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1.  Controlled synthesis and tunable properties of ultrathin silica nanotubes through spontaneous polycondensation on polyamine fibrils 
Summary
This paper describes a facile approach to a biomimetic rapid fabrication of ultrathin silica nanotubes with a highly uniform diameter of 10 nm and inner hollow of around 3 nm. The synthesis is carried out through a spontaneous polycondensation of alkoxysilane on polyamine crystalline fibrils that were conveniently produced from the neutralization of a solution of protonated linear polyethyleneimine (LPEI–H+) by alkali compounds. A simple mixing the fibrils with alkoxysilane in aqueous solution allowed for the rapid formation of silica to produce LPEI@silica hybrid nanotubes. These 10-nm nanotubes were hierarchically organized in a mat-like morphology with a typical size of 1–2 micrometers. The subsequent removal of organic LPEI via calcination resulted in silica nanotubes that keep this morphology. The morphology, the structure, the pore properties and the formation mechanism of the silica nanotubes were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller measurements (BET), and X-ray diffraction (XRD). Detailed studies demonstrated that the formation of the nanotubes depends on the molar ratio of [OH]/[CH2CH2NH] during the neutralization as well as on the basicity of the alkali compound and on the concentration of the silica source. The synthesis of silica nanotubes established here could be easily applied to a fabrication on the kilogram scale. Silica nanotubes that were obtained from the calcination of hybrid nanotubes of LPEI@silica in an N2 atmosphere showed a distinct photoluminescence centered at 540 nm with a maximum excitation wavelength of 320 nm. Furthermore, LPEI@silica hybrid nanotubes were applied to create silica–carbon composite nanotubes by alternative adsorption of ionic polymers and subsequent carbonization.
doi:10.3762/bjnano.4.90
PMCID: PMC3869340  PMID: 24367748
biomimetic silicification; polyethyleneimine; silica–carbon nanocomposite; silica nanotubes; template synthesis
2.  Approaches to nanostructure control and functionalizations of polymer@silica hybrid nanograss generated by biomimetic silica mineralization on a self-assembled polyamine layer 
Summary
We report the rational control of the nanostructure and surface morphology of a polyamine@silica nanoribbon-based hybrid nanograss film, which was generated by performing a biomimetic silica mineralization reaction on a nanostructured linear polyethyleneimine (LPEI) layer preorganized on the inner wall of a glass tube. We found that the film thickness, size and density of the nanoribbons and the aggregation/orientation of the nanoribbons in the film were facile to tune by simple adjustment of the biomimetic silicification conditions and LPEI self-assembly on the substrate. Our LPEI-mediated nanograss process allows the facile and programmable generation of a wide range of nanostructures and surface morphologies without the need for complex molecular design or tedious techniques. This ribbon-based nanograss has characteristics of a LPEI@silica hybrid structure, suggesting that LPEI, as a polymeric secondary amine, is available for subsequent chemical reaction. This feature was exploited to functionalize the nanograss film with three representative species, namely porphyrin, Au nanoparticles and titania. Of particular note, the novel silica@titania composite nanograss surface demonstrated the ability to convert its wetting behavior between the extreme states (superhydrophobic–superhydrophilic) by surface hydrophobic treatment and UV irradiation. The anatase titania component in the nanograss film acts as a highly efficient photocatalyst for the decomposition of the low-surface-energy organic components attached to the nanosurface. The ease with which the nanostructure can be controlled and facilely functionalized makes our nanograss potentially important for device-based application in microfluidic, microreactor and biomedical fields.
doi:10.3762/bjnano.2.84
PMCID: PMC3257501  PMID: 22259759
biomimetic silica mineralization; linear polyethyleneimine; nanofiber; nanograss; thin film

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