Lead (Pb) toxicity has a great impact in terms of toxicity towards living organisms as it severely affects crop growth, yield, and food security; thus, warranting appropriate measures for the remediation of Pb polluted soils. Phytoextraction of heavy metals (HMs) using tolerant plants along with organic chelators has gained global attention. Thus, this study examines the possible influence of citric acid (CA) on unveiling the potential phytoextraction of Pb by using castor beans. For this purpose, different levels of Pb (0, 300, 600 mg kg−1 of soil) and CA (0, 2.5, and 5 mM) were supplied alone and in all possible combinations. The results indicate that elevated levels of Pb (especially 600 mg kg−1 soil) induce oxidative stress, including hydrogen peroxide (H2O2) and malanodialdehyde (MDA) production in plants. The Pb stress reduces the photosynthetic traits (chlorophyll and gas exchange parameters) in the tissues of plants (leaves and roots), which ultimately lead to a reduction in growth as well as biomass. Enzyme activities such as guaiacol peroxidase, superoxide dismutase, ascorbate peroxidase, and catalase are also linearly increased in a dose-dependent manner under Pb stress. The exogenous application of CA reduced the Pb toxicity in plants by improving photosynthesis and, ultimately, plant growth. The upsurge in antioxidants against oxidative stress shows the potential of CA-treated castor beans plants to counteract stress injuries by lowering H2O2 and MDA levels. From the results of this study, it can be concluded that CA treatments play a promising role in increasing the uptake of Pb and reducing its phytotoxicity. These outcomes recommend that CA application could be an effective approach for the phytoextraction of Pb from polluted soils by growing castor beans.
The study under consideration represents the computational calculations of Azo-based direct dye named p-(dimethylamino)azobenzene (DMAB) under the effect of solvents with different relative permittivities. A density functional theory (DFT) method at the B3LYP level with 6-311G++ was applied for the spectroscopic and structural analysis of the title compound. Calculations of geometric parameters (bond orders, bond lengths, and dihedral angles), electron densities, thermodynamic parameters, and orbital energies were performed for the title compound. Mulliken population analysis (MPA) as well as natural population analysis (NPA) was also performed at the B3LYP level with different solvents for finding solvent effects. In order to predict the reactivity of DMAB, molecular electrostatic potential (MESP) calculations were carried out for it. For vibrational analysis, the infrared (IR) spectra were computed for the title compound at the B3LYP/6-311G++ level in the gas phase and in different solvents with good agreement to the experimental FT-IR spectrum. The different modes of vibrations were assigned using potential energy distribution (PED). The computed Raman spectra also showed appreciable agreement with the experimental recorded Raman spectrum. The electronic absorption spectra of the title compound have been computed employing DFT/B3LYP with the 6-311G++ basis set in the gas phase and in four different solvents, that is, DMSO, ethanol, acetonitrile, and water which were compared with the experimental spectra with appreciable agreement. NBO analysis was carried out for understanding the intramolecular and intermolecular bonding of the compound and the density transfer from completely filled to unfilled orbital was found. The HOMO-LUMO energies were determined for analyzing the mechanism of intramolecular charge transfer.
Four cyano groups have been substituted on the aromatic ring of p-hydroquinone (2,3,5,6-tetracyanohydroquinone) in order to study the enhanced photoacidity of this molecule. The acid-base equilibria have been studied using absorption (for ground state pKa) and fluorescence (excited state pKa) spectra. Three distinct species (neutral, anionic and dianionic forms) were observed in the ground state and only two species (anionic and dianionic forms) were found in the excited state when studied at different pH/Ho in water. Absorption and emission characteristics were studied in various organic solvents, including protic and aprotic solvents. Deprotonation was also investigated using binary mixtures. It has been revealed that absorption and emission spectra are considerably changed with change in media. Proton transfer to the solvent has been observed in various solvents.
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