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

Abstract

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.

Keywords: Cell internalization; Cellular contrast agent; Hexarhenium cluster; Luminescence; Polyethyleneimine; Silica nanoparticles; pH-sensing.