Abstract

Luminescent organic-inorganic hybrids containing lanthanides (Ln3+) have been prominent for applications such as luminescent bio-probes in biological assays. In this sense, a luminescent hybrid based on dense silica (SiO2) nanospheres decorated with Eu3+ β–diketonate complexes using dibenzoylmethane (Hdbm) as a luminescent antenna was developed by using a hierarchical organization in four steps: (i) anchoring of 3-aminopropyltriethoxysilane (APTES) organosilane on the SiO2 surface, (ii) formation of a carboxylic acid ligand, (iii) coordination of Eu3+ to the carboxylate groups and (iv) coordination of dbm− to Eu3+. The hybrid structure was elucidated through the correlation of thermogravimetry, silicon nuclear magnetic resonance and photoluminescence. Results indicate that the carboxylic acid-Eu3+-dbm hybrid was formed on the surface of the particles with no detectable changes on their size or shape after all the four steps (average size of 32 ± 7 nm). A surface charge of −27.8 mV was achieved for the hybrid, assuring a stable suspension in aqueous media. The Eu3+ complex provides intense red luminescence, characteristic of Eu3+ 5D0→7FJ electronic transitions, with an intrinsic emission quantum yield of 38%, even in an aqueous suspension. Therefore, the correlation of luminescence, structure, particle morphology and fluorescence microscopy images make the hybrid promising for application in bioimaging.

Highlights

  • Clinical diagnosis by imaging is expanding due to the development of sensitive and non-invasive techniques such as confocal or fluorescence microscopy, appearing as powerful tools for exploratory analyses of several biological processes and internal structural information of healthy and cancerogenous cells [1,2,3]

  • Nanospheres of SiO2 —average size of 32 nm—decorated with luminescent Eu3+ -dbm complexes bonded by carboxylic bridges were successfully synthesized by a step-by-step method

  • As a spectroscopic probe confirmed at least two non-equivalent Eu3+ local sites onto the SiO2 surface composed by Eu3 + bonded to two or three dbm- ligands

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Summary

Introduction

Clinical diagnosis by imaging is expanding due to the development of sensitive and non-invasive techniques such as confocal or fluorescence microscopy, appearing as powerful tools for exploratory analyses of several biological processes and internal structural information of healthy and cancerogenous cells [1,2,3]. Among several biomaterials applied in bioimaging, luminescent biomarkers are widely used as contrast agents for in vivo and in vitro, clinical assays, acting as bio-probes responsible by imaging and clinical information of the cellular environment [4,5]. New strategies towards the development and improvement of the luminescent and structural features of such bio-probes are of large social relevance. Ln3+ or metallic ions in complexes or in inorganic hosts [10,11,12]. Ions in complexes or in inorganic hosts [10,11,12] Each of those materials [9] and Ln

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