Biological insertion of nanostructured germanium and titanium oxides into diatom biosilica Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/kd17cw34k

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  • There is significant interest in titanium oxide and germanium-silicon oxide nanocomposites for optoelectronic, photocatalytic, and solar cell applications. The ability of the marine diatom Pinnularia sp. to uptake soluble metal oxides from cell culture medium, and incorporate them into the micro- and nano-structure of their amorphous silica cell walls, called frustules, was evaluated using an engineered photobioreactor system. The effects of metal oxides on the structural and elemental properties of the frustule were also evaluated. Diatom cell cultures grown in 5 L photobioreactors were initially charged with 0.5 mM of soluble silicon, Si(OH)₄, an obligate substrate required for frustule fomation. Upon exhaustion of Si(OH)₄ cells were exposed to the mixed pulse-addition of soluble silicon and germanium or co-perfusion addition of soluble silicon and titanium, which were incorporated into the frustules. Metals composition of the cell culture medium, diatom biomass and purified frustules were measured, as was the local elemental composition within the frustule pores and the metal oxide crystallinity. Diatom frustules having a germanium composition of 1.6 wt % were devoid of the native intra-pore structures and possessed enhanced photoluminescence and electroluminescence when compared to frustules without Ge. Diatoms cultivated in the presence of soluble titanium incorporated amorphous titania into the frustule, which maintained native structure even when local TiO₂ concentrations within the nanopores approached 60 wt. %. Titanium oxide could also be biomimetically deposited directly within the diatom nanopores by adsorbing poly-L-lysine to the diatom biosilica where it catalyzed the soluble titanium precursor Ti-BALDH into amorphous titania nanoparticles. Both biogenic and biomimetic titania could be converted to anatase titanium by thermal annealing. It was determined that nanostructured metal oxide composites can be fabricated biomimetically or in cell culture to possess properties which may be useful in display or solar cell applications.
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