In the present study, we successfully synthesized N-doped carbon quantum dots (N-CQDs) using a top-down approach, i.e., hydroxyl radical opening of fullerene with hydrogen peroxide, in basic ambient using ammonia for two different reaction times. The ensuing characterization via dynamic light scattering, SEM, and IR spectroscopy revealed a size control that was dependent on the reaction time, as well as a more pronounced -NH2 functionalization. The N-CQDs were probed for metal ion detection in aqueous solutions and during bioimaging and displayed a Cr3+ and Cu2+ selectivity shift at a higher degree of -NH2 functionalization, as well as HEK-293 cell nuclei marking.
Water pollution caused by hexavalent chromium (Cr(VI)) ions represents a serious hazard for human health due to the high systemic toxicity and carcinogenic nature of this metal species. The optical sensing of Cr(VI) through specifically engineered nanomaterials has recently emerged as a versatile strategy for the application to easy-to-use and cheap monitoring devices. In this study, a one-pot oxidative method was developed for the cage opening of C60 fullerene and the synthesis of stable suspensions of N-doped carbon dots in water–THF solutions (N-CDs-W-THF). The N-CDs-W-THF selectively showed variations of optical absorbance in the presence of Cr(VI) ions in water through the arising of a distinct absorption band peaking at 550 nm, i.e., in the transparency region of pristine material. Absorbance increased linearly, with the ion concentration in the range 1–100 µM, thus enabling visual and ratiometric determination with a limit of detection (LOD) of 300 nM. Selectivity and possible interference effects were tested over the 11 other most common heavy metal ions. The sensing process occurred without the need for any other reactant or treatment at neutral pH and within 1 min after the addition of chromium ions, both in deionized and in real water samples.
ZnO has many technological applications which largely depend on its properties, which can be tuned by controlled synthesis. Ideally, the most convenient ZnO synthesis is carried out at room temperature in an aqueous solvent. However, the correct temperature values are often loosely defined. In the current paper, we performed the synthesis of ZnO in an aqueous solvent by varying the reaction and drying temperatures by 10 °C steps, and we monitored the synthesis products primarily by XRD). We found out that a simple direct synthesis of ZnO, without additional surfactant, pumping, or freezing, required both a reaction (TP) and a drying (TD) temperature of 40 °C. Higher temperatures also afforded ZnO, but lowering any of the TP or TD below the threshold value resulted either in the achievement of Zn(OH)2 or a mixture of Zn(OH)2/ZnO. A more detailed Rietveld analysis of the ZnO samples revealed a density variation of about 4% (5.44 to 5.68 gcm−3) with the synthesis temperature, and an increase of the nanoparticles’ average size, which was also verified by SEM images. The average size of the ZnO synthesized at TP = TD = 40 °C was 42 nm, as estimated by XRD, and 53 ± 10 nm, as estimated by SEM. For higher synthesis temperatures, they vary between 76 nm and 71 nm (XRD estimate) or 65 ± 12 nm and 69 ± 11 nm (SEM estimate) for TP = 50 °C, TD = 40 °C, or TP = TD = 60 °C, respectively. At TP = TD = 30 °C, micrometric structures aggregated in foils are obtained, which segregate nanoparticles of ZnO if TD is raised to 40 °C. The optical properties of ZnO obtained by UV-Vis reflectance spectroscopy indicate a red shift of the band gap by ~0.1 eV.
Due to the increasing tattoo practicing in Eastern countries and general concern on tattoo ink composition and safety, the green tattoo inks Green Concentrate by Eternal, for European and “for Asia Market Only” were analyzed, under the premise that only the former falls under a composition regulation. A separation of the additives from the pigment was carried out by successive extraction in solvents of different polarities, i.e., water, acetone and dichloromethane. The solid residues were analyzed by IR and Raman spectroscopies, the liquid fractions by GC/mass spectrometry. The relative pigment load and element traces were also estimated. We found that the European and the Asian inks are based on the same pigment, PG7, restricted in Europe, though at different loads. They have a similar content of harmful impurities, such as Ni, As, Cd and Sb and both contain siloxanes, including harmful D4. Furthermore, they have different physical-chemical properties, the European ink being more hydrophilic, the Asian more hydrophobic. Additionally, the Asian ink contains harmful additives for the solubilization of hydrophobic matrices and by-products of the phthalocyanine synthesis. Teratogenic phthalates are present as well as chlorinated teratogenic and carcinogenic compounds usually associated to the laser treatment for removal purposes, to a larger extent in the European ink. The composition of the inks does not seem to reflect regulatory restrictions, where issued.
Extrinsic chemiluminescence can be an efficient tool for determining pesticides and fungicides, which do not possess any intrinsic fluorescent signal. On this basis, (3-aminopropyl) trimethoxysilane (APTMS)-coated ZnO (APTMS@ZnO) was synthesized and tested as an extrinsic probe for the fungicide penconazole. Several synthetic routes were probed using either a one-pot or two-steps method, in order to ensure both a green synthetic pathway and a good signal variation for the penconazole concentration. The synthesized samples were characterized using X-ray diffraction (XRD), infrared (IR), Raman and ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM) imaging and associated energy-dispersive X-ray (EDX) analysis. The average size of the synthesized ZnO nanoparticles (NPs) is 54 ± 10 nm, in line with previous preparations. Of all the samples, those synthesized in two steps, at temperatures ranging from room temperature (RT) to a maximum of 40 °C, using water solvent (G-APTMG@ZnO), appeared to be composed of nanoparticles, homogeneously coated with APTMS. Chemiluminescence tests of G-APTMG@ZnO, in the penconazole concentration range 0.7–1.7 ppm resulted in a quenching of the native signal between 6% and 19% with a good linear response, thus indicating a green pathway for detecting the contaminant. The estimated detection limit (LOD) is 0.1 ± 0.01 ppm.