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Synthesis and characterization of chiral mesoporous silica

Abstract

Chirality is widely expressed in organic materials, perhaps most notably in biological molecules such as DNA, and in proteins, owing to the homochirality of their components (d-sugars and l-amino acids). But the occurrence of large-scale chiral pores in inorganic materials is rare1. Although some progress has been made in strategies to synthesize helical and chiral zeolite-like materials1,2,3, the synthesis of enantiomerically pure mesoporous materials is a challenge that remains unsolved4. Here we report the surfactant-templated synthesis of ordered chiral mesoporous silica, together with a general approach for the structural analysis of chiral mesoporous crystals by electron microscopy. The material that we have synthesized has a twisted hexagonal rod-like morphology, with diameter 130–180 nm and length 1–6 µm. Transmission electron microscopy combined with computer simulations confirm the presence of hexagonally ordered chiral channels of 2.2 nm diameter winding around the central axis of the rods. Our findings could lead to new uses for mesoporous silica and other chiral pore materials in, for example, catalysis and separation media, where both shape selectivity and enantioselectivity5 can be applied to the manufacturing of enantiomerically pure chemicals and pharmaceuticals.

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Figure 1: Schematic illustration of the two types of interaction between the head group of C14-l-AlaS, its free amino acid C14-l-AlaA and amino groups.
Figure 2: XRD pattern of calcined chiral mesoporous silica, indicating the hexagonal order.
Figure 3: SEM image and schematic drawings of a structural model of chiral mesoporous silica.
Figure 4: TEM images of chiral mesoporous silica.
Figure 5: Schematic drawing of chiral mesoporous silica, its TEM image and the computer-simulated TEM image.

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Acknowledgements

This work was partially supported by Core Research for Evolutional Science and Technology (CREST) of JST Corporation, and by the Swedish Research Council (VR). S.C. thanks the Japan Society for the Promotion of Science for a postdoctoral fellowship to start this work at Yokohama National University.

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Correspondence to Shunai Che.

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The authors declare that they have no competing financial interests.

Supplementary information

Supplementary Figure 1

Adsorption and desorption isotherms of nitrogen and pore size distribution of chiral mesoporous silica. (JPG 27 kb)

Supplementary Figure 2

The TEM images and schematic drawing of the chiral channels into which Co and Pt were inserted. (JPG 59 kb)

Supplementary Figure 3

CD spectra of synthesis gel of chiral mesoporous silica. (JPG 18 kb)

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Che, S., Liu, Z., Ohsuna, T. et al. Synthesis and characterization of chiral mesoporous silica. Nature 429, 281–284 (2004). https://doi.org/10.1038/nature02529

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