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In this work, we investigate by ab initio calculations and optical experiments the sensitivity of graphene quantum dots in their use as devices to measure the presence, and concentration, of heavy metals in water. We demonstrate that the quenching or enhancement in the optical response (absorption, emission) depends on the metallic ion considered. In particular, two cases of opposite behaviour are considered in detail: Cd2+, where we observe an increase in the emission optical response for increasing concentration, and Pb2+ whose emission spectra, vice versa, are quenched along the concentration rise. The experimental trends reported comply nicely with the different hydration patterns suggested by the models that are also capable of reproducing the minor quenching/enhancing effects observed in other ions. We envisage that quantum dots of graphene may be routinely used as cheap detectors to measure the degree of poisoning ions in water.

Deep Eutectic Solvents have gained a lot of attention in the last few years because of their vast applicability in a large number of technological processes, the simplicity of their preparation and their high biocompatibility and harmlessness. One of the fields where DES prove to be particularly valuable is the synthesis and modification of inorganic materials—in particular, nanoparticles. In this field, the inherent structural inhomogeneity of DES results in a marked templating effect, which has led to an increasing number of studies focusing on exploiting these new reaction media to prepare nanomaterials. This review aims to provide a summary of the numerous and most recent achievements made in this area, reporting several examples of the newest mixtures obtained by mixing molecules originating from natural feedstocks, as well as linking them to the more consolidated methods that use “classical” DES, such as reline.

We explore the structure of two ionic liquids based on the choline cation and the monoanion of the maleic acid. We consider two isomers of the anion (H-maleate, the cis-isomer and H-fumarate, the trans-isomer) having different physical chemical properties. H-maleate assumes a closed structure and forms a strong intramolecular hydrogen bond whereas H-fumarate has an open structure. X-ray diffraction, infrared and Raman spectroscopy and molecular dynamics have been used to provide a reliable picture of the interactions which characterize the structure of the fluids. All calculations indicate that the choline cation prefers to connect mainly to the carboxylate group through OH⋯O interactions in both the compounds and orient the charged head N(CH3)3+ toward the negative portion of the anion. However, the different structure of the two anions affects the distribution of the ionic components in the fluid. The trans conformation of H-fumarate allows further interactions between anions through COOH and CO2− groups whereas intramolecular hydrogen bonding in H-maleate prevents this association. Our theoretical findings have been validated by comparing them with experimental X-ray data and infrared and Raman spectra.

Comparative laser and thermal treatments were carried out on PG36, a green phthalocyanine-based pigment, permitted in European countries where legislation on tattoo composition was issued. Prior to the treatments, PG36 was characterized by SEM imaging, EDX, IR and UV–Vis spectroscopies, revealing an excess of Si and C and O as compared to the pure halogenated Cu-phthalocyanine. Laser treatments were carried out with a Nd:YAG device applied to H2O and propan-2-ol dispersions. Pyrolysis and calcinations were carried out in air or under N2 flow. The outcome of the different procedures was analyzed by UV–Vis spectroscopy, GC–mass spectrometry, X-ray diffraction of the solid residues, SEM microscopy and dynamic light scattering. The comparative analysis indicated the production of different fragment compounds depending on the treatment, (pyrolysis or laser), and, to some extent, to the solvent of the dispersion, with pyrolysis generating a larger number of hazardous compounds. Hydrocarbons and cyclic siloxanes present as additives in PG36 were stable or degraded depending on the treatment. The morphology of the products is also treatment-dependent with nanoparticles < 20 nm and fibers being produced upon laser treatments only. Based on the experimental findings, the equivalence of laser and thermal treatments is evaluated.

In this study, a new and very quick method to depolymerize PET plastics is reported. The depolymerization experiments were conducted using a type-IV deep eutectic solvent containing ZnCl2 and urea, and a microwave oven as reactor. Different combinations of power and reaction times were employed while keeping the total energy constant. Successful conversions were obtained carrying out the process at 180 W for 2 min and 360 W for 1 min, whereas at higher powers and shorter times, an inclusion likely occurs of some solvent into the structure of the recovered PET flakes, as suggested by the porosity of the flakes, imaged by SEM microscopy. The flakes increase their crystalline character during the treatment, as indicated by the appearance of narrow diffraction peaks in the XRD patterns, at variance with the broad signals observed in the case of the pristine amorphous polymer. The NMR analysis of the supernatant liquid above the partially solubilized PET shows the presence of terephthalic acid peaks. The infrared spectra of the solid powder achieved upon the acidic treatment of the extract reveal the presence of C=O stretching peaks and the absence of typical CH2 wagging absorptions that satisfactorily comply with the presence of terephthalic acid.

Nitrogen-doped carbon quantum dots are easily obtainable nanomaterials endowed with remarkable fluorescence properties for the detection of contaminations by heavy metals. In this report, we show that nanometric particles with high specificity for silver cations can be prepared by hydrothermal synthesis starting from citric and folic acid solutions. Solutions of these N-CQDs give a strong fluorescence emission in the violet region (385 nm) when excited at 330 nm, which can be quenched selectively by silver (I) cations at sub-nanomolar concentrations, while other cations do not give any effect. This remarkable feature was tentatively correlated with the stronger interactions between silver ion and small portions of the nanomaterial surface by comparing Ag+ and the isoelectronic Cd2+.

In this study, we report a detailed experimental and theoretical investigation of three glycol derivatives, namely ethane-1,2-diol, 2-methoxyethan-1-ol and 1,2-dimethoxy ethane. For the first time, the X-ray spectra of the latter two liquids was measured at room temperature, and they were compared with the newly measured spectrum of ethane-1,2-diol. The experimental diffraction patterns were interpreted very satisfactorily with molecular dynamics calculations, and suggest that in liquid ethane-1,2-diol most molecules are found in gauche conformation, with intramolecular hydrogen bonds between the two hydroxyl groups. Intramolecular H-bonds are established in the mono-alkylated diol, but the interaction is weaker. The EDXD study also evidences strong intermolecular hydrogen-bond interactions, with short O···O correlations in both systems, while longer methyl-methyl interactions are found in 1,2-dimethoxy ethane. X-ray studies are complemented by micro Raman investigations at room temperature and at 80 °C, that confirm the conformational analysis predicted by X-ray experiments and simulations.

The link between morphology and properties is well-established in the nanoparticle literature. In this report, we show that different approaches in the synthesis of copper oxide can lead to nanoparticles (NPs) of different size and morphology. The structure and properties of the synthesized NPs are investigated with powder X-ray diffraction, scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS). Through detailed SEM analyses, we were able to correlate the synthetic pathways with the particles’ shape and aggregation, pointing out that bare hydrothermal pathways yield mainly spheroidal dandelion-like aggregates, whereas, if surfactants are added, the growth of the nanostructures along a preferential direction is promoted. The effect of the morphology on the electronic properties was evaluated through DRS, which allowed us to obtain the electron bandgap in every system synthesized, and to find that the rearrangement of threaded particles into more compact structures leads to a reduction in the energy difference. The latter result was compared with Density Functional Theory (DFT) computational models of small centrosymmetric CuO clusters, cut from the tenorite crystal structure. The computed UV-Vis absorption spectra obtained from the clusters are in good agreement with experimental findings.

Within the framework of plant biostimulation, a pivotal role is played by the achievement of low-cost, easily prepared nanoparticles for priming purposes. Therefore, in this report, two different synthetic strategies are described to engineer zinc oxide nanoparticles with an inulin coating. In both protocols, i.e., two-step and gel-like one-pot protocols, nanoparticles with a highly pure ZnO kernel are obtained when the reaction is carried out at T ≥ 40 °C, as ascertained by XRD and ATR/FTIR studies. However, a uniformly dispersed, highly homogeneous coating is achieved primarily when different temperatures, i.e., 60 °C and 40 °C, are employed in the two phases of the step-wise synthesis. In addition, a different binding mechanism, i.e., complexation, occurs in this case. When the gel-like process is employed, a high degree of coverage by the fructan is attained, leading to micrometric coated aggregates of nanometric particles, as revealed by SEM investigations. All NPs from the two-step synthesis feature electronic bandgaps in the 3.25–3.30 eV range in line with previous studies, whereas the extensive coating causes a remarkable 0.4 eV decrease in the bandgap. Overall, the global analysis of the investigations indicates that the samples synthesized at 60 °C and 40 °C are the best suited for biostimulation. Proof-of-principle assays upon Vicia faba seed priming with Zn5 and Zn5@inu indicated an effective growth stimulation of seedlings at doses of 100 mgKg−1, with concomitant Zn accumulation in the leaves.

This study investigates the nanostructure of two protic ionic liquids (PILs), [N0 0 0 3][C3CO2] and [N0 0 0 4][C2CO2], with similar polar head groups but varying alkyl chain lengths. An X-ray scattering technique and molecular dynamics simulations have been utilized to characterize the bulk and interfacial properties of these PILs. The findings suggest that the nanostructure of the PILs is primarily determined by the electrostatic forces between charged functional groups playing a dominant role. Despite differences in the alkyl chain lengths, the PILs possess remarkably similar nanostructures. Extending our investigation, we report the impact of water on the nanostructure. Our findings reveal that the addition of water disrupts interactions between cations and anions, weakening Coulombic forces. The disruptive behavior is attributed to the establishment of hydrogen bonds between water and ions. This comprehensive approach provides valuable insights into the nuanced factors shaping the nanostructure of these PILs, which are crucial for tailoring their applications in synthetic chemistry, catalysis, and beyond.