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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.

Drastic climate changes over the years have triggered environmental challenges for wild plants and crops due to fluctuating weather patterns worldwide. This has caused different types of stressors, responsible for a decrease in plant life and biological productivity, with consequent food shortages, especially in areas under threat of desertification. Nanotechnology-based approaches have great potential in mitigating environmental stressors, thus fostering a sustainable agriculture. Zinc oxide nanoparticles (ZnO NPs) have demonstrated to be biostimulants as well as remedies to both environmental and biotic stresses. Their administration in the early sowing stages, i.e., seed priming, proved to be effective in improving germination rate, seedling and plant growth and in ameliorating the indicators of plants’ well-being. Seed nano-priming acts through several mechanisms such as enhanced nutrients uptake, improved antioxidant properties, ROS accumulation and lipid peroxidation. The target for seed priming by ZnO NPs is mostly crops of large consumption or staple food, in order to meet the increased needs of a growing population and the net drop of global crop frequency, due to climate changes and soil contaminations. The current review focuses on the most recent low-cost, low-sized ZnO NPs employed for seed nano-priming, to alleviate abiotic and biotic stresses, mitigate the negative effects of improper storage and biostimulate plants’ growth and well-being. Taking into account that there is large variability among ZnO NPs and that their chemico-physical properties may play a role in determining the efficacy of nano-priming, for all examined cases, it is reported whether the ZnO NPs are commercial or lab prepared. In the latter cases, the preparation conditions are described, along with structural and morphological characterizations. Under these premises, future perspectives and challenges are discussed in relation to structural properties and the possibility of ZnO NPs engineering.

In the present contribution, inulin coated ZnO nanoparticles (ZnO@inu NPs) were investigated for their potential application on crop production systems, by appraisal of their biostimulating effects on Vicia faba L (faba bean). Naked and coated ZnO NPs were synthesized according to purposely implemented eco-friendly protocols and characterized with multiple techniques to determine their crystallographic phase, average particle size, and degree of coating. Faba beans were grown in culture medium supplemented with NPs at 50 or 100 mg kg−1, using ZnO NPs alone, inulin alone, a mixture of the two, or ZnO@inu NPs. Seed germination rate and biometric evaluations on seedlings were carried out, together with Zn localization in the plant tissues. Cellular and molecular effects were ascertained by analyses of photosynthetic pigments, cytotoxicity, genotoxicity, viability, induction of oxidative stress and tissue damage, antioxidant response, and modulation of gene expression. These combined studies indicated a potential role of ZnO@inu NPs in promoting growth and development of V. faba seedlings, acting at a post-germinative phase, probably by stimulating the stem cell mitosis. Finally, inulin as a coating agent for the ZnO NPs favored the bioavailability and adsorption of the nanomaterials into the plant tissues, without altering their bioactivity but mitigating any adverse side effect.

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.

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.