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MASTER THESIS Biomimetic potential of sponge ... - IAP/TU Wien

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On the subject <strong>of</strong> spicule inspired nanostructures many different approaches have been<br />

pursued. Cha and colleagues (2000) soon after their discovery <strong>of</strong> the silicatein controlled<br />

synthesis <strong>of</strong> spicules reported the successful synthesis <strong>of</strong> silica structures by a biomimetic<br />

approach. In the mineralization process, silicatein was replaced by a synthetic peptide<br />

(consisting <strong>of</strong> cysteine and lysine) that catalyzed the deposition <strong>of</strong> regular silica rods.<br />

It has been found out that for the efficient deposition <strong>of</strong> silica two amino acids in the<br />

sequence <strong>of</strong> silicatein were crucial (Zhou et al., 1999). The identification <strong>of</strong> this essential<br />

feature <strong>of</strong> silicatein helped researchers to find simple chemical compounds that catalyze the<br />

formation <strong>of</strong> silica structures. In this line <strong>of</strong> research, Park and Choi (2010) used small simple<br />

molecules, an amino acid derivative and a surfactant, to catalyze the formation <strong>of</strong><br />

individually separated microspheres at near-neutral pH.<br />

A different approach in nanotechnology is the use <strong>of</strong> (recombinant) silicatein to catalyze<br />

the deposition <strong>of</strong> other metal oxides than silica. Conceptually, it is not clear whether this<br />

classifies as biomimetics because the naturally occurring enzyme is used directly, and no<br />

abstraction is being made at that level. However, as stated by André and co-workers (2012),<br />

the emulation <strong>of</strong> the chemistry behind natural mineralization processes is indispensable for<br />

the use <strong>of</strong> known biomineralization agents like silicatein in technological processes. Thus, at<br />

the scale <strong>of</strong> chemical conditions relevant for the mineralization process some degree <strong>of</strong><br />

abstraction is recognizable.<br />

Examples <strong>of</strong> successful attempts to use silicatein, immobilized on synthetic surfaces, for<br />

mineralization <strong>of</strong> metal oxides include the formation <strong>of</strong> layered titania (TiO 2 ) and zirconia<br />

(ZrO 2 ) (Tahir et al., 2005) and the formation <strong>of</strong> gallium oxide (GaOH ⁄ Ga 2 O 3 ) nanocrystals on<br />

filaments (Kisailus et al., 2005). In the examples presented here, the absence <strong>of</strong> alkali and<br />

acid (near-neutral pH) was stressed as distinctive to previous protocols for the synthesis <strong>of</strong><br />

similar compounds. André and colleagues (2011) went one step further by including not only<br />

silicatein, but also silintaphin (a protein interacting with silicatein in vivo) that enhanced the<br />

deposition <strong>of</strong> the metal oxide used. Specifically, TiO 2 nanorods were coated with silicatein<br />

and silintaphin and subsequently catalyzed the deposition <strong>of</strong> either zirconia or silica.<br />

Irrespective <strong>of</strong> the assembled molecules, there have been identified two key features <strong>of</strong><br />

the polycondensation reaction by silicatein or a biomimetic analogue. The hydrolysis <strong>of</strong> the<br />

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