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

NATURE MATERIALS, no. 1 (2005): 51-U5

Cited by: 299|Views16
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Abstract

Morphosynthesis strategies inspired by biomineralization processes gives access to a wide range of fascinating and useful crystalline mesostructures. 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 pract...More

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Introduction
  • Chiral mineralized structures as found in marine and snail shells have attracted intense interest for a long time.
  • A helical superstructure of CaCO3 particles with micrometre size was occasionally observed by Gower et al.[16] using chiral as well as achiral polyaspartate additives, the origin of these polycrystalline structures is not yet well understood.
Highlights
  • Chiral mineralized structures as found in marine and snail shells have attracted intense interest for a long time
  • We report on the formation of helices of achiral BaCO3 nanocrystals in the presence of a racemic Double hydrophilic block copolymers (DHBCs) suggesting that a helical alignment can be induced by racemic polymers through selective adsorption on the (110) face of nanocrystals
  • Current synthesis approaches for these unusual helical structures mainly rely on the direct templating effect from some specific supramolecular nanoribbons[11], screw dislocations[12], transcription from chiral gelators[14] or in an unknown way from chiral acidic polypeptides[15]
  • Molecular modelling suggests a straight, but non-helical structure with the phosphonate groups predominately located on one side of the molecule (Supplementary Information, Fig. S1)
  • A herringbone-like supracrystalline packing motif (Fig. 2b centre) results in a straight and non-helical structure, which could be explained by aggregation/attachment of primary orthorhombic particles in a less favourable but probable way (Supplementary nature materials | VOL 4 | JANUARY 2005 | www.nature.com/naturematerials a (020)
  • Molecular modelling of the functional polymer block reveals a stiff structure with the functional groups located predominantly on one side, with a distance of the phosphonate moieties fitting to the (110) carbonate packing motif (Supplementary Information, Fig. S1)
Results
  • Molecular modelling suggests a straight, but non-helical structure with the phosphonate groups predominately located on one side of the molecule (Supplementary Information, Fig. S1).
  • It has to be pointed out that the structural dimensions of the observed inorganic helices are a magnitude bigger than the molecular dimension of an eventually formed block copolymer helix so that a direct polymer template effect can be excluded.
  • It is noteworthy to stress that most of the elongated primary crystals have to be aligned in an almost parallel fashion, as otherwise a helix structure would be significantly disturbed, the alignment is not perfect (Supplementary Information, Fig. S4b,c).
  • A herringbone-like supracrystalline packing motif (Fig. 2b centre) results in a straight and non-helical structure, which could be explained by aggregation/attachment of primary orthorhombic particles in a less favourable but probable way (Supplementary nature materials | VOL 4 | JANUARY 2005 | www.nature.com/naturematerials a (020)
  • The calculated detailed surface patterns of the cleavage planes (Supplementary Information, Fig. S5) show that the positive (110) faces are favourable for the adsorption of the negative phosphonated block copolymer.
  • Molecular modelling of the functional polymer block reveals a stiff structure with the functional groups located predominantly on one side, with a distance of the phosphonate moieties fitting to the (110) carbonate packing motif (Supplementary Information, Fig. S1).
  • Branching of the helix, which would be possible according to Fig. 4, is not observed as a result of the fast helix growth, depleting the regions parallel to the helix axis of building units so that primary particle attachment takes place at the helix tips.
  • At increased starting pH and the related lower overall charge of the nanocrystals, the helices become dense and stiff (Fig. 3a), indicating that particle attachment prevails over polymer adsorption.
Conclusion
  • Increasing the polymer concentration and adjusting to starting pH 4 leads to the reverse process, the lateral growth is restricted, and only short parallel arranged fibre bundles are formed (Fig. 3b and Supplementary Information, Fig. S4d).
  • On the mesoscale, new modes of spontaneous symmetry breaking, as non-homogeneous polymer adsorption, can obviously be activated, generating chiral contributions in the mutual interaction potentials of the building blocks.
Summary
  • Chiral mineralized structures as found in marine and snail shells have attracted intense interest for a long time.
  • A helical superstructure of CaCO3 particles with micrometre size was occasionally observed by Gower et al.[16] using chiral as well as achiral polyaspartate additives, the origin of these polycrystalline structures is not yet well understood.
  • Molecular modelling suggests a straight, but non-helical structure with the phosphonate groups predominately located on one side of the molecule (Supplementary Information, Fig. S1).
  • It has to be pointed out that the structural dimensions of the observed inorganic helices are a magnitude bigger than the molecular dimension of an eventually formed block copolymer helix so that a direct polymer template effect can be excluded.
  • It is noteworthy to stress that most of the elongated primary crystals have to be aligned in an almost parallel fashion, as otherwise a helix structure would be significantly disturbed, the alignment is not perfect (Supplementary Information, Fig. S4b,c).
  • A herringbone-like supracrystalline packing motif (Fig. 2b centre) results in a straight and non-helical structure, which could be explained by aggregation/attachment of primary orthorhombic particles in a less favourable but probable way (Supplementary nature materials | VOL 4 | JANUARY 2005 | www.nature.com/naturematerials a (020)
  • The calculated detailed surface patterns of the cleavage planes (Supplementary Information, Fig. S5) show that the positive (110) faces are favourable for the adsorption of the negative phosphonated block copolymer.
  • Molecular modelling of the functional polymer block reveals a stiff structure with the functional groups located predominantly on one side, with a distance of the phosphonate moieties fitting to the (110) carbonate packing motif (Supplementary Information, Fig. S1).
  • Branching of the helix, which would be possible according to Fig. 4, is not observed as a result of the fast helix growth, depleting the regions parallel to the helix axis of building units so that primary particle attachment takes place at the helix tips.
  • At increased starting pH and the related lower overall charge of the nanocrystals, the helices become dense and stiff (Fig. 3a), indicating that particle attachment prevails over polymer adsorption.
  • Increasing the polymer concentration and adjusting to starting pH 4 leads to the reverse process, the lateral growth is restricted, and only short parallel arranged fibre bundles are formed (Fig. 3b and Supplementary Information, Fig. S4d).
  • On the mesoscale, new modes of spontaneous symmetry breaking, as non-homogeneous polymer adsorption, can obviously be activated, generating chiral contributions in the mutual interaction potentials of the building blocks.
Funding
  • We thank the Max Planck Gesellschaft and the Deutsche Forschungsgemeinschaft for financial support
  • 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)
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