Theoretical Insights into Different Complexation Modes of Dioxovanadium(V) Compounds with Pyridoxal Semicarbazone/Thiosemicarbazone/S-Methyl-iso-thiosemicarbazone Ligands.

Vanadium complexes have gained considerable attention as biologically active compounds. In this contribution, three previously reported dioxovanadium(V) complexes with pyridoxal semicarbazone, thiosemicarbazone, and S-methyl-iso-thiosemicarbazone ligands are theoretically examined. The intermolecular stabilization interactions within crystallographic structures were investigated by Hirshfeld surface analysis. These experimental structures were optimized at the B3LYP-D3BJ/6-311++G(d,p)(H,C,N,O,S)/def2-TZVP(V) level of theory, and crystallographic and optimized bond lengths and angles were compared. High correlation coefficients and low mean absolute errors between these two data sets proved that the selected level of theory was appropriate for the description of the system. The changes in structures and stability were examined by adding explicit solvent molecules. The Quantum Theory of Atoms in Molecules (QTAIM) was employed to analyze the intramolecular interactions with special emphasis on the effect of substituents. A good correlation between electron density/Laplacian and interatomic distance was found. Through molecular docking simulations towards Bovine Serum Albumin (BSA), the binding affinity of complexes was further investigated. The spontaneity of binding in the active position of BSA was shown. Further experimental studies on this class of compounds are advised.

Synthesis, Structural Characterization, Cytotoxicity, and Protein/DNA Binding Properties of Pyridoxylidene-Aminoguanidine-Metal (Fe, Co, Zn, Cu) Complexes.

Pyridoxylidene-aminoguanidine (PLAG) and its transition metal complexes are biologically active compounds with interesting properties. In this contribution, three new metal-PLAG complexes, Zn(PLAG)(SO4)(H2O)].∙H2O (Zn-PLAG), [Co(PLAG)2]SO4∙2H2O (Co-PLAG), and [Fe(PLAG)2]SO4∙2H2O) (Fe-PLAG), were synthetized and characterized by the X-ray crystallography. The intermolecular interactions governing the stability of crystal structure were compared to those of Cu(PLAG)(NCS)2 (Cu-PLAG) within Hirshfeld surface analysis. The structures were optimized at B3LYP/6-31+G(d,p)(H,C,N,O,S)/LanL2DZ (Fe,Co,Zn,Cu), and stability was assessed through Natural Bond Orbital Theory and Quantum Theory of Atoms in Molecules. Special emphasis was put on investigating the ligand's stability and reactivity. The binding of these compounds to Bovine and Human serum albumin was investigated by spectrofluorometric titration. The importance of complex geometry and various ligands for protein binding was shown. These results were complemented by the molecular docking study to elucidate the most important interactions. The thermodynamic parameters of the binding process were determined. The binding to DNA, as one of the main pathways in the cell death cycle, was analyzed by molecular docking. The cytotoxicity was determined towards HCT116, A375, MCF-7, and A2780 cell lines. The most active compound was Cu-PLAG due to the presence of PLAG and two thiocyanate ligands.

The Effect of Metal Ions (Fe, Co, Ni, and Cu) on the Molecular-Structural, Protein Binding, and Cytotoxic Properties of Metal Pyridoxal-Thiosemicarbazone Complexes.

Thiosemicarbazones and their transition metal complexes are biologically active compounds and anticancer agents with versatile structural properties. In this contribution, the structural features and stability of four pyridoxal-thiosemicarbazone (PLTSC) complexes with Fe, Co, Ni, and Cu were investigated using the density functional theory and natural bond orbital approach. Special emphasis was placed on the analysis of the donor atom-metal interactions. The geometry of compounds and crystallographic structures were further examined by Hirshfeld surface analysis, and the main intermolecular interactions were outlined. It has been shown that the geometry and the number of PLTSC units in the structure determine the type and contribution of the specific interactions. The binding of all four complexes to bovine and human serum albumin was investigated through spectrofluorometric titration. The dependency of the thermodynamic parameters on the present metal ion and geometry was explained by the possible interactions through molecular docking simulations. The binding of complexes to DNA, as one of the possible ways the compounds could induce cell death, was examined by molecular docking. The cytotoxicity was measured towards HCT116, A375, MCF-7, A2780, and MCF5 cell lines, with Cu-PLTSC being the most active, as it had the highest affinity towards DNA and proteins.

Design of Liquid Crystal Materials Based on Palmitate, Oleate, and Linoleate Derivatives for Optoelectronic Applications.

Herein, liquid crystalline derivatives based on palmitate, oleate, and linoleate moieties with azomethine cores were synthesized, and their physical, chemical, optical, and photophysical properties were investigated in detail. The mesomorphic activity of these materials was examined through polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The observed results revealed that the stability of the thermal mesophase depends on the terminal polar as well as on the fatty long-chain substituents. Purely smectogenic phases were detected in all three terminal side chains. A eutectic composition with a low melting temperature and a broad smectic A range was found by constructing a binary phase diagram and addressing it in terms of the mesomorphic temperature range. The energy bandgap of the palmitate-based derivative (Ia) was determined as 3.95 eV and slightly increased to 4.01 eV and 4.05 eV for the oleate (Ib) and linoleate (Ic) derivatives, respectively. The optical constants (n, κ, εr, and εi) were extracted from the fitting of measured spectroscopic ellipsometer data. The steady-state spectra of these samples exhibited a broad emission in the range 400-580 nm, which was found to be blue shifted to 462 nm for both Ib and Ic derivatives. The average fluorescence decay lifetime of the Ia derivative was found to be 598 ps, which became faster for the Ib and Ic derivatives and slower for the sample with a chloride end polar group.

Synthesis of MnSe-Based GO Composites as Effective Photocatalyst for Environmental Remediations.

In this work, a manganese selenide/graphene oxide (MnSe/GO)-based composite was prepared for wet-chemical assisted method against organic dye; herein, methylene blue (MB) dye removal from the water was employed as a metal selenide-based photocatalyst. The synthesized MnSe/GO composite was systematically characterized by X-ray diffraction (XRD), Fourier transform electron microscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and UV-visible diffuse reflectance spectroscopy (UV-vis. DRS). The structural characteristic revealed the adequate synthesis of the sample with good crystallinity and purity of the obtained products. The morphological analysis indicates the formation of MnSe nanoflakes composed of tiny particles on their surface. At the same time, the GO nanosheets with high aggregation were formed, which may be due to the van der Waals forces. The bond interaction and compositional analysis studies confirmed and supported the structural findings with high purity. The optical analysis showed the bandgap energies of MnSe and their composites MnSe (1.7 eV), 7% GO-MnSe (2.42 eV), 14% GO-MnSe (2.6 eV), 21% GO-MnSe (3.02 eV), and 28% GO-MnSe (3.24 eV) respectively, which increase the bandgap energy after GO and MnSe recombination. Among different contents, the optimized 21% GO-MnSe composite displayed enhanced photocatalytic properties. For instance, a short time of 90 min was taken compared with other concentrations due to the narrow bandgap of MnSe and the highly conductive charge carrier's support, making the process to remove MB from water faster. These results show that the selenide-based photocatalyst can be an attractive candidate for future advanced photocatalysis applications.

Solvent Regeneration Methods for Combined Dearomatization, Desulfurization, and Denitrogenation of Fuels Using Deep Eutectic Solvents.

Deep eutectic solvents (DESs) can be used as potential solvents for various applications. However, their recovery depends on both economic and environmental considerations. In this study, the possibilities for the recovery of methyl triphenyl phosphonium bromide/triethylene glycol (MTPPB/TEG 1:4) after the application of combined dearomatization, desulfurization, and denitrogenation of fuels are investigated. The DES was first prepared and characterized for its density, viscosity, and water content. Then, the single-stage liquid-liquid extraction was conducted in addition to testing the repetitive use of the DES. After that, two regeneration methods were studied: the stripping method (with n-heptane) and the washing method (with distilled water or diethyl ether). In addition, a parametric study was conducted to optimize the regeneration methods. The results showed that washing the used DES with distilled water was significantly more effective than stripping the DES with n-heptane. In terms of quinoline reduction, distilled water reduced the quinoline content in the DES from 3.2 to 2.1 wt %, while n-heptane showed a minor reduction in the quinoline content (3.2 to 3 wt %). It was also found that a much more effective recovery could be achieved by (i) increasing the DES-to-regeneration solvent mass ratio and (ii) increasing the number of wash cycles. Furthermore, the regeneration temperature did not have a significant effect on the recyclability of the DES. The results demonstrated that the regenerated DES was as effective in extraction as a fresh batch of DES.

Synthesis, Crystal Structure, Theoretical Calculations, Antibacterial Activity, Electrochemical Behavior, and Molecular Docking of Ni(II) and Cu(II) Complexes with Pyridoxal-Semicarbazone.

New Ni (II) and Cu (II) complexes with pyridoxal-semicarbazone were synthesized and their structures were solved by X-ray crystallography. This analysis showed the bis-ligand octahedral structure of [Ni(PLSC-H)2]·H2O and the dimer octahedral structure of [Cu(PLSC)(SO4)(H2O)]2·2H2O. Hirshfeld surface analysis was employed to determine the most important intermolecular interactions in the crystallographic structures. The structures of both complexes were further examined using density functional theory and natural bond orbital analysis. The photocatalytic decomposition of methylene blue in the presence of both compounds was investigated. Both compounds were active toward E. coli and S. aureus, with a minimum inhibition concentration similar to that of chloramphenicol. The obtained complexes led to the formation of free radical species, as was demonstrated in an experiment with dichlorofluorescein-diacetate. It is postulated that this is the mechanistic pathway of the antibacterial and photocatalytic activities. Cyclic voltammograms of the compounds showed the peaks of the reduction of metal ions. A molecular docking study showed that the Ni(II) complex exhibited promising activity towards Janus kinase (JAK), as a potential therapy for inflammatory diseases, cancers, and immunologic disorders.

Synthesis, Crystal Structure, Quantum Chemical Analysis, Electrochemical Behavior, and Antibacterial and Photocatalytic Activity of Co Complex with Pyridoxal-(S-Methyl)-isothiosemicarbazone Ligand.

New complex Co(III) with ligand Pyridoxal-S-methyl-isothiosemicarbazone, (PLITSC) was synthesized. X-ray analysis showed the bis-ligand octahedral structure of the cobalt complex [Co(PLITSC-H)2]BrNO3·CH3OH (compound 1). The intermolecular interactions governing the crystal structure were described by the Hirsfeld surface analysis. The structure of compound 1 and the corresponding Zn complex (([Zn(PLTSC)(H2O)2]SO4·H2O)) were optimized at the B3LYP/6-31 + G (d,p)/LanL2DZ level of theory, and the applicability was assessed by comparison with the crystallographic structure. The natural bond orbital analysis was used for the discussion on the stability of formed compounds. The antibacterial activity of obtained complexes towards S. aureus and E. coli was determined, along with the effect of compound 1 on the formation of free radical species. Activity of compound 1 towards the removal of methylene blue was also investigated. The voltammograms of these compounds showed the reduction of metal ions, as well as the catalyzed reduction of CO2 in acidic media.

Crystallographic study, biological assessment and POM/Docking studies of pyrazoles-sulfonamide hybrids (PSH): Identification of a combined Antibacterial/Antiviral pharmacophore sites leading to in-silico screening the anti-Covid-19 activity.

The discovery and development of new potent antimicrobial and antioxidant agents is an essential lever to protect living beings against pathogenic microorganisms and free radicals. In this regard, new functionalized pyrazoles have been synthesized using a simple and accessible approach. The synthesized aminobenzoylpyrazoles 3a-h and pyrazole-sulfonamides 4a-g were obtained in good yields and were evaluated in vitro for their antimicrobial and antioxidant activities. The structures of the synthesized compounds were determined using IR, NMR, and mass spectrometry. The structure of the compound 4b was further confirmed by single crystal X-ray diffraction. The results of the in vitro screening show that the synthesized pyrazoles 3 and 4 exhibit a promising antimicrobial and antioxidant activities. Among the tested compounds, pyrazoles 3a, 3f, 4e, 4f, and 4g have exhibited remarkable antimicrobial activity against some microorganisms. In addition, compounds 3a, 3c, 3e, 4a, 4d, 4f, and 4g have shown a significant antioxidant activity in comparison with the standard butylhydroxytoluene (BHT). Hence, compounds 3a, 4f, and 4g represent interesting dual acting antimicrobial and antioxidant agents. In fact, pyrazole derivatives bearing sulfonamide moiety (4a-g) have displayed an important antimicrobial activity compared to pyrazoles 3a-h, this finding could be attributed to the synergistic effect of the pyrazole and sulfonamide pharmacophores. Furthermore, Molecular docking results revealed a good interaction of the synthesized compounds with the target proteins and provided important information about their interaction modes with the target enzyme. The results of the POM bioinformatics investigations (Petra, Osiris, Molinspiration) show that the studied heterocycles present a very good non toxicity profile, an excellent bioavailability, and pharmacokinetics. Finally, an antiviral pharmacophore (O δ-, O δ-) was evaluated in the POM investigations and deserves all our attention to be tested against Covid-19 and its Omicron and Delta mutants.

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO2P Source.

Introducing a small phosphorus-based fragment into other molecular entities via, for example, phosphorylation/phosphonylation is an important process in synthetic chemistry. One of the approaches to achieve this is by trapping and subsequently releasing extremely reactive phosphorus-based molecules such as dioxophosphoranes. In this work, electron-rich hexaphenylcarbodiphosphorane (CDP) was used to stabilize the least thermodynamically favorable isomer of HO2P to yield monomeric CDP·PHO2. The title compound was observed to be a quite versatile phosphonylating agent; that is, it showed a great ability to transfer, for the first time, the HPO2 fragment to a number of substrates such as alcohols, amines, carboxylic acids, and water. Several phosphorous-based compounds that were generated using this synthetic approach were also isolated and characterized for the first time. According to the initial computational studies, the addition-elimination pathway was significantly more favorable than the corresponding elimination-addition route for "delivering" the HO2P unit in these reactions.

Effect of light-dark conditions on inhibition of Gram positive and gram negative bacteria and dye decomposition in the presence of photocatalyst Co/ZnO nanocomposite synthesized by ammonia evaporation method.

Environmental pollution and various bacterial strains cause severe health problems. Thus a need exists to synthesize new materials and develop new techniques which can be used against these hazardous pathogens and components. In this research work, sustainable and effective Co/ZnO nanocomposites were prepared via a new hydrothermal technique and ammonia evaporation method. The synthesized nanomaterial was analytically characterized through various techniques such as X-ray diffraction (XRD), UV-vis spectroscopy, Scanning electron microscope (SEM), High transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), Energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The as prepared nanocomposite was tested for photodegradation of methylene blue (MB). This test was performed both in visible light and in dark condition. The results demonstrate that the said material is more efficient in light compared to dark conditions and decomposed more than 80% MB dye only in 60 min. The synthesized nanomaterial Co/ZnO was also tested against highly drug resistant bacteria Escherichia coli and Staphylococcus aureus both in light and dark. Hence, the antibacterial assessment indicates the zone of inhibition in visible light of Co/ZnO counter with Escherichia coli is 15 (±0.2) and for Staphylococcus aureus is 18 (±0.4) mm and in dark for Escherichia coli is 11 (±0.6) and for Staphylococcus aureus is 14 (±0.1) mm. Moreover, the detail mechanism, reactive oxygen species production and bacterial surface damage were also observed. We demonstrate that Co/ZnO nanomaterial is stable, eco-friendly photocatalyst shows high strength against MB degradation and also shows strong inhibition effect against pathogens in visible light.

Uncaria rhynchophylla mediated Ag/NiO nanocomposites: A new insight for the evaluation of cytotoxicity, antibacterial and photocatalytic applications.

The increase of microbial resistance poses threats to human health. Therefore, efficient treatment of microbial resistance is a global challenge.. During this study, the Ag/NiO nanocomposite was fabricated via simple and ecofriendly method, using Uncaria rhynchophylla extract as a reducing and capping agent to avoid the aggregation of as synthesized nanomaterials. Here, a range of characterization techniques were employed to characterize the sample which includes UV-vis spectroscopy, X-ray diffraction, FTIR spectroscopy, electron diffraction spectroscopy (EDX), scanning electron microscopy (SEM). Furthermore, the resultant nanocomposite demonstrated an efficient ability for the inhibition of both gram-positive and gram negative pathogenic multidrug resistant bacteria. Additionally, the Ag/NiO nanocomposite showed a durable antioxidant effect against DPPH that could still reach 63% at very low concentration, i.e. 0.5 mg/mL. Interestingly, the synthesized nanocomposite is efficient for the production of reactive oxygen species (ROS) and shows no hemolytic activity. Likewise, the Ag/NiO nanocomposite displayed excellent photocatalytic activity to degrade 85% methylene blue (MB) by 4 mg/25 mL and could be used for waste water treatment. It is believed that synthesized nanostructure with desirable morphology and preparation simplicity can be promising material for antimicrobial, antioxidant and catalytic applications.

Synthesis and crystal structures of [Ph3PCH2PPh3]I2 di-chloro-methane disolvate and [Ph3PCH2PPh3](BI4)2.

Reaction of BI3 with carbodi-phospho-rane, C(PPh3)2, gives a mixture of the dicationic compounds, methyl-enebis(tri-phenyl-phospho-nium) diiodide di-chloro-methane disolvate, C37H32P22+·2I-·2CH2Cl2 or [Ph3PCH2PPh3]I2·2CH2Cl2 (I), methyl-enebis(tri-phenyl-phospho-nium) bis-(tetra-iodo-borate), C37H32P22+·2BI4- or [Ph3PCH2PPh3](BI4)2 (II). Solvents are the source of the protons at the ylidic C atom. The P-C-P angle is 124.1 (2)° for (I) and 121.7 (3)° for (II), while the two P-C bond lengths are 1.804 (4) and 1.807 (5) Šin (I), and 1.817 (5) and 1.829 (5) Šin (II). In the crystal of (I), the protons of the central P-CH2-P C atom exhibit weak C-H⋯I hydrogen bonds with the respective anions. The anions in turn are linked to the di-chloro-methane solvent mol-ecules by C-H⋯I hydrogen bonds. In the crystal of (II), one of the BI4- anions is linked to a phenyl H atom via a weak C-H⋯I hydrogen bond.

Synthesis, structural studies and biological activity of a dioxovanadium(v) complex with pyridoxal semicarbazone.

Reaction between the NH4VO3 and pyridoxal semicarbazone (PLSC) in a methanol/ammonia solution forms an orange, diamagnetic, mononuclear NH4[VO2(PLSC-2H)] complex in which vanadium is in the oxidation state +5, and pyridoxal semicarbazone is coordinated in its dianionic form. The complex cocrystallizes with a neutral molecule of PLSC and two water molecules. The coordination environment around vanadium can be described as an almost ideal square-pyramid. The complex was characterized by elemental analysis, conductometric and magnetochemical measurements, IR spectra, X-ray diffraction, and in vitro cytotoxicity analysis.

Bis[4-(2-carbamoylhydrazin-1-yl-idene-κN,O)-5-hydroxy-methyl-2-methyl-pyridinium-3-olato-κO]cobalt(II) dinitrate dihydrate.

The asymmetric unit of the title compound, [Co(C(9)H(12)N(4)O(3))(2)](NO(3))(2)·2H(2)O, consists of a discrete cationic [Co(PLSC)(2)](2+) complex unit [PLSC is 4-(2-carbamoylhydrazin-1-yl-idene)-5-hydroxy-methyl-2-methyl-pyridinium-3-ol-ato], two NO(3) (-) and two water mol-ecules. The two tridentate PLSC ligands of the cation are zwitterions related to each other by a non-crystallographic C(2) axis. The Co(II) ion is in a disorted octa-hedral coordination environment. The crystal structure is composed of alternating NO(3)/H(2)O and complex layers supported by extensive C-H⋯O, N-H⋯O and N-H⋯N hydrogen bonding.

Dibromo(pyridoxal semicarbazone-kappa3N1,O3,O3')copper(II).

The title compound, dibromo(3-hydroxy-5-hydroxymethyl-2-methyl-4-pyridinecarboxaldehyde semicarbazone-kappa(3)N(1),O(3),O(3'))copper(II), [CuBr(2)(C(9)H(12)N(4)O(3))], consists of discrete complex units with the tridentate pyridoxal semicarbazone ligand as a zwitterion in an almost planar configuration. The Cu(II) ions are in a distorted square-pyramidal coordination, with the equatorial Br atom at a distance of 2.4017 (6) A and the apical Br atom at a distance of 2.6860 (6) A.

Transition metal complexes with thiosemicarbazide-based ligands. XLIV. Aqua(3-hydroxy-5-hydroxymethyl-2-methylpyridine-4-carboxaldehyde 3-methylisothiosemicarbazone-kappa(3)O,N1,N4)nitratocopper(II) nitrate.

Part XLIII: Novakovic et al. (2002). The title complex, [Cu(NO(3))(C(10)H(14)N(4)O(2)S)(H(2)O)](NO(3)), is the first metal complex with a Schiff base derived from isothiosemicarbazide and pyridoxal (pyridoxal is 3-hydroxy-5-hydroxymethyl-2-methylpyridine-4-carboxaldehyde). The Cu(II) environment is a square pyramid, the equatorial plane of which is formed by the tridentate ONN-coordinated isothiosemicarbazone and one water molecule, while the nitrate ligand is in the apical position. The existence of numerous strong intermolecular hydrogen bonds, and weak C-H...O and C-H...pi interactions, leads to a three-dimensional supramolecular structure.

Transition metal complexes with thiosemicarbazide-based ligands. XLIII. Chlorobis(3-methylisoemicarbazide-kappa(2)N(1),N(4))zinc(II) chloride.

In the title compound, [ZnCl(C(2)H(7)N(3)S)(2)]Cl, the Zn(II) ion is five-coordinated in a distorted trigonal-bipyramidal arrangement, with the hydrazine N atoms located in the apical positions. The structure is stabilized by N[bond]H...Cl hydrogen bonds, which involve both the Cl atoms and all the hydrogen donors, except for one of the two thioamide N atoms. A comparison of the geometry of thiosemicarbazide and S-methylisothiosemicarbazide complexes with Zn(II), Cu(II) and Ni(II) shows the pronounced influence of the hydrogen-bond network on the coordination geometry of Zn(II) compounds.