Carboxyl Functionalization of N-MWCNTs with Stone-Wales Defects and Possibility of HIF-1α Wave-Diffusive Delivery

Nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) are widely used for drug delivery. One of the main challenges is to clarify their interaction with hypoxia-inducible factor 1 alpha (HIF-1α), the lack of which leads to oncological and cardiovascular diseases. In the presented study, N-MWCNTs were synthesized by catalytic chemical vapor deposition and irradiated with argon ions. Their chemical state, local structure, interfaces, Stone-Wales defects, and doping with nitrogen were analyzed by high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Using experimental data, supercells of functionalized N-MWCNTs with an oxygen content of 2.7, 4 and 6 at. % in carboxyl groups were built by quantum chemical methods. Our analysis by the self-consistent charge density functional tight-binding (SCC DFTB) method shows that a key role in the functionalization of CNTs with carboxyl groups belongs to Stone-Wales defects. The results of research in the decoration of CNTs with HIF-1α demonstrate the possibility of wave-diffusion drug delivery. The nature of hybridization and relaxation determines the mechanism of oxygen regulation with HIF-1α molecules, namely, by OH-(OH-C) and OH-(O=C) chemical bonds. The concentration dependence of drug release in the diffusion mode suggests that the best pattern for drug delivery is provided by the tube with a carboxylic oxygen content of 6 at. %.