Abstract
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 properties1. 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 materials2,3,4,5. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures6,7,8,9,10,11,12, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant13,14. 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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References
Johnson, L. N. Asymmetry at the molecular level in biology. Eur. Rev. 13, 77–95 (2005)
Gabashvili, A., Medina, D. D., Gedanken, A. & Mastai, Y. Templating mesoporous silica with chiral block copolymers and its application for enantioselective separation. J. Phys. Chem. B 111, 11105–11110 (2007)
Johnson, B. F. G. et al. Superior performance of a chiral catalyst confined within mesoporous silica. Chem. Commun. 1167–1168 (1999)
Fireman-Shoresh, S., Popov, I., Avnir, D. & Marx, S. Enantioselective, chirally templated sol-gel thin films. J. Am. Chem. Soc. 127, 2650–2655 (2005)
Hodgkinson, I. & Wu, Q. H. Inorganic chiral optical materials. Adv. Mater. 13, 889–897 (2001)
Kresge, C. T., Leonowicz, M. E., Roth, W. J., Vartuli, J. C. & Beck, J. S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359, 710–712 (1992)
Yang, P., Zhao, D., Margolese, D. I., Chmelka, B. F. & Stucky, G. D. Generalized syntheses of large-pore meosporous metal oxides with semicrystalline frameworks. Nature 396, 152–155 (1998)
Yang, H., Coombs, N., Sokolov, I. & Ozin, G. A. Free-standing and oriented mesoporous silica films grown at the air–water interface. Nature 381, 589–592 (1996)
Armatas, G. S. & Kanatzidis, M. G. Hexagonal mesoporous germanium. Science 313, 817–820 (2006)
Inagaki, S., Guan, S., Ohsuna, T. & Terasaki, O. An ordered mesoporous organosilica hybrid material with a crystal-like wall structure. Nature 416, 304–307 (2002)
Sun, D. et al. Hexagonal nanoporous germanium through surfactant-driven self-assembly of Zintl clusters. Nature 441, 1126–1130 (2006)
Attard, G. S., Glyde, J. C. & Göltner, C. G. Liquid-crystalline phases as templates for the synthesis of mesoporous silica. Nature 378, 366–368 (1995)
Che, S. et al. Synthesis and characterization of chiral mesoporous silica. Nature 429, 281–284 (2004)
Qiu, H., Inoue, Y. & Che, S. Supramolecular chiral transcription and recognition by mesoporous silica prepared by chiral imprinting of a helical micelle. Angew. Chem. Int. Ed. 48, 3069–3072 (2009)
Broer, D. J., Lub, J. & Mol, G. N. Wide-band reflective polarizers from cholesteric polymer networks with a pitch gradient. Nature 378, 467–469 (1995)
Yang, D.-K., West, J. L., Chien, L.-C. & Doane, J. W. Control of reflectivity and bistability in displays using cholesteric liquid crystals. J. Appl. Phys. 76, 1331–1333 (1994)
Kopp, V. I., Fan, B., Vithana, H. K. M. & Genack, A. Z. Low-threshold lasing at the edge of a photonic stop band in cholesteric liquid crystals. Opt. Lett. 23, 1707–1709 (1998)
Akagi, K. et al. Helical polyacetylene synthesized with a chiral nematic reaction field. Science 282, 1683–1686 (1998)
Sharma, V., Cme, M., Park, J. O. & Srinivasarao, M. Structural origin of circularly polarized iridescence in jeweled beetles. Science 325, 449–451 (2009)
Mukherjee, S. M. & Woods, H. J. X-ray and electron microscope studies of the degradation of cellulose by sulphuric acid. Biochim. Biophys. Acta 10, 499–511 (1953)
Revol, J.-F., Bradford, H., Giasson, J., Marchessault, R. H. & Gray, D. G. Helicoidal self-ordering of cellulose microfibrils in aqueous suspension. Int. J. Biol. Macromol. 14, 170–172 (1992)
Revol, J.-F., Godbout, L. & Gray, D. G. Solid self-assembled films of cellulose with chiral nematic order and optically variable properties. J. Pulp Pap. Sci. 24, 146–149 (1998)
Dujardin, E., Blaseby, M. & Mann, S. Synthesis of mesoporous silica by sol-gel mineralisation of cellulose nanorod nematic suspensions. J. Mater. Chem. 13, 696–699 (2003)
Thomas, A. & Antonietti, M. Silica nanocasting of simple cellulose derivatives: towards chiral pore systems with long-range order and chiral optical coatings. Adv. Funct. Mater. 13, 763–766 (2003)
Edgar, C. D. & Gray, D. G. Induced circular dichroism of chiral nematic cellulose films. Cellulose 8, 5–12 (2001)
De Vries, H. L. Rotatory power and other optical properties of certain liquid crystals. Acta Crystallogr. 4, 219–226 (1951)
Dong, X. M., Kimura, T., Revol, J.-F. & Gray, D. G. Effects of ionic strength on the isotropic-chiral nematic phase transition of suspensions of cellulose crystallites. Langmuir 12, 2076–2082 (1996)
Robbie, K., Broer, D. J. & Brett, M. J. Chiral nematic order in liquid crystals imposed by an engineered inorganic nanostructure. Nature 399, 764–766 (1999)
Acknowledgements
This work was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada and FPInnovations. K.E.S. is grateful to UBC for a graduate fellowship.
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K.E.S. conducted all of the synthesis and most of the characterization. H.Q. assisted with characterization of the materials. W.Y.H. supplied the NCC and contributed valuable expertise on NCC. M.J.M. initiated and guided this work.
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The file contains Supplementary Figures 1-9 with legends, Supplementary Tables 1-2 and a Supplementary Discussion. (PDF 1292 kb)
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Shopsowitz, K., Qi, H., Hamad, W. et al. Free-standing mesoporous silica films with tunable chiral nematic structures. Nature 468, 422–425 (2010). https://doi.org/10.1038/nature09540
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DOI: https://doi.org/10.1038/nature09540
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