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We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3–5 nm metal particles on the tubes; (2) inside the tube’s central lumen resulting in 10–12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube’s wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.

Halloysite nanotubes (HNTs) with immobilized gold (Au) and silver (Ag) nanoparticles (NPs) belong to a class of nanocomposite materials whose physical properties and applications depend on the geometry of arrangements of the plasmonic nanoparticles on HNT’ surfaces. We explore HNTs:(Au, Ag)-NPs as potential nano-templates for surface-enhanced Raman scattering (SERS). The structure and plasmonic properties of nanocomposites based on HNTs and Au- and Ag-NPs are studied by means of the transmission electron microscopy and optical spectroscopy. The optical extinction spectra of aqueous suspensions of HNTs:(Au, Ag)-NPs and spatial distributions of the electric fields are simulated, and the simulation results demonstrate the corresponding localized plasmonic resonances and numerous “hot spots” of the electric field nearby those NPs. In vitro experiments reveal an enhancement of the protein SERS in fibroblast cells with added HNTs:Ag-NPs. The observed optical properties and SERS activity of the nanocomposites based on HNTs and plasmonic NPs are promising for their applications in biosensorics and biophotonics.

Quantum dots (QD) are widely used for cellular labeling due to enhanced brightness, resistance to photobleaching, and multicolor light emissions. CdS and CdxZn1−xS nanoparticles with sizes of 6–8 nm were synthesized via a ligand assisted technique inside and outside of 50 nm diameter halloysite clay nanotubes (QD were immobilized on the tube’s surface). The halloysite–QD composites were tested by labeling human skin fibroblasts and prostate cancer cells. In human cell cultures, halloysite–QD systems were internalized by living cells, and demonstrated intense and stable fluorescence combined with pronounced nanotube light scattering. The best signal stability was observed for QD that were synthesized externally on the amino-grafted halloysite. The best cell viability was observed for CdxZn1−xS QD immobilized onto the azine-grafted halloysite. The possibility to use QD clay nanotube core-shell nanoarchitectures for the intracellular labeling was demonstrated. A pronounced scattering and fluorescence by halloysite–QD systems allows for their promising usage as markers for biomedical applications.