Luminescent Water-Dispersible Nanoparticles Engineered from Copper(I) Halide Cluster Core and P,N-Ligand with an Optimal Balance between Stability and ROS Generation

Abstract

The present work introduces the solvent exchange procedure as a route for conversion of the Cu4I4L2 complex, where the Cu4I4 cluster core is coordinated with two P,N-ligands (L), into an aqueous colloid. The analysis of both colloidal and supernatant phases revealed some losses in CuI going from the initial Cu4I4L2 complex to Cu2I2L3-based nanoparticles. The comparative analysis of IR, 31P NMR spectroscopy, ESI mass-spectrometry and luminescence data argued for a contribution of the “butterfly”-like structures of the Cu2I2 cluster core to Cu2I2L3-based nanoparticles, although the amorphous nature of the latter restricted structure evaluation from the PXRD data. The green luminescence of the colloids revealed their chemical stability under pH variations in the solutions of some amino acids and peptides, and to specify the temperature and concentration conditions triggering the oxidative degradation of the nanoparticles. The spin trap-facilitated ESR study indicated that the oxidative transformations were followed by the generation of reactive oxygen species (ROS). The physiological temperature level (310 K) enhanced the ROS generation by nanoparticles, but the ROS level was suppressed in the solution of GSH at pH = 7.0. The cytotoxicity of nanoparticles was evaluated in the M-HeLa cell line and is discussed in correlation with their cell internalization and intracellular oxidative transformations.

Keywords

• copper (I) halide cluster
• P,N-ligand
• hydrophilic nanoparticles
• luminescence
• ROS generation
• chemodynamic therapy