In recent decades, the indiscriminate use of antibiotics and their discharge into the environment have caused serious consequences for aquatic and terrestrial organisms. The present study investigates the optimization of cefixime antibiotic decomposition by a powerful catalytic ozonation process. In this study, the MgAl-LDH /zeolite nanocomposite was synthesized and used as an ozonation-adsorption catalyst to degrade Cefixime antibiotic from an aqueous solution. XRD, FE-SEM, and FTIR analyses were scrutinized to reveal the main characteristics of the as-prepared nanocomposite, showing that it was well-synthesized. The investigated variables in the catalytic ozonation of Cefixime by the mentioned nanocomposite included solution pH level (5–9), nanocatalyst dose (0.5–2.5 g/L), Cefixime concentration (5–25 mg/L) and reaction time (5–60 min) which they were optimized by adopting RSM-CCD. The results showed that all variables positively affected the efficiency of the catalytic ozonation process. Nonetheless, the lowest effect of operational factor pH, the degradation of Cefixime was subjected to the initial content of Cefixime in this treatment system. The optimal conditions for cefixime removal by catalytic ozonation process were determined at pH of 7.72, nanocatalyst dosage of 1 g/L, cefixime concentration of 23 mg/L, and reaction time of 55 min. In the optimized operating conditions, the removal efficiency of Cefixime by MgAl-LDH /zeolite nanocomposite was high, up to 98.37

This study investigated the anti-inflammatory, anticancer, antiviral, and antibacterial effects of allicin and its complexes (Allicin/C₂₄, Allicin/B₁₂N₁₂, and Allicin/Al₁₂N₁₂) using advanced computational techniques such as Density Functional Theory (DFT), Quantum Theory of Atoms in Molecules (QTAIM), and molecular docking. The interactions were analyzed in two phases: gas and aqueous. Results revealed that the Allicin/Al₁₂N₁₂ complex exhibited the highest adsorption energy (Ead = -44.43 kcal/mol in the gas phase) and thermodynamic stability (ΔH = -44.36 kcal/mol, ΔG = -29.19 kcal/mol). QTAIM analysis revealed that the Allicin/C₂₄ complex involves very weak noncovalent interactions, the Allicin/B₁₂N₁₂ complex shows weak covalent bonding with considerable ionic character; and the Allicin/Al₁₂N₁₂ complex exhibits stronger covalent interactions with significant electron density sharing. The Allicin/Al₁₂N₁₂ complex showed a reduced energy gap (3.44 eV) and higher reactivity than free allicin (5.42 eV). Molecular docking demonstrated that this complex had the strongest binding affinity with biological targets, such as HER2, TNF-α, COVID-19 main protease, and Staphylococcus aureus. UV-Vis and IR spectroscopy revealed significant electronic and vibrational modifications in the complexes, particularly Allicin/Al₁₂N₁₂. These findings suggest that nanocages, especially Al₁₂N₁₂, can significantly enhance the stability, bioavailability, and therapeutic potential of allicin. The Allicin/Al₁₂N₁₂ complex, with its strong binding affinity and favorable electronic properties, has emerged as a promising candidate for treating cancer, inflammation, bacterial infections, and COVID-19. This study highlights the importance of natural products in drug discovery and the role of computational methods in understanding complex biological interactions.

The interaction between sulfasalazine (SSZ) through different functional groups and poly (lactic acid) (PLA) in the chloroform phase was investigated in this study using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The binding energy and thermodynamic parameters show that the hydrogen double bond interaction between SSZ and PLA in state I (−0.71 eV) is stronger than in states II (−0.64 eV) and III (−0.51 eV). The SSZ and PLA interaction results in an enhanced dipole moment, greater solubility, and more negative values for Gibbs free energy (ΔGsolv) and energy gap (Eg). Considerable changes in absorption peaks of SSZ and PLA indicate surface adsorption of the drug (SSZ) into the carrier (PLA) in UV–Vis spectra. Theoretical UV–Vis analysis demonstrates SSZ interaction with PLA happens in the ultraviolet region with a maximum absorption peak at 380 nm, which is close to experimental UV–Vis analysis. The experimental spectra showed minimal variations in the maximum absorption wavelength, with respect to theoretical calculations. The presence of SSZ was found to cause a modification in the structure of PLA, as evidenced by both experimental and theoretical Infrared (IR) spectra.

This study aimed to investigate the interaction of oleic acid (OA) with poly (lactic acid) (PLA) microparticle in chloroform and dichloromethane phases using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The study was conducted at the B3LYP-D3/6-31+G** level of theory. The binding energy, dipole moment. and thermodynamic parameters show that the interaction between OA and PLA via C=O….H-O bonds in the most stable state (state I) in the chloroform phase is stronger than in the dichloromethane phase. Negative values of the thermodynamic parameters in the most stable complex and the MEP graphs showed that OA has a positive impact on the adsorption behavior of the PLA. The presence of OA altered the structure of PLA based on theoretical UV-Vis and Infrared (IR) spectra. The findings revealed that using the OA surfactant can improve dispersion and compatibility with the PLA matrix. For citation: Safa A.N., Sheibani A., Baei M.T., Sayyed-Alangi S.Z., Lemeski E.T. Oleic acid as an effective surfactant for poly (lactic acid) microparticle: A DFT study. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 6. P. 65-72. DOI: 10.6060/ivkkt.20246706.7069. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

The Petasites hybridus rhizome water extract as green media was used for the preparation of the Ag/Fe3O4/TiO2/CuO@MWCNTs magnetic nanocomposites and its activity was evaluated by using in the one-pot multicomponent reaction of isoquinoline, α-haloketones, 2-amino benzoic acids, diethyl carbonate, electron deficient acetylenic compounds, ammonium acetate, and tert-butyl isocyanide in water at room temperature for the production of novel derivatives of pyrimidobenzazepines in excellent yields. Moreover, reduction of organic pollutants such 4-nitrophenol was performed by synthesized Ag/Fe3O4/TiO2/CuO@MWCNTs in water at room temperature. The outcomes showed this catalyst was decreased organic pollutants in few seconds. Because of having azepine moiety, the synthesized compounds show good antioxidant activity. These synthesized compounds also displayed antimicrobial activity by using the disk diffusion procedure and two Gram-positive and Gram-negative bacteria. The employed process for production of benzazepines has some benefits such as short time of reactions, excellent efficiency of product, easy separation of catalyst and products.

In this research we investigated the preparation of new (5Z, 8Z)-7H-pyrido[2,3-d]azepine derivatives in high yields via multicomponent reaction of isatins, alkyl bromides, activated acetylenic compounds and ammonium acetate using ionic liquid 1-octhyl-3-methyl imidazolium bromide ([OMIM]Br) as a stabilizer and soft template at room temperature in the presence of Fe3O4/TiO2/Carbon nanotubes magnetic nanocomposites as a reusable and effective nanocatalyst that are synthesized using ionic liquid [OMIM]Br as a stabilizer, soft template, green media and moderate base. Because of having a NH group in the synthesized pyridine derivatives, we investigate antioxidant property of some synthesized compounds by diphenyl-picrylhydrazine (DPPH) radical trapping and power of ferric reduction experiment. Short time of reaction, high yields of product, easy separation of catalyst and products are some advantages of this procedure.

Antioxidative activity of chrysin (CYS) on the B12N12 nanocage has been evaluated by density functional theory with B3PW91-D3 and M06-2X-D3 methods. Adsorption behavior and study of topologies demonstrated that the CYS has chemisorbed to the nanocage and shows notable changes in the electronic properties of B12N12. The antioxidant properties of the CYS and CYS/B12N12 systems have been studied in the different environments by the M06-2X-D3 method. The findings demonstrated that in the vacuum phase and water, benzene, and ethanol solvents, the BDE (5O-H), PDE, PA values of CYS/B12N12 are smaller than those of CYS system. The current study implied that B12N12 nanocage can increase the antioxidative properties of the CYS.

The functionalization of boron nitride (B12N12/B16N16) nanoclusters with glycine in gaseous and aqueous environments were studied. The corresponding changes of spectroscopic, electronic, and thermodynamic properties of the B12N12 and B16N16 nanoclusters were evaluated by means of the density functional theory (DFT) calculations. Analysis of the binding energies shows that the interaction of glycine amino acid toward B12N12 is more remarkable than B16N16 in the gas and solvent environments. Thermodynamic properties also indicate that the glycine molecule energetically prefers to interact with the B12N12 and B16N16 nanoclusters through its amine group rather than carbonyl and hydroxyl groups. Our calculations also demonstrated that the electronic features of B12N12 and B16N16 nanoclusters on the adsorption of glycine from its carbonyl group in the aqueous environment is more altered than the amine and hydroxyl groups. Molecular docking shows that the [(NH2)-Glycine](2)/B12N12 complex has a good binding affinity with protein tumor necrosis factor-alpha (TNF-alpha) and interleukin-1 beta (IL-1 beta) in comparison with the other glycine-BN nanocluster complexes thus making this hybrid bio-inorganic medium a promising material for biomedical and drug-delivery applications. (C) 2021 Elsevier B.V. All rights reserved.

The external electric field can effectually enhance the electronic and optical features of low dimensional systems. Hence, the corresponding atomic structure and adsorption feature changes of a B12N12 fullerene under different applied external electric fields for dimethyl methylphosphonate (DMMP) detection were evaluated. The adsorption of DMMP on the B12N12 surface has been calculated using density functional theory (DFT) and time dependent density functional theory (TDDFT) by the PBE (Perdew-BurkeErnzerhof) functional to study the effects of the parallel (E-X) and transverse (E-Y) external electric fields on the structural and optoelectronic features of the pure fullerene. Through the analysis of the binding energy it is found that B12N12 fullerenes, in the presence of a parallel external electric field (E-X = 0.15 a.u.), are energetically favored when compared to B12N12 fullerenes in the presence of a transverse external electric field (E-Y = 0.15 a.u.). The results demonstrate that a transverse external electric field ranging from 0.005 a.u. to 0.015 a.u. could enhance the DMMP sensitivity of the B12N12 fullerene (with a significant reduction of energy band gap), which potentially could aid in the development of a room temperature DMMP gas sensor. The adsorption and desorption of DMMP could be controlled by external electric field too, which has the potential for applications in itself, relative to DMMP collection and storage. (C) 2021 Elsevier B.V. All rights reserved.

In this study, geometries, binding, optical and electronic features and charge-transfer characteristics of magnesium oxide nanotubes (MgONTs) interacting with uracil pyrimidine were evaluated in both vacuum and solvent (water and toluene) environments by using density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The binding energy of uracil was estimated to be in a range of -0.543 to -1.864 eV in vacuum, -0.347 to -1.709 eV in toluene, and -0.193 to -1.592 eV in water environments. Furthermore, the values of the binding and reaction energies are all negative meaning that the binding of uracil on MgONT is energetically favorable and the synthesis of the complex structure is possible. The results illustrate that the adsorption energy values of uracil on MgONT also follow the order of vacuum > toluene > water. Our analysis demonstrates that solvent polarity is so significant on the stability and reactivity of uracil. In contrast to vacuum and toluene environments, the dipole moment value of MgONT in water environment was significantly increased upon adsorption of uracil. Our findings illustrate that MgONT was more sensitive for detecting the uracil in vacuum environment than water and toluene environments to exploit as a biochemical sensor. (C) 2021 Published by Elsevier B.V.

Adsorption and antiradical activity of apigenin on the surface of B12N12 nanocluster has been investigated by using density functional theory (DFT) within B3PW91-D and M06-2X-D methods. Adsorption values and analysis of topologies showed that the molecule has chemisorbed to the nanocluster surface and induces significant changes in electronic properties of the fullerene. Antioxidative activities of the APG and APG/B12N12 complex have been investigated using the M06-2X-D level of theory based on the hydrogen atom transfer (HAT), single electron transfer followed by proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET). For this purpose, the bond dissociation enthalpy (BDE), ionization potential (IP), proton dissociation enthalpy (PDE), proton affinity (PA) and electron transfer enthalpy (ETE) values were calculated in gas, benzene, ethanol, and water phases to better understand the antioxidative properties of the investigated compounds. The results showed that in the gas and the solvent phases, the BDE and IP values of APG are slightly smaller than those of APG/B12N12 complex. Also, in gas and the phases, the PA values of APG/B12N12 complex are much smaller than those of APG especially in the gas and benzene phases. This work confirms the adsorption of APG on B12N12 nanocluster would enhance the antiradical activity of the APG.

The first-principles calculations to investigate the adsorption behavior of thiocyanate anion (SCN-) on the external surface of H-capped (6, 0), (3, 3), and Al and Ga doped (3, 3) single-walled boron nitride nanotubes (SWBNNTs) has been performed. Binding energy and the equilibrium distance corresponding to the most stable state of SCN-/(3, 3) BNNT is found to be -1.747 eV and 1.546 A, respectively, which can represent mainly a polar covalent bond. The calculation results have shown that both doped aluminum and gallium can enhance the adsorption energy of SCN- into the (3, 3) BNNTs. For the SCN- /BNNT complexes, the energy gaps, NBO, dipole moments, natural atomic orbital occupancies and global indices have been computed using DFT theoretical method at B3LYP level and 6-31G** basis set. Finally, a novel type of the adsorbent that can be used to remove of SCN- anion has been reported.

This study provides details of the electronic and optical structures and binding energies of sarin (SF) and chlorosarin (SC) with Al–N and Al–P surfaces of Al12N12 and Al12P12 nanoclusters in the gas phase. The adsorption mechanism of SF and SC on these nanoclusters containing the Al3+ central cation was studied. Optimized geometries and thermodynamic parameters of SF and SC adsorption complexes were calculated. SF and SC are chemisorbed on these nanoclusters because of the formation of PO···Al bonds. The chemical bond is formed between an oxygen atom of SF and SC and an aluminum atom of fullerene‐likes (chemisorption). However, the binding energies of the complexes with the Al12N12 nanocluster are larger than these values for the Al12P12 nanocluster. The interaction enthalpy and Gibbs free energy of all studied systems were found to be negative. We can conclude that SF and SC will be adsorbed preferably on Al12N12 nanocluster.

The interaction energies and optoelectronic properties of sarin (SF) and chlorosarin (SC) on the B12N12 with and without the presence of an electric field have been studied using density functional theory (DFT) calculations.

Density functional theory calculations were carried out to investigate the adsorption behaviors of dopamine (DPM) on the BN nanostructures in gas and solvent phases. Our results revealed that the adsorption of DPM on BN nano-cages was stronger than other BN nanotubes. It was found that the adsorption of two DPM (−1.30 eV) upon B12N12 was weaker than those of a single DPM (−1.41 eV). The Ga-doped B12N12 had better conditions for the detection of DPM than that of the Al-doped B12N12 nano-cage. The solvation effects for the most stable systems were calculated which showed that it had positive impacts upon the adsorption behavior of the applied systems than those studied in gas phase. The available results are expected to provide a useful guidance for the adsorption of DPM and generation of the new hybrid compounds.

The physisorption and chemisorption of Thiophene (C4H4S) onto the B12N12, B11AlN12, and B11SiN12 fullerenes have been investigated in both gas and solvent environments by means of density functional theory calculation. We found that the higher physisorption of C4H4S in the top site of boron atom of B12N12 fullerene is − 0.14 eV (II), while in the top sites of Si and Al in B11AlN12 and B11SiN12 fullerenes were − 0.58 (VII) and − 1.08 eV (V), respectively. We believe that B11AlN12 fullerene is responsible for the increase of binding energy and reduction of the energy band gap in comparison with B11SiN12 fullerene. This data demonstrates that the increase of charge transfer and dipole moment led to the accretion of binding energy. Therefore, B11AlN12 fullerene will give additional insights of reducing sulfur contents and it also can serve as an adsorbent in the detection of the C4H4S molecule.

The stability, geometry, and electronic properties of C-20 and its AlnPnC20-2n heterofullerenic derivatives where n = 1-10 are probed, at density functional theory (OFT). Vibrational frequency calculations show that exclusive of Al6P6C8 and Al10P8C2, other species are true minima. Exploring of the optimized structures demonstrates the shrinkage of C=C double bonds to compensate for the longer C-Al, C-P and Al-P single bonds. The calculated binding energy, HOMO-LUMO gap and nucleus independent chemical shift at the cage center (NICS (0)) of Al1P1C18 shows it the most stable structure. While substituting of 1, 2, 3, 4, 6, and 7 Al-P units enhances kinetic stability of the resulting heterofullerenes against electronic excitations via increasing their HOMO-LUMO gap, doping of 5, 8, 9, and 10 Al-P units increases the conductivity of heterofullerenes through decreasing their band gap. Substitutional doping leads to a high point charge upon the surfaces of all derivatives, especially the highest delocalization on Al6P6C8, with range of -2.056 to -1.261 charged carbons, +1.493 to +1.586 charged aluminums, and +0.513 to +0.801 charged phosphor atoms, followed by Al4P4C12. These high charge distributions on the surfaces of the studied analogous can develop their storage capacity and henceforth characterize them worthy of investigation for hydrogen storage. Also, Al1P1C18, Al2P2C16, and Al10P10 are shown as the most aromatic and anti-aromatic nanocages with NICS (0) of -41.60, -39.82, and +22.59 ppm, respectively, compared to C-20 (-19.61 ppm). The computed higher dipole moment of Al1P1C18 and Al5P5C10 (4.06 and 3.29 Debye, respectively) exhibits higher reactivity potential and greater affinity of them to more polar solvents. Thus, in both gas phase and polar solvent, Al1P1C18 structure is expected to be stabilized to a greater extent than the other species, which has been confirmed by the thermodynamic and kinetic data. (C) 2018 Elsevier B.V. All rights reserved.

DFT calculations are applied to compare and contrast germanium atom(s) substituted C20-nGen heterofullerenes with n=1-5, where the substitution is completely isolated from each other by means of one carbon atom in equatorial position. The structural stabilities, geometry, and electronic properties of C-20 and its heterofullerene derivatives are compared and contrasted at M062X/6-311++G**, B3LYP/AUG-cc-pVTZ, B3LYP/6-311++G**, B3LYP/6-311+G*, and B3PW91/6-311++G** levels of theory. Vibrational frequency analysis shows that all of the heterofullerenes are real minima. Contrary to identical bonds in C-20, contractions of C=C double bonds are encountered at the expense of longer C?Ge bonds in C20-nGen. In contrast to previous reports on silicon doped heterofullerenes, none of the computed heterofullerenes collapses to open cage structures. Successive Ge doping on C-20 induces more positive atomic charge on Ge atoms and more negative charge on C atoms. High charge transfer on the surfaces of our stable heterofullerenes provokes further investigations on their possible application for hydrogen storage. As to band gap, binding energy, heat of atomization per carbon, nucleus-independent chemical shift, aromaticity, and the smallest vibrational frequency C19Ge immerges with the highest value. The reactivity in terms of ionization potential, nucleophilicity, electrophilicity, hardness, softness, maximum electronic charge, and proton affinity issues predicts C19Ge as the most stable heterofullerene against electronic excitation.

The absorption feasibility of benzene molecule in the C 24 , Si@C 24 , Si-doped C 24 , and C 20 fullerenes has been studied based on calculated electronic properties of these fullerenes using Density functional Theory (DFT). It is found that energy of benzene adsorption on C 24 , Si@C 24 , and Si-doped C 24 fullerenes were in range of –2.93 and –51.19 kJ/mol with little changes in their electronic structure. The results demonstrated that the C 24 , Si@C 24 , and Si-doped C 24 fullerenes cannot be employed as a chemical adsorbent or sensor for benzene. Silicon doping cannot significantly modify both the electronic properties and benzene adsorption energy of C 24 fullerene. On the other hand, C 20 fullerene exhibits a high sensitivity, so that the energy gap of the fullerene is changed almost 89.19% after the adsorption process. We concluded that the C 20 fullerene can be employed as a reliable material for benzene detection.

The present theoretical study suggests the adsorption of the chemical warfare agents (Soman, Chlorosoman, Sarin, and Chlorosarin) over the pure and cobalt-decorated C24 fullerenes by using PBE functional. For all four species, adsorption on the C24 fullerene takes place via a CoOP dative covalent bond between a cobalt-decorated site. It has been indicated that the interaction between the chemical warfare agents and the cobalt-decorated C24 fullerene is more stable than that of the pure C24 fullerene. We found that the cobalt-decorated C24 fullerene is the most favorable site for Sarin and Soman in comparison with Chlorosarin and Chlorosoman. In addition, the interactions of chemical warfare agents with cobalt-decorated C24 fullerene can be responsible to alter of the structural and electronic properties.