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In this paper, we evaluated adsorption of phosgene gas molecule (COCl2), on the hexagonal-aluminum nitride (h-AlN) nanosheet by using first-principles van der Waals density functional theory calculations (vdW-DF) method. The nature of interaction between the phosgene molecule and h-AlN is discovered by geometries, adsorption energies, Mulliken, Hirshfeld as well as Voronoi charges analyses. The density of states (DOS) was calculated and the results show that HOMO/LUMO energy gap of h-AlN is significantly reduced upon the COCl2 adsorption. The projected density of states (PDOS) of the adsorption systems suggested that the enhancement of adsorption was owing to the hybridization between Al atom of h-AlN sheet and the O atom of phosgene molecule. Interestingly, the results reveal that the Eg of h-AlN is very sensitive to the presence of COCl2 molecule as its value reduces from 3.337 eV in pure h-AlN to 1.966 eV (41.08% change) after the COCl2 adsorption which would result in electrical conductance increment. Global reactivity descriptor values such as electronegativity (χ), global hardness (η), global softness (S), electronic chemical potential (μ), electrophilicity index (ω), and electro accepting power (ω+) were calculated. Additionally, the stability of the most stable phosgene/h-AlN complex was evaluated by means of DFT molecular dynamics (MD) simulation at room temperature under constant volume and temperature conditions with PBE method. Based on the DFT calculation results, the h-AlN nano sheet is expected to be potential novel sensor for detecting the presence of COCl2 gas. [ABSTRACT FROM AUTHOR]

The symmetry breaking of molecules depends on its context and origin. It is well shown the pseudo Jahn – Teller effect (PJTE) describes the origin of symmetry breaking of planar configurations. Based on the PJTE theory, the configurations, electronic parameters and conformational changes in molecular systems are predicted. Optimization of the D2h and C2h configurations of tetrahalodigermene Ge2X4 (X = Cl, Br, I) by ab initio calculations showed that the C2h configurations are more stable than planar ones. The different energy between high-symmetry D2h geometries and low-symmetry C2h geometries decrease from Ge2Cl4 to Ge2I4. Instability of the high-symmetry D2h configurations is arising from the PJT coupling of the ground Ag state and the exited B2g state in the Qb2g direction. The PJTE problem creates stable geometries of Ge2X4 (X = Cl, Br, I) analogs with C2h configurations. It is expected that when the energy gap between the desired states with D2h configurations decreases, the PJT stabilization energy (EPJT) increases. Despite this expectation, with increasing the energy gap from Ge2Cl4 to Ge2I4, EPJT decreases. According to the results of the canonical molecular orbital (CMO) analysis, the contributions of the b3u and b1u molecular orbitals in the vibronic coupling constant (F) decrease from Ge2Cl4 to Ge2I4. Consequently, assuming the primary force constant is positive, the negative curvatures of ground state electronic configuration curves in adiabatic potential energy surfaces (APESs) decreases from Ge2Cl4 to Ge2I4. The trend observed for the variations of the chemical hardness (η) of Ge2X4 analogs obey the maximum hardness principle. [ABSTRACT FROM AUTHOR]

This study investigates the interaction between C20 and the cis-PtCl2(NH3)2 complex using MPW1PW91 quantum chemical calculations in gas and solution phases. Two interaction modes between C20 and the cis-PtCl2(NH3)2 complex are considered: I-isomer (η2-C20) and II-isomer (η1-C20). It also determines the effects of the solvent polarity on the dipole moment, electronic spatial extent (ESE), structural parameters, and frontier orbital energies of two possible isomers of the C20…cis-PtCl2(NH3)2 complex. The bonding interaction between C20 and the cis-PtCl2(NH3)2 complex was examined through energy decomposition analysis (EDA). The metal-ligand bonds are evaluated using the percentage composition of the specific groups of frontier orbitals. The quantum theory of atoms in molecules (QTAIM) analysis is applied to assess the Pt-C bonds within the complex. Finally, the Pt-C spin-spin coupling constants are calculated using the gauge independent atomic orbital (GIAO) method. [ABSTRACT FROM AUTHOR]

The effect of solvent on the structural, frontier orbital energies, global density-based descriptors, vibrational frequencies, and 31P NMR chemical shifts was examined for the syn-Cp2Ti(η2-C6H4-2-OMe)(PMe3) complex by the self-consistent reaction field theory (SCRF) based on the polarizable continuum model (PCM). The studied spectroscopic parameters were correlated with the Kirkwood-Bauer-Magat (KBM) equation. Also, the response of the global density-based descriptors (chemical potential and hardness) in the presence of external electric field was studied. EDA, QTAIM, ELF, LOL, and NBO analyses were used for illustration of the Ti-C bond in this complex. [ABSTRACT FROM AUTHOR]

The structural, electronic, and spectroscopic properties of the anticancer active molecule of iproplatin were investigated in the gas and liquid phases. Based on the polarizable continuum model (PCM), the solvent effect on the structural parameters, frontier orbitals, and spectroscopic parameters of the complex was investigated. The results indicate that the polarity of solvents plays a significant role in the structure and pro perties of the complex. H and C NMR chemical shifts were calculated using the Gauge-invariant atomic orbital (GIAO) method. Pt-Cl and Pt-OH bonds were investigated through a vibrational analysis. Moreover, time dependent density functional theory (TD-DFT) was used to calculate the energy, oscillatory strength, and wavelength absorption maximum (λ) of electronic transitions and its nature within the complex. [ABSTRACT FROM AUTHOR]

In this study, the potential of aluminum nitride (h-AlN), boron nitride (h-BN) and silicon carbide (h-SiC) nanosheets as the drug delivery systems (DDS) of isoniazid (INH) was scrutinized through density functional theory (DFT) and molecular dynamic (MD) simulations. We performed DFT periodic calculations on the geometry and electronic features of nanosheets adsorbed with INH by the DFT functional (DZP/GGA-PBE) employed in the SIESTA code. In the energetically favorable model, an oxygen atom of the C-O group of the INH molecule interacts with a Si atom of the h-SiC at 2.077 Å with an interaction energy of -1.361 eV. Charge transfer (CT) calculation by employing the Mulliken, Hirshfeld and Voronoi approaches reveals that the monolayers and drug molecules act as donors and acceptors, respectively. The density of states (DOS) calculations indicate that the HOMO-LUMO energy gap (HLG) of the h-SiC nanosheet declines significantly from 2.543 to 1.492 eV upon the adsorption of the INH molecule, which causes an electrical conductivity increase and then produces an electrical signal. The signal is linked to the existence of INH, demonstrating that h-SiC may be an appropriate sensor for INH sensing. The decrease in HLG for the interaction of INH and h-SiC is the uppermost (up to 41%) representing the uppermost sensitivity, whereas the sensitivity trend is σ (h-SiC) > σ (h-AlN) > σ (h-BN). Quantum theory of atoms in molecules (QTAIM) investigations is employed to scrutinize the nature of the INH/nanosheet interactions. The QTAIM analysis reveals that the interaction of the INH molecule and h-SiC has a partially covalent nature, while INH/h-AlN model electrostatic interaction occurs in the system and noncovalent and electrostatic interaction for the INH/h-BN model. Finally, the state-of-the-art DFT-MD simulations utilized in this study can mimic ambient conditions. The results obtained from the MD simulation show that it takes more time to bond the INH drug and h-SiC, and the INH/h-SiC system becomes stable. The results of the current research demonstrate the potential of h-SiC as a suitable sensor and drug delivery platform for INH drugs to remedy tuberculosis.

We have investigated the interactions between a 5-aminolevulinic acid (ALA) drug and ZnO nanostructures including ZnO monolayers and ZnO nanotubes (ZnONTs) using density functional theory (DFT) calculations. In the context of the dispersion corrected Perdew-Burke-Ernzerhof (PBE) approach, the energetics, charge transfer, electronic structure and equilibrium geometries have been estimated. As ALA is adsorbed onto/into the ZnONTs and on the ZnO monolayer with interaction energies ( E int ) of -2.55/-2.75 eV and -2.51 eV, respectively, the calculated E int values and bonding distances (∼2 Å) reveal that the interaction type is chemisorption. The ZnO nanostructures showed promising performance in the ALA drug functionalization, taking into account the interaction energy values. The band gap almost remains unchanged for both of the substrates under consideration after ALA adsorption, and the semiconductor properties of the substrates are preserved, according to the analyzed density of states (DOSs) spectra. The interaction nature of the ALA-ZnO nanostructures according to the atom in molecule (AIM) analysis was found to be polar attraction with partial covalent bonding between O and Zn. Our DFT based molecular dynamic (MD) simulation results demonstrate that, in the aqueous solution, ALA moves toward the interior sidewall of the ZnONTs and ZnO nanosheet surface and binds to the Zn atom through its O (carbonyl/hydroxyl groups) and N atoms and the hydroxyl H atom was dissociated and binds to the O atom of the ZnO surface. However, in the case of ALA adsorption onto the outer surface of ZnONTs, only the O atoms of carbonyl groups bind to the Zn atom and the structure of the drug remains undestroyed during the adsorption. The current findings shed light on the polar drug adsorption/encapsulation behavior on/into ZnO nanostructures, which may encourage further use of ZnO-based nanomaterials in the field of drug delivery and bio-functionalized nanomaterials.

In this work, we focus our attention on the influence of 2nd-row transition metals on the structural geometries, electronic structures, and absorption characteristics of porphyrin linked with the C 60 fullerene with oligo-p-phenyleneethynylenes (MP-C 60 -oligo-PPEs) compounds. The DFT/B3PW91-D3 and CAM-B3LYP-D3/6-31G (d) calculations revealed that various metals embedded within the porphyrin moiety give different bridge conformations and different HOMO-LUMO energy levels. We calculate the UV-Vis spectra and absorption parameters using the time-dependent ZINDO/S approach. Our findings indicate that all the compounds have enhanced absorptions in the visible light range, and their molecular orbital energies adopt the condition of sensitizers. However, all of the complexes except down spin states exhibit considerably charge spatial separation. The results suggest that the ZnP-C 60 -oligo-PPEs triad can meet the necessary conditions of the sensitizer of dye-sensitized solar cells (DSSCs) in comparison with other counterparts and could be an optimum triad compound for potential application in photovoltaic devices., (Copyright © 2022 Elsevier B.V. All rights reserved.)

A simple and fast method named microfunnel-filter-based emulsification microextraction is introduced for an efficient determination of some organophosphorus pesticides including diazinon, malathion, and chlorpyrifos in the environmental samples including the river, sea, and well water. This method is based upon the dispersion of a low-toxicity organic solvent (dihexyl ether), as the extractant, in a high volume of an aqueous sample solution (45 mL). It is implemented without a centrifugation step, and using a syringe filter and a micro-funnel, the phase separation and transfer of the enriched analytes to the gas chromatograph are simply achieved. By filtration of the extractant phase, a suitable sample clean-up is obtained, and the total extraction time is just a few minutes. The factors influencing the extraction efficiency are optimized, and under the optimal conditions, the proposed method provides a good linearity (in the range of 15-1500 ng/mL (R 2  > 0.996). A high enrichment factor is obtained (in the range of 306-342), and the method provides low limits of detection and quantification (in the ranges of 4-8 and 15-25 ng/mL, respectively)., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study aimed to synthesize methoxy polyethylene glycol propionaldehyde (mPEG 20,000 -ALD) for the preparation of PEGylated nanoliposomal cisplatin. Nanocarriers such as liposomes are developed for a wide range of drug delivery systems. PEG with high molecular weight (Mw) is used to coat the liposomes. In this study, simulated Fourier transform infrared (FTIR) spectra of mPEG-ALD were obtained using density functional theory (DFT) calculations and then compared with actual FTIR spectrum of mPEG 20,000 -ALD (Mw = 20 kDa). We found that the intensity of C = O stretching vibration at 1,700 cm -1 related to the carbonyl functional group of mPEG 20,000 -ALD was very weak. The results of DFT calculations of mPEG-ALD showed that by increasing the Mw of mPEG-ALD, the intensity of C = O stretching vibration related to the carbonyl functional group of mPEG-ALD was decreased, so we concluded the hypothesis of decreasing the intensity of C = O stretching vibration at 1,700 cm -1 as a result of increasing the Mw of mPEG-ALD. In vitro release of cisplatin showed that the percentages of released cisplatin from PEGylated nanoliposomal cisplatin and free cisplatin were determined to be 46 ± 2% and 97 ± 3% after 35 h, respectively. Cytotoxicity of free cisplatin and PEGylated nanoliposomal cisplatin was evaluated and related half-maximal inhibitory concentration on human ovarian cancer cell line A2780CP was obtained to be 76.6 ± 3.1 and 46.6 ± 2.3 μg/mL, respectively.

The present study describes the preparation and capability of the graphene oxide/almond shell (GO@AS) composite by a freeze-drying method. The composite showed excellent ability to uptake nickel and cadmium ions, which were characterized by Fourier transform infrared spectrum and scanning electron microscopy techniques. The optimized values of pH, contact time, and adsorbent doses were found to be 7.5, 30-180 min, and 0.1 g, respectively. Also, adsorption isotherms of metal ions on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum sorption capacities of GO@AS calculated from Langmuir isotherm model were 121.95 mg/g for Cd (II) and 69.93 mg/g for Ni (II). A higher adsorption capacity was for Cd (II) on GO@AS. PRACTITIONER POINTS: Synthesis of graphene oxide-almond shell composite. Removal of Cd and Ni ions from water by graphene oxide-almond shell composite. Study of isotherm adsorption models., (© 2019 Water Environment Federation.)