Effect of MnO2 Nanoparticles Stabilized with Cocamidopropyl Betaine on Germination and Development of Pea (Pisum sativum L.) Seedlings.

This study aimed to synthesize, characterize, and evaluate the effect of cocamidopropyl betaine-stabilized MnO2 nanoparticles (NPs) on the germination and development of pea seedlings. The synthesized NPs manifested as aggregates ranging from 50-600 nm, comprising spherical particles sized between 19 to 50 nm. These particles exhibited partial crystallization, indicated by peaks at 2θ = 25.37, 37.62, 41.18, 49.41, 61.45, and 65.79°, characteristic of MnO2 with a tetragonal crystal lattice with a I4/m spatial group. Quantum chemical modelling showed that the stabilization process of MnO2 NPs with cocamidopropyl betaine is energetically advantageous (∆E > 1299.000 kcal/mol) and chemically stable, as confirmed by the positive chemical hardness values (0.023 ≤ η ≤ 0.053 eV). It was revealed that the interaction between the MnO2 molecule and cocamidopropyl betaine, facilitated by a secondary amino group (NH), is the most probable scenario. This ascertain is supported by the values of the difference in total energy (∆E = 1299.519 kcal/mol) and chemical hardness (η = 0.053 eV). These findings were further confirmed using FTIR spectroscopy. The effect of MnO2 NPs at various concentrations on the germination of pea seeds was found to be nonlinear and ambiguous. The investigation revealed that MnO2 NPs at a concentration of 0.1 mg/L resulted in the highest germination energy (91.25%), germinability (95.60%), and lengths of roots and seedlings among all experimental samples. However, an increase in the concentration of preparation led to a slight growth suppression (1-10 mg/L) and the pronounced inhibition of seedling and root development (100 mg/L). The analysis of antioxidant indicators and phytochemicals in pea seedlings indicated that only 100 mg/L MnO2 NPs have a negative effect on the content of soluble sugars, chlorophyll a/b, carotenoids, and phenols. Conversely, lower concentrations showed a stimulating effect on photosynthesis indicators. Nevertheless, MnO2 NPs at all concentrations generally decreased the antioxidant potential of pea seedlings, except for the ABTS parameter. Pea seedlings showed a notable capacity to absorb Mn, reaching levels of 586.5 µg/L at 10 mg/L and 892.6 µg/L at 100 mg/L MnO2 NPs, surpassing the toxic level for peas according to scientific literature. However, the most important result was the observed growth-stimulating activity at 0.1 mg/L MnO2 NPs stabilized with cocamidopropyl betaine, suggesting a promising avenue for further research.

Acid-Base and Photocatalytic Properties of the CeO2-Ag Nanocomposites.

In this work, CeO2 nanoparticles, as well as CeO2 nanocomposites with plasmonic silver nanoparticles, were synthesized using a simple sol-gel process. The concentration of silver in the composites varied from 0.031-0.25 wt%. Cerium hydroxide dried gel was calcined at temperatures from 125 to 800 °C to obtain CeO2. It was shown that, at an annealing temperature of 650 °C, single-phase CeO2 nanopowders with an average particle size in the range of 10-20 nm can be obtained. The study of acid-base properties showed that with an increase in the calcination temperature from 500 to 650 °C, the concentration of active centers with pKa 9.4 and 6.4 sharply increases. An analysis of the acid-base properties of CeO2-Ag nanocomposites showed that with an increase in the silver concentration, the concentration of centers with pKa 4.1 decreases, and the number of active centers with pKa 7.4 increases. In a model experiment on dye photodegradation, it was shown that the resulting CeO2 and CeO2-Ag nanopowders have photocatalytic activity. CeO2-Ag nanocomposites, regardless of the silver concentration, demonstrated better photocatalytic activity than pure nanosized CeO2.

Synthesis and Characterization of Calcium Silicate Nanoparticles Stabilized with Amino Acids.

This work presents the development of a method for the synthesis of calcium silicate nanoparticles stabilized with essential amino acids. CaSiO3 nanoparticles were obtained through chemical precipitation. In the first stage, the optimal calcium-containing precursor was determined. The samples were examined using scanning electron microscopy. It was found that Ca(CH3COO)2 was the optimal calcium-containing precursor. Then, the phase composition of calcium silicate was studied using X-ray phase analysis. The results showed the presence of high-intensity bands in the diffractogram, which characterized the phase of the nanosized CaSiO3-wollastonite. In the next stage, the influence of the type of amino acid on the microstructure of calcium silicate was studied. The amnio acids studied were valine, L-leucine, L-isoleucine, L-methionine, L-threonine, L-lysine, L-phenylalanine, and L-tryptophan. The analysis of the SEM micrographs showed that the addition of amino acids did not significantly affect the morphology of the CaSiO3 samples. The surface of the CaSiO3 samples, both without a stabilizer and with amino acids, was represented by irregularly shaped aggregates consisting of nanoparticles with a diameter of 50-400 nm. Further, in order to determine the optimal amino acid to use to stabilize nanoparticles, computerized quantum chemical modeling was carried out. Analysis of the data obtained showed that the most energetically favorable interaction was the CaSiO3-L-methionine configuration, where the interaction occurs through the amino group of the amino acid; the energy value of which was -2058.497 kcal/mol. To confirm the simulation results, the samples were examined using IR spectroscopy. An analysis of the results showed that the interaction of calcium silicate with L-methionine occurs via the formation of a bond through the NH3+ group of the amino acid.