Photoluminescence of Silica Nanostructures from Bioreactor Culture of Marine Diatom Nitzschia frustulum

Abstract

The marine diatom Nitzschia frustulum is a single-celled photosynthetic organism that uses soluble silicon as the substrate to fabricate intricately patterned silica shells called frustules consisting of 200 nm diameter pores in a rectangular array. Controlled photobioreactor cultivation of the N. frustulum cell suspension to silicon starvation induced changes in the nanostructure of the diatom frustule, which in turn imparted blue photoluminescence (PL) to the frustule biosilica. The photoluminescent properties were imbedded within a patterned substrate precisely ordered at the nano, submicron and microscales. The peak PL intensity increased by a factor of 18 from the mid-exponential to late stationary phase of the cultivation cycle, and the peak PL wavelength increased from 440 to 500 nm. TEM analysis revealed that the emergence of blue photoluminescence was associated with the appearance of fine structures on the frustule surface, including 5 nm nanopore arrays lining the base of the frustule pores, which were only observed at the late stationary phase when both silicon consumption and cell division were complete for two photoperiods. Photoluminescence was quenched by thermal annealing of diatom biosilica in air at 800 °C for 1.0 hr, commensurate with the loss of silanol (≡Si-OH)groups on the diatom biosilica, as confirmed by FT-IR. Consequently, the likely origin of blue photoluminescence in the diatom biosilica was from surface silanol groups and their distribution on the frustule fine structures.