Alerts
    Get e-Alerts

    ACS Sustainable Chemistry & Engineering

    Cite this: ACS Sustainable Chem. Eng. 2019, 7, 1, 412–420
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acssuschemeng.8b03772
    Published November 3, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Article Views

    1587

    Altmetric

    -

    Citations

    35
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.