Surface modification of silica nanoparticles by hexarhenium anionic cluster complexes for pH-sensing and staining of cell nuclei.

The surface deposition of luminescent anionic cluster complex [{Re6S8}(OH)6]4- advantages to the design and synthesis of composite luminescent silica nanoparticles (SNs) for intracellular imaging and sensing, while the encapsulation of the cluster units into SNs lacks for efficient luminescence. The deposition of the Re6 clusters resulted from their assembly at the silica surface functionalized by amino-groups provides the synthetic route for the composite SNs with bright cluster-centered luminescence invariable in pH range from 4.0 to 12.0. The pH-dependent supramolecular assembly of the cluster units with polyethyleneimine (PEI) at the silica surface is an alternative route for the synthesis of the composite SNs with high cluster-centered luminescence sensitive to pH-changes within 4.0-6.0. The sensitivity derives from the pH-driven conformational changes of PEI chains resulting in the release of the clusters from the PEI-based confinement under the acidification within pH 6.0-4.0. The potential of the composite SNs in cellular contrasting has been also revealed by the cell viability and flow cytometry measurements. It has been found that the PEI-supported embedding of the cluster units facilitates cell internalization of the composite SNs as well as results in specific intracellular distribution manifested by efficient staining of the cell nuclei in the confocal images.

ROS-generation and cellular uptake behavior of amino-silica nanoparticles arisen from their uploading by both iron-oxides and hexamolybdenum clusters.

The present work introduces combination of superparamagnetic iron oxides (SPIONs) and hexamolybdenum cluster ([{Mo6I8}I6]2-) units within amino-decorated silica nanoparticles (SNs) as promising design of the hybrid SNs as efficient cellular contrast and therapeutic agents. The heating generated by SNs doped with SPIONs (Fe3O4@SNs) under alternating magnetic field is characterized by high specific absorption rate (SAR = 446 W/g). The cluster units deposition onto both Fe3O4@SNs and "empty" silica nanoparticles (SNs) results in Fe3O4@SNs[{Mo6I8}I6] and SNs[{Mo6I8}I6] with red cluster-centered luminescence and ability to generate reactive oxygen species (ROS) under the irradiation. The monitoring of spin-trapped ROS by ESR spectroscopy technique indicates that the ROS-generation decreases in time for SNs[{Mo6I8}I6] and [{Mo6I8}I6]2- in aqueous solutions, while it remains constant for Fe3O4@SNs[{Mo6I8}I6]. The cytotoxicity is low for both Fe3O4@SNs[{Mo6I8}I6] and SNs[{Mo6I8}I6], while the flow cytometry indicates preferable cellular uptake of the former versus the latter type of the nanoparticles. Moreover, entering into nucleus along with cytoplasm differentiates the intracellular distribution of Fe3O4@SNs[{Mo6I8}I6] from that of SNs[{Mo6I8}I6], which remain in the cell cytoplasm only. The exceptional behavior of Fe3O4@SNs[{Mo6I8}I6] is explained by residual amounts of iron ions at the silica surface.