Calculation Of Fukui Functions Research Articles

(E)-2-Benzylidenecyclanones: Part XIX. Reaction of (E)-2-(4′-X-Benzylidene)-1-tetralones with Cellular Thiols: Comparison of Thiol Reactivities of Open-Chain Chalcones and Their Six- and Seven-Membered Cyclic Analogs

Non-enzyme-catalyzed thiol addition onto the α,β-unsaturated carbonyl system is associated with several biological effects. Kinetics and diastereoselectivity of non-enzyme catalyzed nucleophilic addition of reduced glutathione (GSH) and N-acetylcysteine (NAC) to the six-membered cyclic chalcone analogs 2a and 2b were investigated at different pH values (pH 3.2, 7.4 and 8.0). The selected compounds displayed in vitro cancer cell cytotoxicity (IC50) of different orders of magnitude. The chalcones intrinsically reacted with both thiols under all incubation conditions. The initial rates and compositions of the final mixtures depended both on the substitution and the pH. The stereochemical outcome of the reactions was evaluated using high-pressure liquid chromatography with UV detection (HPLC-UV). The structures of the formed thiol-conjugates and the retro-Michael products (Z)-2a and (Z)-2b were confirmed by high-pressure liquid chromatography-mass spectrometry (HPLC-MS). Frontier molecular orbitals and the Fukui function calculations were carried out to investigate their effects on the six-membered cyclic analogs. Data were compared with those obtained with the open-chain (1) and the seven-membered (3) analogs. The observed reactivities do not directly relate to the difference in in vitro cancer cell cytotoxicity of the compounds.

Interfacial engineering between carbon vacancies modified graphitic carbon nitride and CoAl-LDH formed heterojunctions for improved photocatalytic performance: Degradation pathway, DFT calculations, and mechanism insights

The construction of green, low-cost heterojunctions with interfacial interaction is crucial to enhance their photocatalytic performance and broaden their utility in practical applications. Here, we prepared CoAl-LDH/Carbon Nitride with carbon vacancies (Cv-CN) heterojunction by electrostatic self-assembly strategy to explore its photocatalytic properties. 30 wt% CoAl-LDH/70 wt% Cv-CN (CCN-2) exhibited the optimal photocatalytic degradation performance after 120 min of light exposure, with a degradation efficiency of 93.1 %. Fukui function calculations, in conjunction with LC-MS/MS analysis, were employed to explore potential degradation pathways during the photocatalytic degradation of tetracycline. The photocatalytic performance of CoAl-LDH/Cv-CN heterojunction was further analyzed by photocatalytic hydrogen production experiments, and after five hours, the hydrogen production rate of CCN-2 was 2515 µmol/g (Cv-CN: 1554 µmol/g, CoAl-LDH: hardly produced any hydrogen). According to the experimental results and data analysis, an effective charge-carrier separation and transfer pathway is established through the interfacial engineering between CoAl-LDH and Cv-CN forming the heterojunction at the interface of CoAl-LDH and Cv-CN. The heterojunction structure formed by interfacial engineering between CoAl-LDH and Cv-CN enables effective photocatalytic removal of antibiotics and hydrogen production providing new insights into the treatment of aqueous environments and clean energy production.

Combined experimental and quantum computational studies on 5-Fluorouracil salicylic acid cocrystal: Assessment on anti-breast cancer potential through docking simulation

5-fluorouracil salicylic acid (5FUSA) cocrystal was synthesised via mechanochemical and solution evaporation technique and spectroscopic experiments and theoretical research were conducted. Methods for the experiments included XRD, FTIR, and UV spectroscopy. Following that, 5FUSA was the subject of quantum chemistry investigations employing the DFT/B3LYP/6–311++G (d, p) basis level. First, the resultant simulated XRD pattern was compared to the relevant experimental pattern. The estimated FT-IR frequencies were gathered from the same level of theory and compared to the experimental data. To learn more about the reactive properties of the 5FUSA, the molecular electrostatic potential plot was generated, and Fukui function calculations were also performed. In order to examine intramolecular interactions and verify the bioactivity of the 5FUSA molecule, the natural bond orbital study was also carried out. We examined the UV–Vis absorption wavelengths (λ) via theoretical (TD-DFT) and experimental methods. The non-linear optical properties were identified, and it was discovered that it had three times the NLO activity of urea. The inter- and intramolecular interactions of the 5FUSA were explored using the Hirshfeld surface and finger print approaches. At various temperatures thermodynamic parameters were calculated and topological analyses were conducted using the (ELF, LOL, and RDG). The anticancer activity of 5FUSA cocrystal was studied using molecular docking and the docking scores ranges between -8.1 to -9.0 Kcal/mol against breast tumor proteins.

Condensed Fukui function and experimental evaluation of the corrosion inhibition properties of some antipyrinyl‐imidazotriazole and their derivatives for copper in an acidic environment

AbstractThe effectiveness of synthesized antipyrinyl‐imidazotriazole and its derivatives as inhibitors for the corrosion of copper alloy in 0.5 M H2SO4 solution was tested using weight loss, electrochemical impedance spectroscopy (EIS) and potentiodyanmic polarization techniques. The generated results confirmed that the tested compounds have strong inhibition efficiencies for the protection of the corrosion of copper alloy in 0.5 M H2SO4. Maximum inhibition efficiencies (IEs) evaluated from electrochemical measurements at inhibitor's concentrations of 0.040 g/L were 85% (5‐(4‐Antipyrinyl)‐3H‐imidazo[1,2‐b][1,2,4]triazole), 60% (6‐Antipyrinyl‐imidazo[2,1‐b]thiazole) and 72% (2‐Antipyrinyl‐7‐ethoxy‐imidazo[2,1‐b]benzothiazole). It was observed that the inhibition efficiency was strongly influenced by the flow rate of the solution and was reduced to 79 (5‐(4‐Antipyrinyl)‐3H‐imidazo[1,2‐b][1,2,4]triazole), 60% (6‐Antipyrinyl‐imidazo[2,1‐b]thiazole), and 44% (2‐Antipyrinyl‐7‐ethoxy‐imidazo[2,1‐b]benzothiazole) at an agitation speed of 400 rpm. EI from weight loss was comparable with those from PDP of mixed‐type inhibition style and EIS of diffusion model. The low inhibition efficiency for 6‐Antipyrinyl‐imidazo[2,1‐b]thiazole was significantly enhanced from 60% to 90% through a synergistic effect of 0.0001 M KI. The Temkin and Frumkin isotherms indicate the physical adsorption of inhibitors on copper surface. Condensed Fukui function calculations reveal a common center for electrophilic attacks in the three molecules: the nitrogen in the bridged pyrrole rings (labeled as N11).

Rational construction of visible-light-driven perylene diimides/Fe2O3@C derived from MIL-88A (Fe) heterojunction with S-scheme electron transfer pathway to activate peroxymonosulfate for degradation of antibiotics

The novel composite photocatalytic material perylene diimides/Fe2O3@C (PDIs/Fe2O3@C) was constructed by a simple hydrothermal-calcination method and an oil bath method. 20 % PDIs/Fe2O3@C displayed a 16.4-fold increase in the rate of tetracycline (TC) removal over Fe2O3@C at 8 min. The main factor that enhanced photocatalytic performance was due to the combination of PDIs with Fe2O3@C, which effectively improved the phenomenon during the self-assembly of highly agglomerative PDIs, increased the specific surface area of Fe2O3@C, exposed more reaction sites, and promoted the activation of peroxymonosulfate (PMS) by Fe2+/Fe3+; and secondly, the composite of two different materials, both organic and inorganic, which effectively promoted the photogenerated electron transfer and the separation of electron-hole pairs, the a new S-scheme electron transport pathway is formed, which effectively promoted the photogenerated electron transfer as well as the e−-h+ separation, which was more favorable for the activation of PMS. The whole reaction pathway and product toxicity were thoroughly evaluated by Fukui function calculations, Liquid Chromatograph Mass Spectrometer (LC-MS), and Toxicity Estimation Software Tool (T.E.S.T.) simulation results, which demonstrated the rationality of the degradation pathway and the greatly reduced product toxicity. Moreover, the composites were effective and versatile for all other antibiotics (chlortetracycline (CTC), ciprofloxacin (CIP) and sulfadiazine (SDZ)). As an advanced oxidation process, the activation of PDIs/Fe2O3@C under visible light shows its potential application in pollutant degradation, which provides new perspectives and ideas for further effective treatment of real wastewater.

In-situ Salen-type ligand formation-driven of a heterometallic Cu(II)-Hg(II) complex: Synthetic update, crystallographic features, DFT calculations, and unveil antimicrobial profiles

This article vividly describes the synthesis and structural characterization of one 6-Bromo-2-hydroxy-3-methoxybenzaldehyde ligand involving heteronuclear complex, [Cu(L)Hg(Cl)2]. X-ray single-crystal determined the complex crystal structure and characterized it by various physical methods, including elemental, FT-IR, Raman, PXRD, UV–vis, NMR, and SEM-EDX techniques. X-ray diffraction analysis reveals that the compound adopts a monoclinic space group Cc during crystallization. The crystal structure exhibits unique supramolecular interactions, like intermolecular C-H∙∙∙π H-bonding and X-bonding (X = Halogen) between Br(1) and Br(2) atoms. Hirshfeld surfaces (HS) and 2-D fingerprint plots confirm significant H…Cl (21.9 %) contacts. Further, dispersion energy dominates due to Br atoms' higher electron/electron cloud. The complex underwent DFT calculations based on the Gaussian software package at B3LYP, HF, and M062x levels, utilizing the lanl2dz, sdd, and def2tzvp basis sets. The HOMO-LUMO, ESP, Global reactivity, Interaction energy and energy frameworks, and Fukui function investigated the complex properties in a multidimensional spectrum. The complex showed promising NLO activity, which has broad technological applications. Fukui function calculation identifies regions prone to nucleophilic (Nu-) and electrophilic (E+) attacks. The complex and synthetic components were examined for antimicrobial function against Gram+ve and Gram-ve bacterial and fungal strains. Molecular docking (MD) and Protein-Ligand Interaction Profilers (PLIP) further support the antimicrobial findings.

Visible light-driven LaFeO3-biochar composites for removal of sulfamethoxazole by enhanced electron transfer coupled with peroxymonosulfate

In this study, we prepared a novel biochar and LaFeO3-bonded nanosphere composite (LFBC) using a co-precipitation-pyrolysis method for the degradation of sulfamethoxazole (SMX). Under visible light conditions, LFBC-activated peroxymonosulfate (PMS) completely removed SMX within 25 min with rate constants 23 and 59 times higher than those of LaFeO3 and biochar, respectively. Both free radical and non-free radical pathways participated in the SMX degradation process, with the non-free radical pathway playing a primary role. It is noteworthy that the interaction between LaFeO3 and Biochar facilitated electron transfer and active sites, promoted the redox cycle of Fe3+/Fe2+, and greatly enhanced the catalytic performance of the composites. Degradation pathway and toxicity evaluation of pollutant removal processes in LFBC/PMS/vis systems based on intermediate identification and Fukui function calculations. This work proved the excellent synergistic performance of LFBC in light utilization and PMS activation, providing a potential utilization for efficient treatment of antibiotic wastewater and antibiotic-resistant bacteria.

Spectroscopic, Quantum Chemical and Molecular Docking Studies on N-(9H-Purin-6-yl) Benzamide: A Potent Antimalarial Agent

This study presents a comprehensive analysis of N-(9H-purin-6-yl) Benzamide (NPB) using a combination of Density Functional Theory (DFT) calculations and experimental techniques. The molecular configuration of NPB was optimized using DFT/B3LYP method employing the 6-311++G (d,p) basis set. The fundamental frequencies were calculated and assigned, which agree well with the experimental results. The UV-Vis spectroscopic analyses, HOMO-LUMO energy gap assessment, Molecular Electrostatic Potential calculation, and Mulliken charge analysis, Fukui function calculation and Natural bond orbital analysis were performed for the NPB molecule. The UV-Visible spectral analysis, which predicts the transition of bonding and anti-bonding π-electrons from the purine ring to the aromatic ring of the NPB molecule. A smaller energy gap in the HOMO-LUMO analysis reveals that the NPB molecule is more reactive and Mulliken atomic charge distribution analysis indicates that the carbon atoms are highly influenced by their substituents. Natural Bond Orbital (NBO) analysis was employed to investigate the bonding within the NPB molecule. The Fukui function analysis indicates that the biological activity of the NPB molecule. In order to analyze the structure of NPB molecule, the thermodynamic properties in the temperature range 100–1000 K were obtained by thermodynamic analysis software SHERMO calculator. The molecular docking analysis was carried out for antimalarial proteins (5ZNC, 2BMA, 7E27, 7E26) using auto-docking simulations. This computational method confirms the bioactivity and drug-likeness parameters of the NPB molecule. The molecular docking results predicts the formation of hydrogen bonds between the ligand (NPB) and the protein receptors. Based on these findings, this study establishes that the distinctive methodology applied to identify NPB molecule as a potential candidate for an antimalarial drug designing, which is suitable for in vivo and in vitro investigations.

O2 plasma-modified carbon nanotube for sulfamethoxazole degradation via peroxymonosulfate activation: Synergism of radical and non-radical pathways boosting water decontamination and detoxification

Sulfamethoxazole (SMX), a widely used antibiotic, has triggered increasing attention due to its extensive detection in wastewater effluent, causing serious ecological threats. Herein, a carbon-based heterogeneous catalyst was developed by the O2 plasma-etching process, regulating oxygen-containing functional groups (OFGs) and defects of carbon nanotubes (O-CNT) to activate peroxymonosulfate (PMS) for highly efficient SMX abatement. Through adjusting the etching time, the desired active sites (i.e., C=O and defects) could be rationally created. Experiments collectively suggested that the degradation of SMX was owing to the contribution of synergism by radical (•OH (17.3%) and SO4•– (39.3%)) and non-radical pathways (1O2, 43.4%), which originated from PMS catalyzed by C=O and defects. In addition, the possible degradation products and transformation pathways of SMX in the system were inferred by combining the Fukui function calculations and the LC-MS/MS analysis. And the possible degradation pathway was effective in reducing the environmental toxicity of SMX, as evidenced by the T.E.S.T. software and the micronucleus experiment on Vicia faba root tip. Also, the catalytic system exhibited excellent performance for different antibiotics removal, such as amoxicillin (AMX), carbamazepine (CBZ) and isopropylphenazone (PRP). This study is expected to provide an alternative strategy for antibiotics removal in water decontamination and detoxification.

Spectroscopic investigations, quantum chemical, molecular docking and drug likeness studies of t-butyl-3,4,5-trimethyl-2-pyrrole carboxylate

The geometrical structure of t‑butyl‑3,4,5-trimethyl-2-pyrrole carboxylate (TBTPC) was computed by DFT calculations using the B3LYP method and the 6–311++G(d,p) basis set using the Gaussian 09 software. Vibrational wavenumbers were assigned using the VEDA 4.0 program. Natural bond orbital (NBO) analysis predicts the hyper-conjugative interaction and stabilization interaction of the TBTPC compound. HOMO, LUMO, and other molecular properties were calculated. The density of states (DOS) spectrum was also predicted. The ultraviolet-visible spectrum has been experimentally and theoretically validated and simulated. The electrophilic and nucleophilic reactive sites of the TBTPC molecule were determined using the Fukui function calculation and the molecular electrostatic potential (MEP) surface. Molecular docking analysis of the TBTPC ligand helps to investigate its inhibitory nature against Lysine-specific demethylase 1A (LSD1), α-amylase, BCL-1, and monoamine oxidase (MAO). From the molecular docking results, TBTPC has promising inhibition activity against gastric cancer.

Simultaneously Achieving Fast Intramolecular Charge Transfer and Mass Transport in Holey D-π-A Organic Conjugated Polymers for Highly Efficient Photocatalytic Pollutant Degradation.

Simultaneously realizing efficient intramolecular charge transfer and mass transport in metal-free polymer photocatalysts is critical but challenging for environmental remediation. Herein, we develop a simple strategy to construct holey polymeric carbon nitride (PCN)-based donor-π-acceptor organic conjugated polymers via copolymerizing urea with 5-bromo-2-thiophenecarboxaldehyde (PCN-5B2T D-π-A OCPs). The resultant PCN-5B2T D-π-A OCPs extended the π-conjugate structure and introduced abundant micro-, meso-, and macro-pores, which greatly promoted intramolecular charge transfer, light absorption, and mass transport and thus significantly enhanced the photocatalytic performance in pollutant degradation. The apparent rate constant of the optimized PCN-5B2T D-π-A OCP for 2-mercaptobenzothiazole (2-MBT) removal is ∼10 times higher than that of the pure PCN. Density functional theory calculations reveal that the photogenerated electrons in PCN-5B2T D-π-A OCPs are much easier to transfer from the donor tertiary amine group to the benzene π-bridge and then to the acceptor imine group, while 2-MBT is more easily adsorbed on π-bridge and reacts with the photogenerated holes. A Fukui function calculation on the intermediates of 2-MBT predicted the real-time changing of actual reaction sites during the entire degradation process. Additionally, computational fluid dynamics further verified the rapid mass transport in holey PCN-5B2T D-π-A OCPs. These results demonstrate a novel concept toward highly efficient photocatalysis for environmental remediation by improving both intramolecular charge transfer and mass transport.

Visible-Light-Driven Peroxymonosulfate Activation for Accelerating Tetracycline Removal Using Co-TiO2 Nanospheres

Heterogeneous catalysts have been widely used for peroxymonosulfate (PMS) activation to remove persistent contaminants in water. This study successfully prepared cobalt-doped TiO2 using a simple two-step approach for activating PMS to remove tetracycline (TC). The batch experiments showed complete TC degradation within 25 min caused by Co-TiO2 (0.1 g/L) activation of PMS (1 mM) under visible light. The system also demonstrated excellent catalytic efficiency in various water environments, such as artificial seawater, tap water, and wastewater. According to the radical capture tests and electron spin resonance analysis, the contribution of active species involved in the degradation of TC with the Vis/Co-TiO2/PMS system were in the following order: 1O2> SO4•−> O2•−> •OH. The possible TC degradation pathway was proposed using intermediate identification and Fukui function calculation. This study provides a promising method toward organic pollutants degradation and provides a novel perspective on the rational design of competent and stable catalysts.

Adsorption and photocatalytic degradation process of oxytetracycline using mesoporous Fe-TiO2 based on high-resolution mass spectrometry

In this study, the adsorption and photocatalytic degradation of oxytetracycline (OTC) were systematically investigated using different metal-doped anatase-phase mesoporous TiO2 nanocatalysts (M−TiO2, M = Fe, Co, Ni, Cr). The results showed that doping with different metals had a significant effect on the ability of TiO2 to adsorb and degrade OTC. Comparing the photoelectric properties of four photocatalysts (Fe-TiO2, Co-TiO2, Ni-TiO2 and Cr-TiO2), it was observed that the mutual synergy between the separation ability of the photogenerated carriers and the adsorption ability of pollutants was the fundamental reason for the excellent photocatalytic performance of Fe-TiO2. The relative intensities of the high-resolution mass spectrometry (HRMS) peaks were used to track and analyse the degradation products of pollutants at different adsorption or light-irradiation times during the photocatalytic process. The ability of the pollutants to undergo dark-state adsorption significantly influenced their degradation paths and products. The possible mechanism of the photocatalytic decomposition of pollutants using Fe-TiO2 along different paths was proposed according to the Fukui function calculation and MS results. To the best of our knowledge, this is the first time that quantitative HRMS results have been used to assess the degradation pathways of pollutants.

NaOH-modified biochar supported Fe/Mn bimetallic composites as efficient peroxymonosulfate activator for enhance tetracycline removal

In this study, NaOH-modified biochar supported Fe/Mn bimetallic composite (Fe-Mn/AW-BC) was prepared to remove tetracycline (TC) through activating peroxymonosulfate(PMS). Results showed that about 97.9 % of TC was degraded and the rate constant of Fe-Mn/AW-BC + PMS system was 37 folds higher than BC + PMS system. Experimental results confirmed that both radical and non-radical pathway were contribute to the catalytic system. Density functional theory (DFT) results also suggested that Fe-Mn/AW-BC sample was favorable for adsorbing PMS based on the length OO bond from PMS and the Eads of catalysts. The superior activation ability was ascribed to the accelerating formation of reaction active species and other oxidation species by bimetallic structures of Fe-Mn and oxygenated functional groups of BC. Additionally, the redox cycles of Fe3+/Fe2+ and Mn3+/Mn2+ under Fe-Mn-BC synergism promoted the generation of the radicals, whereas the carbon shell effectively inhibited metals leaching of Fe-Mn/AW-BC, and 77.8 % of TC can be still removed within 60 min after five consecutive cycles. Notably, Fe-Mn/AW-BC system has special characteristic of wide pH usable range and broad-spectrum adaptability towards various organic pollutants and various water environments. Based on intermediate identification and Fukui function calculation, the degradation pathways of TC were also proposed. This study highlights the applications of biochar for the environmental catalysis.

Ferrocenoyl-adenines: substituent effects on regioselective acylation.

A series of N6-substituted adenine–ferrocene conjugates was prepared and the reaction mechanism underlying the synthesis was explored. The SN2-like reaction between ferrocenoyl chloride and adenine anions is a regioselective process in which the product ratio (N7/N9-ferrocenoyl isomers) is governed by the steric property of the substituent at the N6-position. Steric effects were evaluated by using Charton (empirical) and Sterimol (computational) parameters. The bulky substituents may shield the proximal N7 region of space, which prevents the approach of an electrophile towards the N7 atom. As a consequence, the formation of N7-isomer is a kinetically less feasible process, i.e., the corresponding transition state structure increases in relative energy (compared to the formation of the N9-isomer). In cases where the steric hindrance is negligible, the electronic effect of the N6-substituent is prevailing. That was supported by calculations of Fukui functions and molecular orbital coefficients. Both descriptors indicated that the N7 atom was more nucleophilic than its N9-counterpart in all adenine anion derivatives. We demonstrated that selected substituents may shift the acylation of purines from a regioselective to a regiospecific mode.

Hybridizing electron-mediated H5PMo10V2O40 with CdS/g-C3N4 for efficient photocatalytic performance of Z-scheme heterojunction in wastewater treatment

Photocatalytic technology has been considered as a promising method to alleviate environmental pollution owing to the dual characteristics of redox. The novel V-based H5PMo10V2O40 (HPA-2) photocatalyst with Z-scheme heterostructure was constructed. The energy level of HPA-2 matches well with CdS and g-C3N4 (CN) according to Mott-Schottky and UV–Vis diffused reflectance tests, which allows the efficient separation of photogenerated electrons. The optimized CdS/HPA-2/CN showed superior ability in Rhodamine B (RhB) degradation and reduction of Cr (Ⅵ) under visible light irradiation. The maximum rate constant reached 0.092 min−1 for RhB degradation at 60 min and 0.260 min−1 for Cr (Ⅵ) reduction at 20 min, respectively. The photocatalytic mechanism was analyzed by adding scavengers. The effect of active species for RhB degradation was determined as h+ > ·O2− > ·OH, while ·O2− and e− were essential for the reduction of Cr (Ⅵ). Besides, cyclic tests exhibit excellent repeatability and stable structure of CdS/HPA-2/CN after four cycles. Meanwhile, the detailed degradation process of RhB involving de-ethylation, hydroxylation, substitution and decarboxylation was determined according to LC-MS and evaluated by Fukui function calculation. Furthermore, total organic carbon content decreased to 6.2% of the initial value. In this work, as an electron mediator, HPA-2 provides the inspiration for construction of Z-scheme heterojunction, and CdS/HPA-2/CN exhibits enormous potential in the environmental remediation by photocatalysis.

Density functional studies and spectroscopic analysis (FT-IR, FT-Raman, UV–visible, and NMR) with molecular docking approach on an anticancer and antifungal drug 4‑hydroxy-3-methoxybenzaldehyde

4‑hydroxy-3-methoxybenzaldehyde was investigated quantum chemically by DFT approach, surface analysis by Hirshfeld and experimentally by NMR (FT-IR, UV-Visible 1HNMR and 13CNMR). The B3LYP method and the 6–311 ++ G (d, p) basis set were applied to optimize the molecular structure and to calculate the wavenumbers of normal vibrational modes. A detailed description of the intermolecular interactions of the crystal surface was carried out by means of Hirshfeld surface analysis and fingerprint plots found. The calculated bond lengths and angles were compared with the experimental bond lengths and bond angle parameters and found to be in good agreement. VEDA successfully carried out for the distribution of potential energy. 1HNMR and 13CNMR shifts were estimated using the GIAO method and the results compared with experimental spectra. The molecule reactivity region MEP, molecular stability, NBO, and HOMO-LUMO taken into account. Highest occupied and lowest unoccupied energies were computed and found to be -6.413 eV and -1.873 eV, respectively, indicating charge transfer inside the molecule. Chemical descriptors indicate the reactivity of the molecule as a whole, and Fukui function calculations were used to examine the reactive locations of the compound. NBO analysis indicates that the greatest second order perturbation energy E(2) = 31.26 kcal/mol associated with electron delocalization from the donor LP(2) of O2 → π*(C1-C3) acceptor interaction. Many of the proteins for ligand have been used to examine the biological activity, and the results show that the titled compound may have anti-cancer, antioxidant, and antibacterial activities. The drug-likeness was also studied and molecular docking was done using different proteins and with binding energy -5.9. This system has also been subjected to docking and molecular dynamic simulations in order to better visualize binding sites and the effect of ligand on 7POM conformation. The binding free energy of the receptor protein complex was computed to revalidate the inhibitor affinity for the receptor protein complex predicted by docking and molecular dynamic simulation studies. Binding free energy of docked complex estimated by using MM/PBSA approach.

Synthesis, photophysical, photochemical, and DFT properties of a zinc phthalocyanine with 2-(2-isopropyl-5-methylphenoxy)phenoxy peripheral groups

The 2-nitrophenol and 4-nitrophthalonitrile reagents were mixed in the presence of potassium carbonate in dimethylformamide (DMF) under N2 at room temperature. Then, by adding thymol(5-methyl-2-isopropylphenol) and continuing the reaction, 4-(2-(2-isopropyl-5-methylphenoxy)phenoxy)phthalonitrile was obtained. Zinc phthalocyanine (4) was formed from the reaction of ZnCl2 and 4-(2-(2-isopropyl-5-methylphenoxy)phenoxy)phthalonitrile (3) at 190 °C. Both compounds were soluble in most organic solvents. Compounds 3 and 4 were characterized by mass, infrared, electronic absorption and nuclear magnetic resonance spectroscopies. The concentration–absorption relationship of 4 was examined by UV spectroscopy. The photophysical and photochemical properties of 4 were investigated. The geometry-optimized structures of 4 were investigated with the DFT approach, B3PW91/6-31G (d,p), and B3LYP/LanL2DZ basis set. Energy properties, first order hyperpolarizability, and Fukui function calculations were also performed. Natural bond orbital analysis was performed to explain the charge transfer (or) charge delocalization due to intramolecular interactions in phthalocyanine.

Experimental Spectroscopic, Quantum Computational, Hirshfeld Surface, Molecular Docking, and Electronic Excitation Studies on an Antibiotic Agent: SDZ

In this report sulfadiazine (SDZ) has been experimentally and quantum chemically investigated. Computational analysis was carried out theoretically using the density functional theory (DFT) approach/B3LYP and 6-311++G(d,p) level to obtain optimized geometrical structure and vibrational modes analysis and other various calculations. A detailed description of the intermolecular interactions of the crystal surface were carried out by means of Hirshfeld surface analysis and fingerprint plots. Exploration of electron excitation from occupied to unoccupied orbitals in a single electron pair occurs, with dimethyl sulfoxide (DMSO) and MeOH as solvents and electron density distribution (EDD) and hole density distribution (HDD) maps were drawn in an excited state. The molecule reactivity region MEP, molecular stability, natural bond orbital (NBO), HOMO–LUMO, dipole moment (μ), polarizability (α), and hyperpolarizability (β) nonlinear optical (NLO), have all been taken into account. NBO analysis was carried out and the hybridization of atoms that form bonds was evaluated. The charge transfer of the title molecule has been examined by TD-DFT method The UV–Vis spectrum was obtained by employing the TDDFT/PCM method and compared with experimental spectra. Calculated HOMO→LUMO energy gap and charge transfer in the molecule was investigated. Chemical descriptors indicate the reactivity of the molecule as a whole, and Fukui function calculations were used to examine the reactive locations of the compound. The electrophilicity index was calculated and the bio-activity of the molecule was studied. However, biological research like drug-likeness and molecular docking are also done on the molecule.

Oligolayered Co@MXene with a Co···SO3 cation-π bridge for ultra-rapid catalytic oxidation of a novel “forever chemical” OBS

Sodium p-perfluorous nonenoxybenzene sulfonate (OBS) as a novel alternative to perfluorooctane sulfonate (PFOS), belongs to the family of per- and polyfluoroalkyl substances (PFASs). We demonstrated that Co-based oligolayered MXene (Co@o-MXene) achieved the complete oxidation of OBS during catalytic ozonation with peroxymonosulfate (PMS). The optimized catalyst exhibited 78.5% OBS oxidation in only 2 min, and the oxidation route was thoroughly investigated by Fukui function calculations and QTOF-MS/MS analysis. However, within the fluoroprotein (FP) foam solution, high TOC removal was performed via the newly designed two-stage ozonation process. Systematic studies indicated that OBS can donate electrons through a Co···SO3 cation-π bridge on the surface of o-MXene/PMS accompanied by the generation of reactive oxygen species (ROS), the strong adsorption energy (Eads) value of PMS, enhanced total density of states (TDOS) and uneven electron density in this reaction system. This work extended the potential of newly developed MXene family materials to decompose PFAS.