XPS Study of Grafting Paramagnetic Ions onto the Surface of Detonation Nanodiamonds

Grafting of paramagnetic transition and rare earth metal ions onto the surface of detonation nanodiamonds (DNDs) was successfully implemented in the recent decade and opened new opportunities in the biomedical application of these compounds, particularly as novel contrast agents for magnetic resonance imaging. The grafting was studied mainly using EPR, NMR, and magnetic measurements. Such a highly surface-sensitive, quantitative, chemical analytic technique as X-ray photoelectron spectroscopy (XPS) was very rarely used. In this paper, we report the XPS study of grafting transition and rare-earth metal ions (Cu²⁺, Co²⁺, Mn²⁺, and Gd³⁺) onto the surface of DNDs. Binding energies for metal, carbon, oxygen, and nitrogen atoms were determined and attributed to the corresponding ion states and atomic groups. Comparing XPS and EPR findings, we showed that the developed synthesis route resulted in almost complete grafting of manganese and gadolinium atoms in the form of paramagnetic ions Mn²⁺ and Gd³⁺ to the diamond surface, while only 30% of the copper atoms on the surface are in the paramagnetic state Cu²⁺, and the rest 70% are in the non-magnetic Cu⁺ state. It was not possible to draw a similar conclusion regarding Co²⁺ ions due to the lack of data on the amount of these paramagnetic ions on the DND surface.