The mechanisms underlying the cytotoxic action of pure fullerene suspension (nano-C60) and water-soluble polyhydroxylated fullerene [C60(OH)n] were investigated. Crystal violet assay for cell viability demonstrated that nano-C60 was at least three orders of magnitude more toxic than C60(OH)n to mouse L929 fibrosarcoma, rat C6 glioma, and U251 human glioma cell lines. Flow cytometry analysis of cells stained with propidium iodide (PI), PI/annexin V-fluorescein isothiocyanate, or the redox-sensitive dye dihydrorhodamine revealed that nano-C60 caused rapid (observable after few hours), reactive oxygen species (ROS)-associated necrosis characterized by cell membrane damage without DNA fragmentation. In contrast, C60(OH)n caused delayed, ROS-independent cell death with characteristics of apoptosis, including DNA fragmentation and loss of cell membrane asymmetry in the absence of increased permeability. Accordingly, the antioxidant N-acetylcysteine protected the cell lines from nano-C60 toxicity, but not C60(OH)n toxicity, while the pan-caspase inhibitor z-VAD-fmk blocked C60(OH)n-induced apoptosis, but not nano-C60-mediated necrosis. Finally, C60(OH)n antagonized, while nano-C60 synergized with, the cytotoxic action of oxidative stress-inducing agents hydrogen peroxide and peroxynitrite donor 3-morpholinosydnonimine. Therefore, unlike polyhydroxylated C60 that exerts mainly antioxidant/cytoprotective and only mild ROS-independent pro-apoptotic activity, pure crystalline C60 seems to be endowed with strong pro-oxidant capacity responsible for the rapid necrotic cell death.
ZnO nanoparticles doped with different Eu 3+ percentages were synthesized in water (ZnO:Eu(x%)-W) and other solvents (methanol ZnO:Eu(x%)-M and ethanol ZnO:Eu(x%)-E). X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), optical absorption and photoluminescence (PL) spectroscopy were used for characterization of the nanoparticles. Our results showed influence of europium doping and solvents on size, particles agglomeration, light absorption and photocatalytic activity. Improvement in photocatalytical activity with addition of Eu 3+ doping was detected. Particle size increased with Eu 3+ doping in water samples, while it decreased in methanol. Agglomeration was more prominent in ZnO:Eu(x)-W samples.Greater amount of surface OH groups in case of ZnO:Eu(x%)-M samples was detected by PL, XPS and FTIR measurements. Influence of europium doping, as an electron trap, and surface OH groups, as a hole trap, was studied in sunlight photocatalytic degradation of cationic methylene blue (MB) and anionic methyl orange (MO). Improved photocatalytic behavior was discussed and influence of active species was further investigated using hole and hydroxyle radical scavengers. The degradation pathway of MB and MO, using high performance liquid chromatohraphy (HPLC), is also examined.
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