We have studied the simultaneous synthesis and morphogenesis of polymer materials with hierarchical structures from nanoscopic to macroscopic scales. The morphologies of the original materials can be replicated to the polymer materials. In general, it is not easy to achieve the simultaneous synthesis and morphogenesis of polymer material even using host materials. In the present work, four biominerals and three biomimetic mesocrystal structures are used as the host materials or templates and polypyrrole, poly(3-hexylthiopehene), and silica were used as the precursors for the simultaneous syntheses and morphogenesis of polymer materials. The host materials with the hierarchical structure possess the nanospace for the incorporation of the monomers. After the incorporation of the monomers, the polymerization reaction proceeds in the nanospace with addition of the initiator agents. Then, the dissolution of the host materials leads to the formation and morphogenesis of the polymer materials. The scheme of the replication can be classified into the three types based on the structures of the host materials (types I-III). The type I template facilitates the hierarchical replication of the whole host material, type II mediates the hierarchical surface replication, and type III induces the formation of the two-dimensional nanosheets. Based on these results, the approach for the coupled synthesis and morphogenesis can be applied to a variety of combinations of the templates and polymer materials.

The processes for the synthesis of polymers in a mesocrystal structure were studied for understanding of the mechanisms. The mesocrystal structure has the nanoscale pores between the unit crystals for incorporation of guest molecules. The monomers can be incorporated and polymerized in the nanospace of the mesocrystals. In the present work, a sea urchin spine and poly(3,4-ethylenedioxythiophene) (PEDOT) were adopted as a model of the original mesocrystal and replicated polymer material, respectively. A sea urchin spine, as an original material, has the hierarchical architectures based on the mesocrystal structure consisting of the oriented carbonate nanocrystals. The monomers were introduced in the nanoscale pores. The composite of the original carbonate and PEDOT was obtained after the incorporation and the polymerization. After dissolution of the original carbonate, the resultant PEDOT architecture showed the hierarchical morphologies similar to those of the original sea urchin spine. The morphology replication processes were compared with those of the different polymers. The important factors for the morphology replication are studied. The present work suggests that the approach can be applied to morphogenesis of a variety of polymer materials.

Oriented nanocrystals, as seen in biominerals, have both the macroscopic hierarchical morphologies and the nanoscale interspace among the unit crystals. Here we studied the incorporation effects of the specific interspace in the oriented nanocrystals on the morphologies, properties, and applications of organic crystals. Organic crystals, such as 9-vinylcarbazole (VCz), azobenzene (AB), and pyrene (PY), were introduced into the specific interspace of oriented nanocrystals from the melts. The morphologies and properties of the incorporated organic crystals were systematically studied in these model cases. The incorporation of the organic crystals provided the composites with the original oriented nanocrystals. The incorporated organic crystals formed the single-crystalline structures even in the nanoscale interspace. The melts of the organic compounds were crystallized and grown in the interspace of the original materials. The incorporated organic crystals showed the specific phase transition behavior. The freezing points of the organic crystals were raised by the incorporation into the nanospace while the melting points were not changed. The hierarchical morphologies of the organic crystals were obtained after the dissolution of the original materials. The hierarchical morphologies of the original materials were replicated to the organic crystals. The incorporated organic crystal was polymerized without deformation of the hierarchical morphologies. The hierarchical polymer can be applied to the donor material for the generation of a larger amount of the charge-transfer complex with the acceptor molecule than the commercial polymer microparticles. The present work shows the potential use of the nanoscale interspace generated in the oriented nanocrystals.

Simultaneous synthesis and morphogenesis of polymer materials are achieved through the replication by using mesocrsytals in biological and biomimetic architectures as the host materials. Mesocrystalline structures have nanoscopic space within the interspace of the unit crystals. Introduction of monomers and subsequent polymerization in the nanospace affords the synthesis and morphogenesis of polymer materials. The polymer architectures are formed after dissolution of the original host mesocrystals. For more information see the Full Paper by Y. Oaki, H. Imai et al. on