Antioxidative and Photo-Induced Effects of Different Types of N-Doped Graphene Quantum Dots.

Due to the increasing number of bacterial infections and the development of resistivity toward antibiotics, new materials and approaches for treatments must be urgently developed. The production of new materials should be ecologically friendly considering overall pollution with chemicals and economically acceptable and accessible to the wide population. Thus, the possibility of using biocompatible graphene quantum dots (GQDs) as an agent in photodynamic therapy was studied. First, dots were obtained using electrochemical cutting of graphite. In only one synthetic step using gamma irradiation, GQDs were doped with N atoms without any reagent. Obtained dots showed blue photoluminescence, with a diameter of 19-89 nm and optical band gap of 3.23-4.73 eV, featuring oxygen-containing, amino, and amide functional groups. Dots showed antioxidative activity; they quenched •OH at a concentration of 10 µg·mL-1, scavenged DPPH• radicals even at 5 µg·mL-1, and caused discoloration of KMnO4 at 30 µg·mL-1. Under light irradiation, dots were able to produce singlet oxygen, which remained stable for 10 min. Photoinduced effects by GQDs were studied on several bacterial strains (Listeria monocytogenes, Bacillus cereus, clinical strains of Streptococcus mutans, S. pyogenes, and S. sangunis, Pseudomonas aeruginosa, and one yeast strain Candida albicans) but antibacterial effects were not noticed.

Gamma-Ray-Induced Structural Transformation of GQDs towards the Improvement of Their Optical Properties, Monitoring of Selected Toxic Compounds, and Photo-Induced Effects on Bacterial Strains.

Structural modification of different carbon-based nanomaterials is often necessary to improve their morphology and optical properties, particularly the incorporation of N-atoms in graphene quantum dots (GQDs). Here, a clean, simple, one-step, and eco-friendly method for N-doping of GQDs using gamma irradiation is reported. GQDs were irradiated in the presence of the different ethylenediamine (EDA) amounts (1 g, 5 g, and 10 g) and the highest % of N was detected in the presence of 10 g. N-doped GQDs emitted strong, blue photoluminescence (PL). Photoluminescence quantum yield was increased from 1.45, as obtained for non-irradiated dots, to 7.24% for those irradiated in the presence of 1 g of EDA. Modified GQDs were investigated as a PL probe for the detection of insecticide Carbofuran (2,2-Dimethyl-2,3-dihydro-1-benzofuran-7-yl methylcarbamate) and herbicide Amitrole (3-amino-1,2,4-triazole). The limit of detection was 5.4 µmol L-1 for Carbofuran. For the first time, Amitrole was detected by GQDs in a turn-off/turn-on mechanism using Pd(II) ions as a quenching agent. First, Pd(II) ions were quenched (turn-off) PL of GQDs, while after Amitrole addition, PL was recovered linearly with Amitrole concentration (turn-on). LOD was 2.03 µmol L-1. These results suggest that modified GQDs can be used as an efficient new material for Carbofuran and Amitrole detection. Furthermore, the phototoxicity of dots was investigated on both Gram-positive and Gram-negative bacterial strains. When bacterial cells were exposed to different GQD concentrations and illuminated with light of 470 nm wavelength, the toxic effects were not observed.