Some natural structures show three-dimensional morphologies on the micro- and nano- scale, characterized by levels of symmetry and complexity well far beyond those fabricated by best technologies available. This is the case of diatoms, unicellular microalgae, whose protoplasm is enclosed in a nanoporous microshell, made of hydrogenated amorphous silica, called frustule. We have studied the optical properties of Arachnoidiscus sp. single valves both in visible and ultraviolet range. We found photonic effects due to diffraction by ordered pattern of pores and slits, accordingly to an elaborated theoretical model. For the first time, we experimentally revealed spatial separation of focused light in different spots, which could be the basis of a micro-bio-spectrometer. Characterization of such intricate structures can be of great inspiration for photonic devices of next generation.
1 December 2017 in Science of The Total Environment
In this work the possibility to exploit the ability of multiple scattering and localization of light shown by diatom silica shells (frustules) for photoluminescence amplification in a random laser was investigated. To this aim polymethylmethacrylate matrix composite random lasers based on rhodamine B and frustules as gain medium and scatterers, respectively, were prepared by solvent casting. Two different kinds of frustules were used, the first represented by diatomite, a fossil material composed of a mixture of frustules from different diatom species, without specific shape, size and porosity; the second were living diatom frustules from freshwater biofilm, a more homogeneous biosilica, dominated by one frustule type. Chemical properties, morphology and photoluminescence of both biosilica fillers were investigated. Random laser experiments were carried out on polymer composites. The diatomite material was characterised by rectangular and circular pores, ranging from 25 nm to 1 μm in size and showed weak photoluminescence upon excitation at 405 nm. Biofilm frustules were more homogeneous in size and microstructure, with average length of about 20 μm and pore diameters between 20 and 100 nm. The frustule photoluminescence, observed after irradiation at 488, 515, 543 and 635 nm was higher than in diatomite. In addition, the two biosilica materials differed with respect to the presence of superficial silanol groups, that were not detected in diatomite. Random laser experiments showed an incoherent random lasing effect in all polymer composites. The laser threshold diminished at increasing frustule content, with a lowest value recorded using biofilm frustules (308 kW cm−2). This is probably due to the frustule size exhibited in this almost monospecific biosilica, that was in the range of most typical morphology-dependent resonators.
Diatoms can represent the major component of phytoplankton and contribute massively to global primary production in the oceans. Over tens of millions of years they developed an intricate porous silica shell, the frustule, which ensures mechanical protection, sorting of nutrients from harmful agents, and optimization of light harvesting. Several groups of microalgae evolved different strategies of protection towards ultraviolet radiation (UVR), which is harmful for all living organisms mainly through the formation of dimeric photoproducts between adjacent pyrimidines in DNA. Even in presence of low concentrations of UV-absorbing compounds, several diatoms exhibit significant UVR tolerance. We here investigated the mechanisms involved in UVR screening by diatom silica investments focusing on single frustules of a planktonic centric diatom, Coscinodiscus wailesii, analyzing absorption by the silica matrix, diffraction by frustule ultrastructure and also UV conversion into photosynthetically active radiation exerted by nanostructured silica photoluminescence. We identified the defects and organic residuals incorporated in frustule silica matrix which mainly contribute to absorption; simulated and measured the spatial distribution of UVR transmitted by a single valve, finding that it is confined far away from the diatom valve itself; furthermore, we showed how UV-to-blue radiation conversion (which is particularly significant for photosynthetic productivity) is more efficient than other emission transitions in the visible spectral range.