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Green Templating of Ultraporous Cross-Linked Cellulose Nanocrystal Microparticles

  • Daniel Levin
    Daniel Levin
    Department of Chemistry and Chemical Biology, McMaster University, 1280 Main St. W., Hamilton, Ontario L8S 4M1 Canada
    More by Daniel Levin
  • Sokunthearath Saem
    Sokunthearath Saem
    Department of Chemistry and Chemical Biology, McMaster University, 1280 Main St. W., Hamilton, Ontario L8S 4M1 Canada
  • Daniel A. Osorio
    Daniel A. Osorio
    Department of Chemical Engineering, McMaster University, Hamilton, Ontario L8S 4M1, Canada
  • Aline Cerf
    Aline Cerf
    LAAS-CNRS, Université de Toulouse, CNRS, INSA, UPS, 7 Avenue du Colonel Roche, 31400 Toulouse, France
    More by Aline Cerf
  • Emily D. Cranston
    Emily D. Cranston
    Department of Chemical Engineering, McMaster University, Hamilton, Ontario L8S 4M1, Canada
  • , and 
  • Jose M. Moran-Mirabal*
    Jose M. Moran-Mirabal
    Department of Chemistry and Chemical Biology, McMaster University, 1280 Main St. W., Hamilton, Ontario L8S 4M1 Canada
    *E-mail: [email protected]
Cite this: Chem. Mater. 2018, 30, 21, 8040–8051
Publication Date (Web):October 12, 2018
https://doi.org/10.1021/acs.chemmater.8b03858
Copyright © 2018 American Chemical Society
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Abstract

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Cellulose nanocrystals (CNCs) are rigid rodlike nanoparticles that are derived from natural cellulose. Their high surface area, mechanical strength, and noncytotoxicity have elicited interest in their use for various applications, including composite and construction materials, cosmetic, food, and biomedical products. However, few methods exist to control the morphology and dimensions of assembled CNC structures in the micrometer range. Here, we use water-in-oil droplet microfluidics to template uniform spherical CNC droplets in a nontoxic and sustainable manner. Subsequent evaporation of the water within the droplets promotes the chemical cross-linking of surface-modified CNCs, resulting in ultraporous and flexible micrometer-sized particles. Changing the size of the microfluidic channel or the concentration of the CNC suspension results in microparticles with tunable sizes. The microparticles swell in polar solvents, with larger swelling observed for microparticles fabricated from less-concentrated CNC suspensions. While swelling is pH-independent, it is impacted by ionic strength for microparticles with low cross-link densities. Scanning electron microscopy reveals that the microparticles have macropores and mesopores, supporting a large specific surface area. These porous microparticles have potential for a range of applications, such as drug delivery or sorption agents, or as biodegradable beads for use in cosmetic and food applications.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b03858.

  • Polarized optical microscopy images of sCNC microparticle formation; epifluorescence and confocal images of MP-0.3 and MP-3 microparticles; quantification of batch-to-batch reproducibility of microparticle swelling; physicochemical properties of sulfuric acid hydrolyzed and chemically modified (cross-linkable) CNCs; representative atomic force microscopy height images of sCNCs (PDF)

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Cited By


This article is cited by 5 publications.

  1. Tyler Or, Sokunthearath Saem, Aurore Esteve, Daniel A. Osorio, Kevin J. De France, Jaana Vapaavuori, Todd Hoare, Aline Cerf, Emily D. Cranston, Jose M. Moran-Mirabal. Patterned Cellulose Nanocrystal Aerogel Films with Tunable Dimensions and Morphologies as Ultra-Porous Scaffolds for Cell Culture. ACS Applied Nano Materials 2019, 2 (7) , 4169-4179. https://doi.org/10.1021/acsanm.9b00640
  2. Fusheng Zhang, Dongdong Wang, Haijuan Qin, Liang Feng, Xinmiao Liang, Guangyan Qing. Chemoselectivity of Pristine Cellulose Nanocrystal Films Driven by Carbohydrate–Carbohydrate Interactions. ACS Applied Materials & Interfaces 2019, 11 (14) , 13114-13122. https://doi.org/10.1021/acsami.9b00471
  3. Yishan Kuang, Xia Li, Pengcheng Luan, Xi Zhang, Jun Xu, Lihuan Mo, Jie Gong, Jun Li. Cellulose II nanocrystal: a promising bio-template for porous or hollow nano SiO2 fabrication. Cellulose 2020, 27 (6) , 3167-3179. https://doi.org/10.1007/s10570-020-02973-6
  4. Filipe V. Ferreira, Caio G. Otoni, Kevin J. De France, Hernane S. Barud, Liliane M.F. Lona, Emily D. Cranston, Orlando J. Rojas. Porous nanocellulose gels and foams: Breakthrough status in the development of scaffolds for tissue engineering. Materials Today 2020, https://doi.org/10.1016/j.mattod.2020.03.003
  5. Hyeong Chan Nam, Won Ho Park. Eco-friendly poly(lactic acid) microbeads for cosmetics via melt electrospraying. International Journal of Biological Macromolecules 2019, https://doi.org/10.1016/j.ijbiomac.2019.11.240

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