Synthesis and Characterization of Core-Shell Magnetic Mesoporous Silica and Organosilica Nanostructures

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Synthesis and Characterization of Core-Shell Magnetic Mesoporous Silica and Organosilica Nanostructures Nikola Z. Knezevic,1* Chiara Mauriello Jimenez,2 Martin Albino,3 Aleksandar Vukadinovic,4 Ana Mrakovic,4 Erzsebet Illes,4 Djordje Janackovic,1 Jean-Olivier Durand,2 Claudio Sangregorio5 and Davide Peddis4 Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia Institut Charles Gerhardt Montpellier, UMR 5253, CC 1701 Equipe Ingenierie Moleculaire et Nano-objets, Place Eugene Bataillon, 34095 Montpellier Cedex 05, France 3INSTM and Dept. of Chemistry, Univ. of Florence, 50019, Sesto Fiorentino, Italy 4 Vinca Institute of Nuclear Sciences, University of Belgrade, POB 522, 11001 Belgrade, Serbia 5INSTM and CNR-ICCOM, 50019 Sesto Fiorentino, Italy *Corresponding author: Dr Nikola Z. Knezevic: [email protected] 1 2

ABSTRACT Initial results en route toward construction of complex magnetic core-shell silica and organosilica nanotheranostics are presented. Magnetite nanoparticles are synthesized by three different methods and embedded within mesoporous silica and organosilica frameworks by different surfactant-templated procedures to produce three types of core-shell nanoparticles. Magnetite nanoparticles (15 nm in diameter) are embedded within mesoporous silica nanoparticles to produce cell-like material with predominantly one magnetite nuclei-resembling core per nanoparticle, with final particle diameter of ca. 150 nm, specific surface area of 573 m2/g and hexagonally structured tubular pores (2.6 nm predominant diameter), extended throughout the volume of nanoparticles. Two forms of spherical core-shell nanoparticles composed of magnetite cores embedded within mesoporous organosilica shells are also obtained by employing ethylene and ethane bridged organobisalkoxysilane precursors. The obtained nanomaterials are characterized by high surface area (978 and 820 m2/g), tubular pore morphology (2 and 2.8 nm predominant pore diameters), different diameters (386 and 100-200 nm), in case of ethylene- and ethane-composed organosilica shells, respectively. Different degree of agglomeration of magnetite nanoparticles was also observed in the obtained materials, and in the case of utilization of surfactant-pre-stabilized magnetite nanoparticles for the syntheses, their uniform and non-agglomerated distribution within the shells was noted. INTRODUCTION Intuitively, the use of inorganic materials in biological systems appears incompatible, though their effective applicability in drug delivery and imaging of biological tissues has been demonstrated by various research studies.[1] In particular, silicon-based materials are being showcased as the new generation of bioapplicable materials.[2-4] Recent research advances led to a development of nanoparticles which are even entirely made of silicon atoms, the porous silicon nanoparticles (pSiNPs) consisting of Si-Si framework, while the surface contains Si-H and Si-OH moieties. This material is actually the newest member of Si-based nanopar