Abstract

In vivo incorporation of a series of organometallic photoluminescent complexes in Phaeodactylum tricornutum diatom shells (frustules) is investigated as a biotechnological route to luminescent biosilica nanostructures. [Ir(ppy)2bpy]+[PF6]−, [(2,2′-bipyridine)bis(2-phenylpyridinato)iridium(III) hexafluorophosphate], [Ru(bpy)3]2+ 2[PF6]−, [tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate], AlQ3 (tris-(8-hydroxyquinoline)aluminum), and ZnQ2 (bis-8-hydroxyquinoline-zinc) are used as model complexes to explore the potentiality and generality of the investigated process. The luminescent complexes are added to the diatom culture, and the resulting luminescent silica nanostructures are isolated by an acid-oxidative treatment that removes the organic cell matter without altering both frustule morphology and photoluminescence of incorporated emitters. Results show that, except for ZnQ2, the protocol successfully leads to the incorporation of complexes into the biosilica. The spontaneous self-adhering ability of both bare and doped Phaeodactylum tricornutum cells on conductive indium tin oxide (ITO)-coated glass slides is observed, which can be exploited to generate dielectric biofilms of living microorganisms with luminescent silica shells. In general, this protocol can be envisaged as a profitable route to new functional nanostructured materials for photonics, sensing, or biomedicine via in vivo chemical modification of diatom frustules with organometallic emitters.

Highlights

  • The luminescent complexes are added to the diatom culture, and the resulting luminescent silica nanostructures are isolated by an acid-oxidative treatment that removes the organic cell matter without altering both frustule morphology and photoluminescence of incorporated emitters

  • Diatom microalgae have recently attracted the interest of materials scientists as they can be envisaged as bio-factories for products of mesoporous biosilica with morphology hardly reproducible by human technologies [1]

  • We have investigated in vivo incorporation of iridium, ruthenium, aluminum, and zinc luminescent organometallic complexes into Phaeodactylum tricornutum diatom microalgae

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Summary

Introduction

Diatom microalgae have recently attracted the interest of materials scientists as they can be envisaged as bio-factories for products of mesoporous biosilica with morphology hardly reproducible by human technologies [1]. Diatom silica cell walls (frustules) are composed of valves and girdles with shape, dimension, and highly periodic nanostructure strictly dependent on the microalgal species [2]. Current literature shows the suitability of diatom frustules or their components for applications in various fields, e.g., as natural photonic crystals and lenses in optics [3,4], biocompatible porous scaffolds for drug delivery and biomedicine [5,6,7,8,9], and nanostructured templates for generation of highly porous conducting materials in electronics [10]. Several approaches for chemical modification of diatom biosilica for specific applications have been developed [11]. Surface chemical modification [12,13] of frustules after cleaning from the organic cell matter represents a common route to biosilica-based materials for sensing or catalysis [14]. The isolation of diatom biosilica shells and their bioclastic conversion [15] into nanostructures with

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