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      Structure and transformation of tactoids in cellulose nanocrystal suspensions

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      Nature Communications
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          Abstract

          Cellulose nanocrystals obtained from natural sources are of great interest for many applications. In water, cellulose nanocrystals form a liquid crystalline phase whose hierarchical structure is retained in solid films after drying. Although tactoids, one of the most primitive components of liquid crystals, are thought to have a significant role in the evolution of this phase, they have evaded structural study of their internal organization. Here we report the capture of cellulose nanocrystal tactoids in a polymer matrix. This method allows us to visualize, for the first time, the arrangement of cellulose nanocrystals within individual tactoids by electron microscopy. Furthermore, we can follow the structural evolution of the liquid crystalline phase from tactoids to iridescent-layered films. Our insights into the early nucleation events of cellulose nanocrystals give important information about the growth of cholesteric liquid crystalline phases, especially for cellulose nanocrystals, and are crucial for preparing photonics-quality films.

          Abstract

          Cellulose nanocrystals suspensions self-assemble into cholesteric liquid crystalline droplets, namely tactoids, which then condense into helical structures upon drying. Here, Wang et al. capture the structural evolution of this nucleation process by trapping and protecting tactoids in a polymer matrix.

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          Helicoidal self-ordering of cellulose microfibrils in aqueous suspension.

          In many skeletal support systems of plants and animals, cellulose, chitin, and collagen occur in the form of microfibrils ordered in a chiral nematic fashion (helicoids). However, these structures remain poorly understood due to the many constituents present in biological tissues. Here we report an in vitro system that attracts by its simplicity. Only one chemical component, cellulose, is present in the form of fibrillar fragments dispersed in water. Above a critical concentration the colloidal dispersion separates spontaneously into a chiral nematic liquid crystalline phase. On drying this phase solidifies into regularly twisted fibrillar layers that mimic the structural organization of helicoids in nature.
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            The shape and size distribution of crystalline nanoparticles prepared by acid hydrolysis of native cellulose.

            The shape and size distribution of crystalline nanoparticles resulting from the sulfuric acid hydrolysis of cellulose from cotton, Avicel, and tunicate were investigated using transmission electron microscopy (TEM) and atomic force microscopy (AFM) as well as small- and wide-angle X-ray scattering (SAXS and WAXS). Images of negatively stained and cryo-TEM specimens showed that the majority of cellulose particles were flat objects constituted by elementary crystallites whose lateral adhesion was resistant against hydrolysis and sonication treatments. Moreover, tunicin whiskers were described as twisted ribbons with an estimated pitch of 2.4-3.2 microm. Length and width distributions of all samples were generally well described by log-normal functions, with the exception of tunicin, which had less lateral aggregation. AFM observation confirmed that the thickness of the nanocrystals was almost constant for a given origin and corresponded to the crystallite size measured from peak broadening in WAXS spectra. Experimental SAXS profiles were numerically simulated, combining the dimensions and size distribution functions determined by the various techniques.
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              Free-standing mesoporous silica films with tunable chiral nematic structures.

              Chirality at the molecular level is found in diverse biological structures, such as polysaccharides, proteins and DNA, and is responsible for many of their unique properties. Introducing chirality into porous inorganic solids may produce new types of materials that could be useful for chiral separation, stereospecific catalysis, chiral recognition (sensing) and photonic materials. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant. Efforts to impart chirality at a larger length scale using self-assembly are almost unknown. Here we describe the development of a photonic mesoporous inorganic solid that is a cast of a chiral nematic liquid crystal formed from nanocrystalline cellulose. These materials may be obtained as free-standing films with high surface area. The peak reflected wavelength of the films can be varied across the entire visible spectrum and into the near-infrared through simple changes in the synthetic conditions. To the best of our knowledge these are the first materials to combine mesoporosity with long-range chiral ordering that produces photonic properties. Our findings could lead to the development of new materials for applications in, for example, tuneable reflective filters and sensors. In addition, this type of material could be used as a hard template to generate other new materials with chiral nematic structures.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                04 May 2016
                2016
                : 7
                : 11515
                Affiliations
                [1 ]Department of Chemistry, University of British Columbia , 2036 Main Mall, Vancouver, British Columbia, Canada V6T 1Z1
                [2 ]FPInnovations , 2665 East Mall, Vancouver, British Columbia, Canada V6T 1Z4
                Author notes
                Author information
                http://orcid.org/0000-0003-0683-4818
                Article
                ncomms11515
                10.1038/ncomms11515
                4857480
                27143197
                b8d11113-eacb-49ed-b176-a37282efa600
                Copyright © 2016, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 18 December 2015
                : 31 March 2016
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