Role of axial ligand on the electronic structures of active intermediates in cytochrome P-450, peroxidase and catalase

DFT method (B3LYP) with 6-31G^* basis set was utilized in the computation of a fully optimized structure, net atomic charges and spin densities of the intermediate of cytochrome P-450-oxoiron(IV) porphyrin cation radical, compound I – in the presence of axial ligand such as thiolate (SMe⁻) imidazole (IM), phenoxide (OPh⁻), methoxide (OMe⁻) and chloride (Cl⁻). The results show doublet states in compound I are about 2–4 kcal/mol more stable than quartet states for all aforementioned ligands, and the doublet state is the ground state in all cases. However, electron donor ability of the ligands are in the order of SMe⁻ > IM > OMe⁻ > OPh⁻ > Cl⁻. Also the active oxidant intermediate of cytochrome P-450 between different mesomeric structures select sulfur oxygen radical type structure and can be viewed as (RS^↓)Fe^↑(IV)(O^↑)(Por). In horseraddish peroxidase (HRP) and peroxidase with histidine axial ligand π cation radical character of porphyrin ring is preferred (Im)Fe^↑(IV)(O^↑)(Por^↓). For the ligands such as OMe⁻, OPh⁻ and Cl⁻ oxidation mainly took place on the iron and the active intermediate can be viewed as (L)Fe^↑(V)(O)(Por) with one unpaired electron localized on the iron.     

Theoretical study of structure, bonding, and aromaticity of borazyne and B-substituted borazynes

The density functional theory (DFT) is used to study the geometries, and electronic structures of triplet and singlet of borazyne and B-substituted of borazyne. The aromaticity of these systems is analyzed in the light of nucleus-independent chemical shift (NICS), average of two-center indices (ATI). These methods show increasing of aromaticity in deactivating groups. The relation between electron density in ring critical point (RCP) and NICS(1.0) is observed. The most important interaction in these molecules has been investigated by natural bonding orbital method (NBO).     

Effect of the Solvent Polarity on the Optical Properties in the (OC)5Cr=(OEt)(Ph) Complex: A Quantum Chemical Study

Russian Journal of Physical Chemistry A - In this study, using the B3LYP* method, quantum chemical computations were applied for analyzing the effects of solvent on the electronic spectrum features...     

Computational study of substituent effect in para substituted platinabenzene complexes

The electronic structure and properties of the platinabenzene and para substituted platinabenzenes have been investigated using the hybrid density functional mpw1pw91 theory. The substituent effect in structure parameters, frontier orbital energies, aromaticity indexes, and hyperpolarizability has been studied. The calculations show that, in all molecules HOMO → LUMO transition makes the major contribution in the most intense electronic transition.     

Potassium phthalimide： An efficient and green organocatalyst for the synthesis of 4-aryl-7-（arylmethylene）-3,4,6,7-tetrahydro-1H- cyclopenta[d]pyrimidin-2（5H）-ones]thiones under solvent-free conditions

An efficient synthesis of Biginelli-type compounds using potassium phthalimide as a green, mild, and commercially available organocatalyst in a one-pot, multi-component cyclocondensation reaction of cyclopentanone, aldehydes, and urea/thiourea is reported. The present methodology is a green approach to access 4-aryl-7-（aryImethylene）-3,4,6,7-tetrahydro-1H-cyclopenta[d]pyrimidin-2（5H）-ones/thiones. It offers several merits such as simple operational procedures, no use of hazardous organic solvents, and cheap and environmentally friendly solid basic catalyst.     

Preparation of CoFe2O4/sawdust and NiFe2O4/sawdust magnetic nanocomposites for removal of oil from the water surface

In this study, CoFe₂O₄/Sawdust and NiFe₂O₄/Sawdust magnetic nanocomposites were synthesized using a hydrothermal method, and then characterized using X-ray powder diffraction, Infrared, scanning electron microscopy, Brunauer–Emmett–Teller/Barrett–Joyner–Halenda, and vibrating-sample magnetometer techniques. In this study, unmodified sawdust (US), modified sawdust (MS), unmodified CoFe₂O₄/sawdust (UCS), modified CoFe₂O₄/sawdust (MCS), unmodified NiFe₂O₄/sawdust (UNS), and modified NiFe₂O₄/Sawdust (MNS) magnetic nanocomposites, which are inexpensive, economical, environmentally friendly absorbents, and have a high selective hydrophobic, were used for the removal of oil from the water surface. The results show that the UCS, MCS, UNS, and MNS magnetic nanocomposites can selectively absorb the oil spreading on the water surface, due to its superhydrophobicity and superoleophilicity, and can be easily collected from water under the influence of a magnetic field. In addition, the results showed that the absorbents reach their equilibrium at the 30-min mark. Among all the absorbents, the MNS magnetic nanocomposite showed the maximum absorption capacity (18.172 g/g) at the 40-min mark. The results of the kinetic studies showed that the second-order kinetic equation with the highest correlation coefficient had the best fit with the experimental results.     

Hammett and Brown correlations in the structure and electronic properties of H2Si=SiHAr (Ar = p-C6H4X; X = NH2, OH,Me, H,F, Cl,CHO, COOH,CN, NO2) molecules

Substituent effect on the structure and electronic properties of H₂Si=SiHAr (Ar = p-C₆H₄X; X = NH₂, OH, Me, H, F, Cl, CHO, COOH, CN, NO₂) molecules are studied at the CAM-B3LYP/6-311G(d,p) level of theory. Energy decomposition analysis (EDA) is used as a useful tool for illustrating the interaction between H₂Si and SiHAr fragments in HArSi=SiH₂ molecules. Energetic analysis reveals that the singlet state of the fragments is more stable than triplet state. Also, interactions are stronger in the presence of electron-withdrawing groups (EWGs) in comparison to electron donating groups (EDGs). EDG and EDG effects are investigated on the stability of fragments, frontier orbital energy, distortion, HOMO–LUMO gap, electron-donating (ω⁻) and electron-accepting (ω⁺) powers of the studied molecules. Then, the correlations between these calculated parameters with the Hammett and Brown constants (σ_p and σ_p⁺, respectively) are provided. Also, time-dependent density functional theory method (TD-DFT) is employed for the determination of the strongest absorption band values (λ_max,el) of these molecules. This absorption band is attributed to the HOMO →LUMO transition.     

Computational study of osmabenzyne: The solvent effects on the structure and spectroscopic properties (IR,NMR)

In this article, the structural, electronic, and spectroscopic properties of osmabenzyne Os{≡CC(SiH₃)=C(CH₃)C(SiH₃)=CH}Cl₂(PH₃)₂ are explored in the gas phase and five solvents. The effects of solvents on the structural parameters, frontier orbital energies, and spectroscopic parameters of the complex are elucidated using the polarizable continuum model. The wavenumbers of selected IR-active vibrations in different solvents are obtained and correlated with the Kirkwood–Bauer–Magat equation. In addition, thermodynamic parameters of solvation are calculated for the complex. ¹H and ¹³C NMR chemical shifts are estimated using the gauge-invariant atomic orbital method.     

Spectroscopic studies and molecular orbital analysis on platinanaphthalenes and ring-fused B-N platinanaphthalenes

The electronic structure and properties of the platinanaphthalenes, and ring-fused B-N platinanaphthalenes isomers have been explored using the hybrid density functional mpw1pw91 theory. The energetic aspect shows that stability of Ptb and Pta isomers are isoenergetic in platinanaphthalenes. On the other hand, BNa1 isomer is the most stable isomer of ring-fused B-N platinanaphthalenes. This is compatible with principles of minimum energy and minimum polarizability in ring-fused B-N platinanaphthalenes. Molecular orbital analysis shows increasing of hardness in ring-fused B-N platinanaphthalenes isomers. Also, electronic spectra analysis indicates that, in all the molecules HOMO-1 → LUMO transition makes the major contribution in most intense electronic transition.