Abstract
Here we report a method for coating of hydrophobic nanocrystals (NCs) with a thin silica layer. By using this approach 11 nm NaGdF4 NCs were coated with a mesoporous silica shell thinner than 20 nm resulting in highly monodisperse core-shell nanocomposite particles smaller than 50 nm. The synthetic protocol used here is based on the two-phase system that ensures high repeatability of the nanoparticle morphology and can be conveniently adapted for large-scale production. The use of an organic solvent as a diluent for tetraethoxysilane allows us to control not only the thickness, but also the porosity of the uniform silica shell. This procedure can be applied for coating NCs of various sizes and can be generalized to encapsulate other nanocrystals, e.g. semi-conductor quantum dots, into silica spheres. Furthermore, it allows facile surface modification with -NH2 groups that can be then used to conjugate biomolecules to the nanoparticle surface, as well as straightforward incorporation of various organic molecules (e.g. dyes or drugs) into the silica shell during its growth. To demonstrate potential applications up-converting NaGd0.80Yb0.18Er0.02F4 NCs were used as cores and zinc phthalocyanine was incorporated into the silica shell as a photosensitizer. Under irradiation with a 980 nm laser diode efficient generation of singlet oxygen was observed indicating that such nanocomposite particles have the capability to be used for photodynamic therapy.
Highlights
Biocompatible, monodisperse, up-converting nanoparticles (UCNPs) doped with rare-earth ions are attracting appreciable attention due to their unique optical properties and possibility of use in many technological elds.[1]
The core up-converting b-NaGd0.80Yb0.18Er0.02F4 NCs (NGF@OA) were synthesized by thermal decomposition of sodium and lanthanide tri uoroacetates dissolved in a mixture of oleic acid and 1-octadecene following the procedure described by Murray et al.[35]
The synthetic protocol used here, based on the biphasic system, ensures high repeatability of the NP morphology. This procedure can be applied for coating NCs of various sizes and the thickness of the silica coating layer can be varied by changing synthetic parameters, such as the amount of NCs and TEOS or reaction temperature and time
Summary
Biocompatible, monodisperse, up-converting nanoparticles (UCNPs) doped with rare-earth ions are attracting appreciable attention due to their unique optical properties and possibility of use in many technological elds.[1]. The most popular reagents used for surface modi cation are (3-aminopropyl)triethoxysilane (APTES) and (3-mercaptopropyl)trimethoxysilane (MPTES) which introduce NH2 and SH groups, respectively, enabling the covalent binding of biological molecules to the surface of NPs. The two most common methods in the literature for coating of nano uoride NCs are analogous to those widely used for preparation of monodisperse colloidal silica particles, i.e. the Stober approach and the microemulsion based method. Modi cation of the method of Yokoi et al enabled Hartlen et al.[21] to obtain silica particles with the controllable size ranging from 15 to 200 nm We used these approaches which proved to be the most efficient in the synthesis of silica spheres as a starting point for exploiting the synthetic route for coating of nanocrystals with silica shells. If photon upconverting NCs, e.g. NaLnF4:Er3+,Yb3+, are used as cores, the incorporated photosensitizer can be excited with radiation in the NIR region
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