Electrophilic Sites Research Articles

The unique reactivity of EKODE lipid peroxidation products allows in vivo detection of inflammation.

Lipid peroxidation is a complex biochemical process associated with oxidative stress, and its products play crucial roles in cellular signaling and the pathophysiology of many diseases. Among the diverse array of lipid peroxidation (LPO) products, epoxyketooctadecenoic acids (EKODEs) have emerged as intriguing molecules with potential impacts on inflammatory diseases. EKODEs arise from linoleic acid reacting with reactive oxygen and nitrogen species present during inflammation. A hallmark of many LPO products is an electrophilic chemical functionality that can react with different biological nucleophiles to form adducts that impact a broad swath of physiologic processes. Here, we present the identification of reactivity patterns exhibited by the EKODE class of LPO products that arise due to the unique chemistry of the EKODE electrophiles, namely α, β-unsaturated epoxyketones of variable regiochemistry. Our initial investigations with models of the EKODE reactive core showed that surrogates of lysine did not react, and histidine nucleophiles formed reversible Michael adducts. However, when models of cysteine nucleophiles were tested, a unique reactivity profile emerged where rapid Michael addition was followed by slow rearrangement and epoxide opening at an unpredicted electrophilic site, affording what we postulated to be an advanced lipoxidation end product (ALE). After confirming the EKODE reactivity in model systems, we produced polyclonal antibodies of a stable epitope of the EKODE-based ALE and used these antibodies to investigate an approach for in vivo monitoring of inflammatory disease progression.

Recent Developments in Stereoselective Reactions of Sulfoxonium Ylides

This review probes the recent developments in stereoselective reactions within the area of sulfoxonium ylide chemistry since the early 2000s. An abundance of research has been applied to sulfoxonium ylide chemistry since its emergence in the early 1960s. There has been a continued effort since then with work in traditional areas, such as epoxidation, aziridination and cyclopropanation. Efforts have also been applied in novel areas, such as olefination and insertion reactions, to develop stereoselective methodologies using organocatalysis and transition metal catalysis. The growing research area of interrupted Johnson–Corey–Chaykovsky reactions is also described, whereby unexpected stereoselective cyclopropanation and epoxidation methodologies have been developed. In general, the most observed mechanistic pathway of sulfoxonium ylides is the formal cycloaddition: (2 + 1) (e.g., epoxides, cyclopropanes, aziridines), (3 + 1) (e.g., oxetanes, azetidines), (4 + 1) (e.g., indanones, indolines). This pathway involves the formation of a zwitterionic intermediate through nucleophilic addition of the carbanion to an electrophilic site. An intramolecular cyclization occurs, constructing the cyclic product. Insertion reactions of sulfoxonium ylides to X–H bonds (e.g., X = S, N or P) are also observed, whereby protonation of the carbanion is followed by a nucleophilic addition of X, to form the inserted product.

Structural and topological analysis of thiosemicarbazone-based metal complexes: computational and experimental study of bacterial biofilm inhibition and antioxidant activity

The structural and electronic behavior of thiosemicarbazone (TSC)-based metal complexes of Mn (II), Fe (II), and Ni (II) have been investigated. The synthesized metal complexes were characterized using elemental analysis, magnetic susceptibility, molar conductivity, FTIR, and UV–Vis spectroscopy, the computational path helped with further structural investigation. The solubility test on the TSC and its complexes revealed their solubility in most organic solvents. DFT computational analysis was performed, and quantum reactivity parameters of the octahedral optimized complexes were calculated to describe the reactivity via the stability states of the synthesized complexes. FMOs map was generated to confirm similar findings and MEP analysis was applied to elaborate the important electrophilic and nucleophilic sites on the studied surfaces. Also, other important topological analyses such as electron localization function and reduced density gradient, to establish the favorable noncovalent interactions, were studied. In silico molecular docking approach was studied against the gram-positive bacteria Bacillus cereus to predict the potent inhibition behavior of the studied complexes. The findings summarized the inhibition prediction of the most interactive [NiL2Cl2], then [FeL2Cl2] complexes as confirmed by the binding energy values (− 7.1 kacl/mol and − 6.4 kacl/mol, respectively). Another In silico results, with gram-positive bacteria (S. aureus), estimated similar results of the experimental finding, where [MnL2Cl2] (− 9.2 kcal/mol) is the more effective predicted antibacterial inhibitor. Fluorescence microscopy was used to examine the inhibition of bacterial biofilm, and the DPPH assay was used to measure antioxidant activity, followed by an understanding of the behavior of the current complexes toward free radicals’ removal. The findings observed less aggregated bacterial strains covered with the studied complexes leading to less dense biofilm covering.

Synthesis, Photophysical Properties and Systematic Evaluation of New Class Fluorescein Based Derivative with Organic Solvents: Spectroscopic and Density Functional Theory Methods for Optoelectronic Applications.

In this report the photophysical property of newly synthesized fluorescein based derivative 2-(5-((2,4-dichlorophenyl)diazenyl)-6-hydroxy-3-oxo-3H-xanthen-9-yl)benzoic acid has studied by spectroscopic and theoretical that is by Density Functional Theory technique. The structural and functional group of the synthesized molecule was confirmed by nuclear magnetic resonance and fourier transform infrared spectroscopy technique, and from the result so far obtained has been confirmed that molecule has a stable structure and confirmed the presence the functional groups present in the sample. The optical properties of the molecule are studied using the spectroscopic technique and it has revealed the solute-solvent interaction behaviour of the molecule and it has been observed that the bathochromic shift was of about 5nm, from the fluorescence measurement it has revealed that the emission has been observed at green region and from the power spectra it has been confirmed the same. The DFT study has been derived for the synthesized molecule the optimized structure, electrostatic potential maps, theoretical energy band gap and HOMO and LUMO visualizations are derived from the Gaussian 09W software and it has been found that the bandgap energy is found to be 2.607eV for benzene solvent and 3.081eV in methanol solvent, the electrophilic and nucleophilic sites exhibited at the substitution group of the molecule. The outcomes of the study clearly endorse the synthesized fluorescein derivative suitable for photonic/optoelectronic applications.

Excited-state antioxidant activity for apigenin based on external electric field-modulated ESIPT behavior: TD-DFT and molecular docking calculations.

Apigenin (Api), a flavonoid possessing dual features of antioxidant activity and intramolecular hydrogen bond (IMHB), is subjected to an external electric field (EEF) to investigate its excited-state antioxidant activity after excited state intramolecular proton transfer (ESIPT) behavior employing the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods, as well as molecular docking. The existence of IMHB is demonstrated by structural parameters and AIM topological analysis, where Api in the enol⁎ form under an EEF of +60×10-4a.u. possesses strong IMHB. The potential energy curves confirm that the ESIPT process varies from barrierless to barriered as the positive EEF grows, thus determining the excited-state form. Api exhibits strong excited-state antioxidant activity in vitro whether or not under an EEF, especially under the EEF of -40×10-4a.u., utilizing HOMO energy. According to average local ionization energy (ALIE), the electrophilic reaction site also changes after ESIPT process under the EEF, and the activity is significantly increased. Furthermore, activation of the antioxidant Keap1-Nrf2-ARE pathway in vivo, namely, the interaction of Keap1 protein with Api, calculated by molecular docking, suggests that an interaction between the Keap1 and excited-state Api exists accompanying lower and variable bind energy under the distinct EEFs. Taken together, combining the modulation of the ESIPT process with the excited-state antioxidant activity is an effective approach to enhance the antioxidant activity of compounds.

Balancing electrophilic and nucleophilic dual sites to construct efficient Mott–Schottky oxygen electrocatalysts

Balancing electrophilic and nucleophilic dual sites to construct efficient Mott–Schottky oxygen electrocatalysts

Characterization of 3-Chloro-4-Fluoronitrobenzene Molecule with New Calculation Methods and Discussions for Advanced Applied Sciences

This current research characterizes 2-chloro-1-fluoro-4-nitrobenzene molecule via the Hartree Fock (HF) and density functional theory (DFT) quantum mechanical computational techniques using B3LYP/6-311++G(d,p) levels of computation. The molecular geometries, thermodynamic quantities at 300 K, NMR chemical shifts, corresponding vibrational spectra, UV-vis spectra, vibrational frequencies, and atomic point charge distributions are extensively investigated. The 1H and 13C NMR chemical shifts, and theoretical vibrational frequencies are compared to the experimental results. It is obtained that all calculations are in agreement with the available experimental data which has the 1H isotropic chemical shifts range from 8.306 ppm to 7.235 ppm, while the computed values range from 9.0368 ppm to 6.8397 ppm, 8.3213 ppm to 6.1242 ppm at DFT and HF GIAO levels, respectively. Besides, calculated 13C chemical shifts vary from 141.83 ppm to 186.394 ppm and from 129.743 ppm to 174.373 ppm by using DFT and HF in CH4, while these values are in the range of 117.00 ppm to 164.59 ppm, experimentally. This points out that the chosen computation sets are highly effective methods for identifying and characterizing the compound. In addition, simulations are performed to examine frontier molecular orbitals, electrostatic potential, and molecular electrostatic potential regions. Key properties such as dipole moment, chemical hardness, transition states, electronegativity, molecular softness, nucleophilic aromatic regions, electrophilicity index, and energy band gap are also analyzed to explore potential future applications such as advanced applied sciences, industry, chemistry, medical, physics, biology, pharmaceuticals, dyes, and agrochemicals of the compound. Additionally, it is noted that the compound contains significant intramolecular charge transfer (ICT) regions, lone electron pairs, electron-donating groups, π-bond conjugation, and particularly reactive electrophilic and nucleophilic aromatic sites. Accordingly, it is pointed out that the molecule has a strong potential for metallic bonding as well as various intermolecular interactions. In summary, this study provides valuable information that will benefit both basic research and technological or industrial applications by increasing the understanding of physical, chemical, structural, and reactive features of the 3-chloro-4-fluoronitrobenzene molecule.

Novel Small Molecule Derived from Hydroxy Naphthaldhyde as Potential Anti-Leukemia Agents: Spectroscopic, DFT, Docking Molecular and ADME/T Investigations

New ligand derived from hydroxy naphthaldhyde (LCAT1) was synthetized and the structure of the formed Schiff base was confirmed by various analytical and spectroscopic methods. Elemental analysis, mass spectrometry and NMR studies confirmed the structure of the ligand. Theoretical calculations (DFT) were performed to study the molecular structure, chemical reactivity and electronic properties of this ligand. This study shows good agreement with the experimental results obtained using infrared spectrometry and UV-visible spectrophotometry. The optimized structure has been used to perform the molecular docking studies. The homology modeling and molecular docking were investigated in order to check their anti-leukemia activities toward several leukemia cells. In addition, in silico ADME/T modeling was employed to evaluate absorption, distribution, metabolism, and excretion pharmacological parameters of the ligand. The DFT study indicates that the evaluated parameters, such as Mulliken charges and molecular orbitals, as well as the MEP results, are consistent with the localization of electrophilic and nucleophilic attack sites. Furthermore, the data indicate significant chemical reactivity associated with low kinetic stability of the ligand. In accordance with the principle of a 90% critical assessment, the homological modeling model used is considered to be the most appropriate. The molecular docking results indicated that our molecule has a strong affinity for DNA by forming hydrogen bonds with the donor’s groups and exhibits a good leukemia activity against cell lines through the formation of strong interaction with their receptors. The results showed high binding energy and remarkable inhibition constants toward receptors 5VOM (−8.03 Kcal/mol, 1. 31 µM), 1NJS (−7.68 Kcal/mol, 2.35 µM), 7JXU. In silico ADME/T modeling showed that the properties of the synthesized ligand are similar to those of the drugs. The predicted toxicity of the ligand reveals that LCAT1 is nontoxic, with no hepatotoxicity, no mutagenicity and no carcinogenicity.

Study anti-viral drugs for their efficiency against multiple SARS CoV-2 drug targets within molecular docking, molecular quantum similarity, and chemical reactivity indices frameworks

The study focused on drug discovery for COVID-19, emphasizing the challenges posed by the pandemic and the importance of understanding the virus’s biology. The research utilized molecular docking and quantum similarity analyses to explore potential ligands for SARS-CoV-2 RNA-dependent RNA polymerase. Docking Results Docking outcomes for various ligands, including Oseltamivir, Prochloraz, Valacyclovir, Baricitinib, Molnupiravir, Penciclovir, Famciclovir, Lamivudine, and Nitazoxanide, were presented. Interactions between ligands and specific residues in the RNA-dependent RNA polymerase were analyzed. Reactivity Descriptors Global parameters, such as electronic chemical potential, chemical hardness, global softness, and global electrophilicity, were computed for the ligands. For the local reactivity descriptors, the Fukui Functions were used. Fukui functions, representing electrophilic and nucleophilic sites, were calculated for selected ligands (Valacyclovir and Penciclovir). Nucleophilic character assignments for specific molecular regions were discussed, providing insights into potential charge-donating interactions. Results and Discussion Challenges in COVID-19 drug discovery, such as virus mutability, rapid evolution, and resource limitations, were summarized. Progress in vaccine development and the need for ongoing research to address variants and breakthrough cases were emphasized. Overlap Operator Analysis Higher MQSM between Lamivudine and Molnupiravir (0.5742) indicates structural and electronic similarity. Lowest MQSM between Oseltamivir and Prochloraz (0.2233) implies structural dissimilarity. Coulomb Operator Analysis Higher MQSM between Lamivudine and Molnupiravir (0.9178) suggests both structural and electronic similarity. Lowest MQSM between Baricitinib and Famciclovir (0.6001) indicates greater structural diversity. Measurements above 0.5 in Table 3 suggest electronic similarity, emphasizing the electronic aspects in molecular analysis. In this sense, it study employed a multi-faceted approach combining molecular docking, quantum similarity analyses, and chemical reactivity assessments to explore potential drug candidates for COVID-19. The findings provide valuable insights into ligand interactions, reactivity patterns, and the challenges associated with drug discovery in the context of the global pandemic.

Promotive Effect of Organic Acids on the Dispersion of Ceria Slurry and the Removal Rate of TEOS in Chemical Mechanical Polishing

Abstract In this study, the effect of organic acids (formic acid, acetic acid, and lactic acid) on the material removal rate (MRR) of TEOS films was investigated. The results showed that formic acid was an effective dispersant for CeO2 slurry. When adding formic acid to the slurry, the average particle size of CeO2 was reduced to 172.5 nm and the Zeta potential was increased to 47.6 mV. Consequently, the MRR of TEOS improved from 408.3 to 695.5 nm/min with a surface roughness of 0.16 nm. The MRR of the pattern wafer was increased from 575.1 to 941.6 nm/min. Molecular dynamics simulation indicated that the oxygen atom attached to the double bond in the carboxyl group serves as the primary electrophilic reaction site. The double electric layer was thickest between formic acid and CeO2, resulting in the best dispersion of CeO2 slurry, which was conducive to improving the MRR of TEOS. The polishing effect of formic acid was verified by adding polyethylene glycol, enhancing the MRR of TEOS was 1351.2 nm/min.

Development and Applications of an Amide Linchpin Reagent

AbstractLinchpin reagents are building blocks that can be chemoselectively functionalized to afford products with a common, useful functional group. In this work, we describe the development and validation of the first amide linchpin reagent and demonstrate its use as a doubly electrophilic building block for the synthesis of a variety of amides, including challenging classes. The linchpin reagent was first functionalized via rhodium‐catalyzed electrophilic amination. Selected masked C‐isocyanate products were then further derivatized with Grignard reagents to produce secondary amides, or tertiary amides if an alkylating agent was added subsequently. The success of this sequence relies on fully controlled reactivity at each electrophilic site, first exploiting the weak N−O bond and then, the ability to form the free isocyanate intermediate in situ. The overall transformation proceeds with high chemoselectivity, demonstrating the ability of this new linchpin reagent to form amides through atypical bond construction. Finally, the potential of this reagent as a more broadly applicable NCO linchpin is demonstrated by the formation of lactams and unsymmetrical ureas.

Development and Applications of an Amide Linchpin Reagent.

Linchpin reagents are building blocks that can be chemoselectively functionalized to afford products with a common, useful functional group. In this work, we describe the development and validation of the first amide linchpin reagent and demonstrate its use as a doubly electrophilic building block for the synthesis of a variety of amides, including challenging classes. The linchpin reagent was first functionalized via rhodium-catalyzed electrophilic amination. Selected masked C-isocyanate products were then further derivatized with Grignard reagents to produce secondary amides, or tertiary amides if an alkylating agent was added subsequently. The success of this sequence relies on fully controlled reactivity at each electrophilic site, first exploiting the weak N-O bond and then, the ability to form the free isocyanate intermediate in situ. The overall transformation proceeds with high chemoselectivity, demonstrating the ability of this new linchpin reagent to form amides through atypical bond construction. Finally, the potential of this reagent as a more broadly applicable NCO linchpin is demonstrated by the formation of lactams and unsymmetrical ureas.

Reactivity of three pyrimidine derivatives, potential analgesics, by the DFT method and study of their docking on cyclooxygenases-1 and 2

Three pyrimidine derivatives, namely 4-[4-(dimethylamino)phenyl]-6-(pyridin-4-yl)pyrimidin-2-amine (DMPN), 4-(4-aminophenyl)-6-[4-(dimethylamino)phenyl]pyrimidin-2-ol (DMPO) and 4-(4-aminophenyl)-6-[4-(dimethylamino)phenyl]pyrimidine-2-thiol (DMPS), with analgesic properties established by a QSAR study, were subjected to reactivity parameter studies using the DFT method, at the B3LYP/6-311++G(d,p) level of theory. Studies of the docking of these molecules to cyclooxygenases 1 (PDB ID: 5U6X) and 2 (PDB ID: 5F19) were also carried out using the CB-Dock online program. Reactivity parameter calculations revealed that the three derivatives are less stable to internal electron transfer, with the lowest energy gap ∆E ranging from 3.63 eV to 3.88 eV, compared with 6.03 eV for ibuprofen (IBP). These derivatives possess the lowest chemical hardnesses η from 1.81eV to 1.94eV versus 3.02eV for IBP and are better electrophiles than IBP with chemical electrophilicity index values ω from 3.20eV to 3.88eV versus 2.64eV for IBP. These derivatives possess greater chemical reactivity than ibuprofen. All three derivatives also feature electrophilic and nucleophilic attack sites. The docking results show that all three derivatives react with cyclooxygenases in the same areas of reactivity as most NSAIDs. These ligands are more active on COX-2 than COX-1, according to complex stability scores which are stronger with COX-2 than with COX-1. In addition, all three derivatives are more active on COX-2 than ibuprofen, with stability score values of -8.6 kcal/mol for DMPN, -9.2 kcal/mol for DMPO, -8.9 kcal/mol for DMPS and -7.6 kcal/mol for IBP. The DMPO ligand forms the most stable complex with COX-2. These three derivatives thus appear to be selective COX-2 inhibitors, with higher stability scores than ibuprofen. All three derivatives also have good absorption, distribution, metabolism and toxicity properties. They can therefore be used as drugs.

Synergism of Computational Simulation Technique and Machine Learning Algorithm for Prediction of Anticorrosion Properties of Some Antipyrine Derivatives.

This study aimed to predict the selected antipyrine compounds' inhibitory efficiencies and anticorrosion properties in a hydrochloric acid (HCl) environment. Molecular descriptors and input variables were obtained using density functional theory (DFT), and the variance inflation factor (VIF) was employed to reduce redundant variables, leading to the selection of seven quantum chemical descriptors as input variables. Using machine learning techniques such as K-nearest neighbor (KNN) and artificial neural network (ANN), a predictive model was built for 39 antipyrine compounds with known corrosion inhibition efficiencies for carbon and low alloy steel in hydrochloric acid solutions. The models' predictive capability was assessed using cross-validation, with the ANN model showing superior performance, achieving a coefficient of determination (R2) value of 0.715 compared to 0.548 for the KNN model. Performance metrics such as the mean square error (MSE), mean absolute error (MAE), and root-mean-square error (RMSE) further confirmed the superiority of the ANN model over the KNN model. The corrosion inhibition efficiencies (CIEs) of the selected antipyrine compounds ranged from 68.78 to 99.79%, with compound A1 demonstrating the highest CIE of 99.79% and compound A3 the lowest, as evaluated by the ANN model. Analysis of Fukui index parameters obtained from the Mulliken population analysis suggested that the nucleophilic and electrophilic sites play a crucial role in the interactions between the inhibitor and the metal atom through electron donor-acceptor interactions. Moreover, the energy of adsorption (Eads) in kcal·mol-1 decreased in the order of A1 (-187.8) > A2 (-132.0) > A2 (-84.4), with the high negative value of Eads indicating strong and spontaneous adsorption. Further analysis using radial distribution functions and molecular dynamics simulations revealed that inhibitor A1 exhibited predominantly chemisorption, inhibitor A2 showed a mixed type, and inhibitor A3 demonstrated predominantly physisorption, aligning well with the results of the predictive studies.

Ionic liquid-catalyzed, microwave-assisted green synthesis of novel Coumarin-Schiff bases: Characterization, molecular docking, biological and DFT studies

A microwave assisted green protocol for the synthesis of coumarin-linked novel Schiff base compounds (CSB-I and CSB-II) were demonstrated by employing [TMG][OAc] ionic liquid (IL) as dual catalyst and solvent. The resulted compounds were characterized by several spectroscopic techniques such as FT-IR, 1H NMR, 13C NMR and GC–MS. The efficiency of the ionic liquid employed is evaluated by recycle and reuse of the same for number of cycles (upto 5). The HOMO and LUMO energy levels for each Schiff base were meticulously calculated using Density Functional Theory (DFT). The electrophilic and nucleophilic sites were identified by Molecular Electrostatic Potential (MESP) 3D plots, based on DFT computational analysis. Further, Global Chemical Reactivity Descriptor (GCRD) parameters including chemical potential (μ), chemical hardness (ղ), softness (S), electrophilicity index (ω) and electronegativity (χ) were also evaluated with precision. The molecular docking studies were also performed to evaluate the behavior of binding interaction of new Schiff bases (CSB-I and CSB-II) with mevalonate-5-diphosphatedecarboxylase (PDB ID: 1FI4) and human lanosterol 14-alpha-demethylase, CYP51 (PDB ID: 3LD6) proteins. The outcome of this study reveals that CSB-I exhibited strong binding to both the proteins as compared to CSB-II. The antibacterial study revealed that CSB-I was highly effective against both Gram-positive and Gram-negative bacteria, while CSB-II showed moderate activity. In antifungal studies, both the compounds showed excellent activity profiles against yeast fungi, while both had only moderate effects on filamentous fungi.

Crystal structure, Hirshfeld surface, DFT and molecular docking studies of 2-{4-[(E)-(4-acetylphenyl)diazenyl]phenyl}-1-(5-bromothiophen-2-yl)ethanone; a compound with bromine...oxygen-type contacts

The title compound, C19H13BrN2O3S, a non-liquid crystal molecule, crystallizes in the orthorhombic system, space group Pna21. The torsion angles associated with ester and azo groups are −177.0 (4)°, -anti-periplanar, and 179.0 (4)°, +anti-periplanar, respectively. The packing is consolidated by a weak C—Br...O=C contact, forming infinite chains running along the [001] direction. A Hirshfeld surface analysis revealed that the major contributions to the crystal surface are from H...H, C...H/H...C, O...H/H...O, Br...H/H...Br and S...H/H...S interactions. The computed three-dimensional energy interactions using the basis set B3LYP\631-G(d,p) show that Edis (217.6 kJ mol−1) is the major component in the structure. The DFT calculations performed at the B3LYP/6–311+ G(d,p) level indicate that the energy gap between HOMO and LUMO is 3.6725 (2) eV. The molecular electrostatic potential (MEP) map generated supports the existence of the Br...O type contact, formed between the electrophilic site of the bromine atom and the nucleophilic site of the ketonic oxygen atom. The molecular docking between the ligand and the Mycobacterium Tuberculosis (PDB ID:1HZP) receptor shows a good binding affinity value of −8.5 kcal mol−1.

Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

AbstractMesoionic compounds are hugely popular in fields such as organic chemistry, organometallic chemistry and homogeneous catalysis. A new sub‐class are the mesoionic imines (MIIs). We present here 5‐amino‐4‐pyridyl‐1,2,3‐triazole as a new and versatile synthon for generating first examples of metallo‐MIIs. In this approach, we make use of metallation at the N‐pyridyl/N3‐triazole chelating pocket (instead of quarternisation of N3‐triazole) and subsequent deprotonation to generate highly versatile and tunable metallo‐MIIs. These unprecedented metallo‐MIIs contain a highly nucleophilic N‐donor site, and a tunable electrophilic metal site. Apart from displaying strong and directed H‐bonding interactions like their “classical” MII analogues, the metallo‐MIIs engage in aromatic C−F activation as well as meta−C−H activation reactions. Facile synthesis of homo and heterodincuelar complexes which contain a mixed coordinative saturation/unsaturation with these metallo‐MIIs is presented. Apart from the metallo‐MIIs we have also used 5‐amino‐4‐pyridyl‐1,2,3‐triazole as a precursor to generate the first examples of amido‐1,2,3‐triazole complexes and the first example of a “normal” (and not mesoionic) 1,2,3‐triazole based imine. Our results establish metallo‐MIIs as a versatile new class of mesoionic compounds that combine the modularity of click reactions, with the functionality of metal fragments to generate electronically ambivalent compounds with a huge potential in synthetic chemistry, catalysis and beyond.

Determination the Anticorrosive Properties of Trimebutine Maleate for Aluminum Corrosion in 2M HCl Gravimetric and Quantum Chemistry Approaches

The present work evaluated the inhibition properties of (R,S)-2-(dimethylamino)-2-phenylbutyl 3,4,5-trimethoxybenzoate or trimebutine maleate (TM) in aluminum corrosion in 2M hydrochloric acid. Tests were carried out using gravimetric methods and density functional theory (DFT). The results indicate that trimebutine maleate is a good inhibitor of aluminum corrosion in 2M hydrochloric acid at low temperatures. Indeed, the inhibition efficiency of this molecule increases with increasing concentration and decreases with increasing temperature. For an inhibitor concentration of 5.2mM and at 298K, we obtained an inhibition efficiency of 93.61%. The adsorption process is spontaneous, exothermic and follows the Langmuir model. The activation parameters were calculated and analyzed. DFT at the B3LYP/6-311G (d.p) level was used to determine molecular parameters such as EHOMO, ELUMO, ΔE, η, S, μ , A, I, χ, ΔN, ω. These theoretical parameters showed that TM is highly reactive and can both donate and receive electrons from aluminum. They thus confirmed the good inhibition performance of the molecule studied. These parameters were used to explain the inhibition efficiencies obtained. Local selectivity was analyzed using Fukui functions and the dual descriptor to determine possible nucleophilic and electrophilic attack sites.

Solvents and their influence on electronic properties in IEFPCM solvation model, anticancer activity, and docking studies on (E)-2-((4-chlorobenzylidene) amino)phenol

The Schiff base (E)-2-((4-chlorobenzylidene)amino)phenol (4CL2AM) has been synthesized from 4-chlorobenzaldehyde and 2-aminophenol. Spectroscopic techniques like FTIR, Raman, UV, fluorescence, and NMR were used to characterize the synthesized compound. The experimental data well matched with the DFT method (B3LYP/cc-pVDZ basis set). The frontier molecular orbital (FMO), molecular electrostatic potential (MEP), and electronic spectra (UV–visible) analysis were conducted on three different solvents such as gas, DMSO, and water. The frontier molecular orbital (FMO) analysis calculated the HOMO-LUMO energy gap as 4.0109 eV, 4.0406 eV, and 4.0411 eV for the gas phase, DMSO, and water respectively. Molecular electrostatic potential (MEP), localized orbital locator (LOL), and electron localize function (ELF) analysis revealed positions of localized and delocalized orbitals as well as electrophilic and nucleophilic attack sites. The natural bond orbital analysis (NBO) predicted highest stabilization energy was 33.37 kcal/mol. The locations of the covalent and non-covalent interactions were investigated by density overlaps region indicator (DORI), interaction region indicator (IRI), and noncovalent interaction (NCI) analysis. Drug likeness and ADME analysis were investigated. In vitro, anticancer activity studies revealed against MCF-7 breast cancer cell lines. In the molecular docking study, the predicted lowest binding energy is −5.77 kcal/mol for the 6NLV-4CL2AM system.

Synthesis, spectroscopic, computational, topology, and molecular docking studies on N,N'-(4-methyl-1,3-phenylene)bis(1-(2,4-dichlorophenyl)methanimine)

The study extensively examined N,N'-(4-methyl-1,3-phenylene)bis(1-(2,4-dichlorophenyl)methanimine) (6D). Advanced spectroscopic techniques, including IR, Raman, NMR, and UV-VIS spectroscopies, were employed to analyse the molecule. The Schiff base was ultimately confirmed using NMR spectrum analysis. The UV-VIS study revealed a notable bathochromic change in the compound, indicating their electronic transitions. By using the HOMO–LUMO bond gap the titled compound reactivity sites were identified. The compound 6D HOMO–LUMO band gap is 3.70 eV. Various wave function investigations like MESP, HOMO–LUMO, RDG, ELF, LOL, and ALIE were conducted to elucidate the distribution of electronic charge, providing valuable insights into the behaviour of molecules. The biological probability of the synthesised compound was extensively assessed using a docking study. Using MEP and HOMO–LUMO investigations, we confirm nucleophilic and electrophilic attacking sites. In the docking study, the protein Bovine cytochrome bc1 complex stigma Tellin bound (PDB ID–1PP9) was downloaded. The docking study identified the most stable minimum binding energy is –6.26 kcal/mol.