Effects of Endohedral Gd-Containing Fullerenols with a Different Number of Oxygen Substituents on Bacterial Bioluminescence

https://doi.org/10.3390/ijms25020708 

Gd@C₈₂O_xH_y endohedral complexes for advanced biomedical applications (computer tomography, cancer treatment, etc.) were synthesized using high-frequency arc plasma discharge through a mixture of graphite and Gd₂O₃ oxide. The Gd@C₈₂ endohedral complex was isolated by high-efficiency liquid chromatography and consequently oxidized with the formation of a family of Gd endohedral fullerenols with gross formula Gd@C₈₂O₈(OH)₂₀. Fourier-transformed infrared (FTIR) spectroscopy was used to study the structure and spectroscopic properties of the complexes in combination with the DFTB3 electronic structure calculations and infrared spectra simulations. It was shown that the main IR spectral features are formed by a fullerenole C₈₂ cage that allows one to consider the force constants at the DFTB3 level of theory without consideration of gadolinium endohedral ions inside the carbon cage. Based on the comparison of experimental FTIR and theoretical DFTB3 IR spectra, it was found that oxidation of the C₈₂ cage causes the formation of Gd@C₈₂O₂₈H₂₀, with a breakdown of the integrity of the parent C₈₂ cage with the formation of pores between neighboring carbonyl and carboxyl groups. The Gd@C₈₂O₆(OOH)₂(OH)₁₈ endohedral complex with epoxy, carbonyl and carboxyl groups was considered the most reliable fullerenole structural model.