Tectonic arrangement of BaCO3 nanocrystals into helices induced by a racemic block copolymer

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Abstract

Morphosynthesis strategies inspired by biomineralization processes gives access to a wide range of fascinating and useful crystalline mesostructures1,2,3. Biomimetic synthesis of inorganic materials with complex shapes can now be used to control the nucleation, tensorial growth, and alignment of inorganic crystals in a way previously not practicable3. Double hydrophilic block copolymers (DHBCs)4 consisting of a hydrophilic block strongly interacting with inorganic minerals, and a non-interacting hydrophilic block, were recently introduced for the control of mineralization reactions. DHBCs are 'improved versions' of the previously used polyelectrolytes or amphiphiles and are extraordinarily effective in crystallization control5,6,7,8,9. Here, we report on the formation of helices of achiral BaCO3 nanocrystals in the presence of a racemic DHBC suggesting that a helical alignment can be induced by racemic polymers through selective adsorption on the (110) face of nanocrystals. This mechanism is the key for a better understanding of the self-assembly of chiral organic–inorganic superstructures that don't follow a direct template route.

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Figure 1: Chemical structure of PEG-b-DHPOBAEE.
Figure 2: Helical nanoparticle superstructures.
Figure 3: Change of helical pitch.
Figure 4: Proposed mechanism leading to spontaneous helix formation.

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Acknowledgements

We thank the Max Planck Gesellschaft and the Deutsche Forschungsgemeinschaft for financial support. S. H. Yu thanks the special funding support from the Chinese Academy of Sciences the Distinguished Youth and Team Funds from the National Science Foundation of China (No. 20325104, No. 20321101), and NSFC No. 50372065, AvH Foundation, and Max Planck Society). The authors thank the Ivoclar AG (Schaan, Liechtenstein) for the gift of the (2-[4-dihydroxy phosphoryl]-2-oxabutyl) monomer. A. Völkel is acknowledged for the ultracentrifuge experiments.

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Correspondence to Shu-Hong Yu or Helmut Cölfen or Markus Antonietti.

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The authors declare no competing financial interests.

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Fig S1, Fig S2, Fig S3, Fig S4, Fig S5, Fig S6 (PDF 505 kb)

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Yu, S., Cölfen, H., Tauer, K. et al. Tectonic arrangement of BaCO3 nanocrystals into helices induced by a racemic block copolymer. Nature Mater 4, 51–55 (2005) doi:10.1038/nmat1268

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