Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Free-standing mesoporous silica films with tunable chiral nematic structures

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.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Figure 1: Schematic of the chiral nematic ordering of NCC crystallites and POM images.
Figure 2: Optical characterization of NCC/silica composite films and the corresponding mesoporous silica films.
Figure 3: Nitrogen and water absorption in a chiral mesoporous silica film.
Figure 4: SEM images of chiral nematic mesoporous silica films and comparison of fingerprint textures in the solid state and liquid crystal phase.

References

  1. Johnson, L. N. Asymmetry at the molecular level in biology. Eur. Rev. 13, 77–95 (2005)

    Article  Google Scholar 

  2. 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)

    CAS  Article  Google Scholar 

  3. Johnson, B. F. G. et al. Superior performance of a chiral catalyst confined within mesoporous silica. Chem. Commun. 1167–1168 (1999)

  4. Fireman-Shoresh, S., Popov, I., Avnir, D. & Marx, S. Enantioselective, chirally templated sol-gel thin films. J. Am. Chem. Soc. 127, 2650–2655 (2005)

    CAS  Article  Google Scholar 

  5. Hodgkinson, I. & Wu, Q. H. Inorganic chiral optical materials. Adv. Mater. 13, 889–897 (2001)

    CAS  Article  Google Scholar 

  6. 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)

    CAS  ADS  Article  Google Scholar 

  7. 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)

    CAS  ADS  Article  Google Scholar 

  8. 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)

    CAS  ADS  Article  Google Scholar 

  9. Armatas, G. S. & Kanatzidis, M. G. Hexagonal mesoporous germanium. Science 313, 817–820 (2006)

    CAS  ADS  Article  Google Scholar 

  10. 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)

    CAS  ADS  Article  Google Scholar 

  11. Sun, D. et al. Hexagonal nanoporous germanium through surfactant-driven self-assembly of Zintl clusters. Nature 441, 1126–1130 (2006)

    CAS  ADS  Article  Google Scholar 

  12. 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)

    CAS  ADS  Article  Google Scholar 

  13. Che, S. et al. Synthesis and characterization of chiral mesoporous silica. Nature 429, 281–284 (2004)

    CAS  ADS  Article  Google Scholar 

  14. 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)

    CAS  Article  Google Scholar 

  15. 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)

    CAS  ADS  Article  Google Scholar 

  16. 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)

    CAS  ADS  Article  Google Scholar 

  17. 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)

    CAS  ADS  Article  Google Scholar 

  18. Akagi, K. et al. Helical polyacetylene synthesized with a chiral nematic reaction field. Science 282, 1683–1686 (1998)

    CAS  ADS  Article  Google Scholar 

  19. Sharma, V., Cme, M., Park, J. O. & Srinivasarao, M. Structural origin of circularly polarized iridescence in jeweled beetles. Science 325, 449–451 (2009)

    CAS  ADS  Article  Google Scholar 

  20. 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)

    CAS  Article  Google Scholar 

  21. 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)

    CAS  Article  Google Scholar 

  22. 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)

    CAS  Google Scholar 

  23. 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)

    CAS  Article  Google Scholar 

  24. 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)

    CAS  Article  Google Scholar 

  25. Edgar, C. D. & Gray, D. G. Induced circular dichroism of chiral nematic cellulose films. Cellulose 8, 5–12 (2001)

    CAS  Article  Google Scholar 

  26. De Vries, H. L. Rotatory power and other optical properties of certain liquid crystals. Acta Crystallogr. 4, 219–226 (1951)

    CAS  Article  Google Scholar 

  27. 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)

    CAS  Article  Google Scholar 

  28. 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)

    CAS  ADS  Article  Google Scholar 

Download references

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.

Author information

Authors and Affiliations

Authors

Contributions

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.

Corresponding author

Correspondence to Mark J. MacLachlan.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Figures 1-9 with legends, Supplementary Tables 1-2 and a Supplementary Discussion. (PDF 1292 kb)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature09540

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing