In vivo doped biosilica from living Thalassiosira weissflogii diatoms with a triethoxysilyl functionalized red emitting

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In vivo doped biosilica from living Thalassiosira weissflogii diatoms with a triethoxysilyl functionalized red emitting fluorophore

M. Lo Presti1, R. Ragni1, D. Vona1, G. Leone1, S. Cicco2, G. M. Farinola1* Dipartimento di Chimica, Università. degli Studi di Bari “Aldo Moro”. Via Orabona, 4, 70126 Bari, Italy.

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CNR ICCOM, Via Orabona, 4, 70126 Bari, Italy

ABSTRACT

Diatoms microalgae represent a natural source of highly porous biosilica shells (frustules) with promising applications in a wide range of technological fields. Functionalization of diatoms’ frustules with tailored luminescent molecules can be envisaged as a convenient, scalable biotechnological route to new light emitting silica nanostructured materials. Here we report a straightforward protocol for the in vivo modification of Thalassiosira weissflogii diatoms’ frustules with a red emitting organic dye based on thienyl, benzothiadiazolyl and phenyl units. The metabolic insertion of the dye molecules into the diatoms shells, combined with an acidic-oxidative isolation protocol of the resulting dye stained biosilica, represents a novel strategy to develop highly porous luminescent biosilica nanostructures with promising applications in photonics.

INTRODUCTION Mesoporous nanostructured and highly porous silica has recently attracted enormous scientific and technological interest as a versatile and tunable material with a broad range of applications including photonics, catalysis, separation, sensing and biomedicine. [1, 2] Nevertheless, the production of silica based mesoporous structures involving chemical approaches is time consuming and often requires use of expensive and toxic materials. Moreover, a good control on size and morphology with synthetic methods is not always ensured. [3] Downloaded from https://www.cambridge.org/core. Cornell University Library, on 19 Jan 2018 at 10:59:37, subject to the Cambridge Core terms of use, available at https://www.cambridge.org/core/terms. https://doi.org/10.1557/adv.2018.60

Silica produced by bio-silicifying microorganisms like diatoms represents an alternative and attractive source to synthetic mesoporous silica for many advantages related to (i) extremely regular nanoarchitectures obtainable both in the micrometer- and sub micrometer range, that in some cases are even artificially irreproducible, [4] (ii) the possibility to avail of large-scale and environmentally friendly production and iii) last, but not least, the possibility of further chemical modifications of silica through biotechnological approaches. Among various organisms able to produce silica nanostructured components via a complex biomineralization process, diatoms have recently caught the interest of materials scientists. Diatoms are single celled photosynthetic microalgae living in both fresh and marine water ecosystems. These unicellular organisms have the organic protoplasm enclosed into a three-dimensional amorphous silica shell, the frustule, exhibiting a Petri dish-like structure made of two valves, the epivalve and the hypovalve,