Synthesis, Crystal Structures, Genotoxicity, and Antifungal and Antibacterial Studies of Ni(II) and Cd(II) Pyrazole Amide Coordination Complexes.

In this study, we synthesized two coordination complexes based on pyrazole-based ligands, namely 1,5-dimethyl-N-phenyl-1H-pyrazole-3-carboxamide (L1) and 1,5-dimethyl-N-propyl-1H-pyrazole-3-carboxamide (L2), with the aim to investigate bio-inorganic properties. Their crystal structures revealed a mononuclear complex [Ni(L1)2](ClO4)2 (C1) and a dinuclear complex [Cd2(L2)2]Cl4 (C2). Very competitive antifungal and anti-Fusarium activities were found compared to the reference standard cycloheximide. Additionally, L1 and L2 present very weak genotoxicity in contrast to the observed increase in genotoxicity for the coordination complexes C1 and C2.

Synthesis, structural characterizations, in vitro biological evaluation and computational investigations of pyrazole derivatives as potential antidiabetic and antioxidant agents.

In this study, a two pyrazole derivatives; 2-(5-methyl-1H-pyrazole-3-carbonyl)-N-phenylhydrazine-1-carboxamide (Pyz-1) and 4-amino-5-(5-methyl-1H-pyrazol-3-yl)-4H-1,2,4-triazole-3-thiol (Pyz-2) were synthesized and characterized by 13C-NMR, 1H-NMR, FT-IR, and mass spectrometry. A complete molecular structures optimization, electronic and thermodynamic properties of Pyz-1 and Pyz-2 in gas phase and aqueous solution were predicted by using hybrid B3LYP method with the 6-311++G** basis sets. Pyz-1 and Pyz-2 were evaluated in vitro for their anti-diabetic, antioxidant and xanthine oxidase inhibition activities. For anti-diabetic activity, Pyz-1 and Pyz-2 showed a potent α-glucosidase and α-amylase inhibition with IC50 values of 75.62 ± 0.56, 95.85 ± 0.92 and 119.3 ± 0.75, 120.2 ± 0.68 µM, respectively, compared to Acarbose (IC50(α-glucosidase) = 72.58 ± 0.68 µM, IC50(α-amylase) = 115.6 ± 0.574 µM). In xanthine oxidase assay, Pyz-1 and Pyz-2 exhibited remarkable inhibitory ability with IC50 values 24.32 ± 0.78 and 10.75 ± 0.54 µM, respectively. The result of antioxidant activities showed that the title compounds have considerable antioxidant and radical scavenger abilities. In addition, molecular docking simulation was used to determine the binding modes and energies between the title compounds and α-glucosidase and α-amylase enzymes.

New triazole-based coordination complexes as antitumor agents against triple negative breast cancer MDA-MB-468 cell line.

The present work describes the synthesis of a new triazole based ligand 3-(3,5-dimethyl-1H-pyrazol-1-yl)-1-methyl-1H-1,2,4-triazole (LM) and demonstration of its coordination diversity giving rise to a family of seven new coordination complexes, namely: [Ni(LM)3](ClO4)2·C2H6OS (5), [Co2(LM)6](ClO4)4·(C2H5)O (6), [Cd(LM)2Cl2] (7), [Cu(LM)2NO3]NO3 (8), [Fe(LM)3](BF4)2 (9), [Zn(LM)3](BF4)2 (10) and [Zn(LM)2NO3]NO3 (11), whose crystal structure was determined by single-crystal X-ray diffraction. Cytotoxic activity was evaluated against the MDA-MB-468 cancer cell line, which serves as a model for triple-negative breast cancer, and compared to the precursor molecule (L), as well as their coordination complexes (H3O){[NiL3](ClO4)3} (1), [CoL3](ClO4)2·2H2O (2), [CdL2Cl2] (3) and [CuL3](NO3)2 (4), for which the crystal structure was earlier determined. Notably, cadmium complexes 3 and 7 exhibit remarkable cytotoxicity and demonstrated a high selectivity index towards cancer cells when compared to peripheral blood mononuclear cells. Such activity highlights their potential function as anticancer agents.

Coordination Complexes Built from a Ditopic Triazole-Pyrazole Ligand with Antibacterial and Antifungal Performances.

Four mononuclear complexes (H3O){[NiL3](ClO4)3} (1), [CoL3](ClO4)2·2H2O (2), [CdL2Cl2] (3) and [CuL3](NO3)2 (4) have been prepared employing a newly synthesized 1,2,4-triazole ligand: 3-(3,5-dimethyl-1H-pyrazol-1-yl)-1H-1,2,4-triazole (L). The structures of the complexes, which crystallized in P63/m (1), P-1 (2), P1 (3), and P21/c (4), are reviewed within the context of the cooperative effect of the hydrogen bonding network and counter anions on the supramolecular formations. Moreover, within the framework of biological activity examination, these compounds showed favorable antibacterial performances compared to those of various species of bacteria, including both Gram-positive and Gram-negative strains. Significant antifungal inhibitory activity towards Fusarium oxysporum f. sp. albedinis fungi was recorded for 3 and 4 over the ligand L.

CuII Pyrazolyl-Benzimidazole Dinuclear Complexes with Remarkable Antioxidant Activity.

Three dinuclear coordination complexes generated from 1-n-butyl-2-((5-methyl-1H-pyrazole-3-yl)methyl)-1H-benzimidazole (L), have been synthesized and characterized spectroscopically and structurally by single crystal X-ray diffraction analysis. Reaction with iron(II) chloride and then copper(II) nitrate led to a co-crystal containing 78 % of [Cu(NO3 )(µ-Cl)(L')]2 (C1 ) and 22 % of [Cu(NO3 )(µ-NO3 )(L')]2 (C2 ), where L was oxidized to a new ligand L' . A mechanism is provided. Reaction with copper chloride led to the dinuclear complex [Cu(Cl)(µ-Cl)(L)]2 (C3 ). The presence of N-H⋅⋅⋅O and C-H⋅⋅⋅O intermolecular interactions in the crystal structure of C1 and C2 , and C-H⋅⋅⋅N and C-H⋅⋅⋅Cl hydrogen bonding in the crystal structure of C3 led to supramolecular structures that were confirmed by Hirshfeld surface analysis. The ligands and their complexes were tested for free radical scavenging activity and ferric reducing antioxidant power. The complex C1 /C2 shows remarkable antioxidant activities as compared to the ligand L and reference compounds.

Mesoporous Silica Modified with 2-Phenylimidazo[1,2-a] pyridine-3-carbaldehyde as an Effective Adsorbent for Cu(II) from Aqueous Solutions: A Combined Experimental and Theoretical Study.

In this study, we will present an efficient and selective adsorbent for the removal of Cu(II) ions from aqueous solutions. The silica-based adsorbent is functionalized by 2-phenylimidazo[1,2-a] pyridine-3-carbaldehyde (SiN-imd-py) and the characterization was carried out by applying various techniques including FT-IR, SEM, TGA and elemental analysis. The SiN-imd-py adsorbent shows a good selectivity and high adsorption capacity towards Cu(II) and reached 100 mg/g at pH = 6 and T = 25 °C. This adsorption capacity is important compared to other similar adsorbents which are currently published. The adsorption mechanism, thermodynamics, reusability and the effect of different experimental conditions, such as contact time, pH and temperature, on the adsorption process, were also investigated. In addition, a theoretical study was carried out to understand the adsorption mechanism and the active sites of the adsorbent, as well as the stability of the complex formed and the nature of the bonds.

Novel family of bis-pyrazole coordination complexes as potent antibacterial and antifungal agents.

A new pyrazole ligand, N,N-bis(2(1',5,5'-trimethyl-1H,1'H-[3,3'-bipyrazol]-1-yl)ethyl)propan-1-amine (L) was synthesized and characterized by 1H-NMR, 13C-NMR, FT-IR and HRMS. The coordination ability of the ligand has been employed for the construction of a new family of coordination complexes, namely: [Cu2LCl4] (1), [ML(CH3OH)(H2O)](ClO4)2 (MII = Ni (2), Co (3)) and [FeL(NCS)2] (4). The series of complexes were characterized using single-crystal X-ray diffraction, HRMS, FT-IR and UV-visible spectroscopy. Moreover, the iron(ii) analogue was investigated by 57Fe Mössbauer spectroscopy and SQUID magnetometry. Single-crystal X-ray structures of the prepared complexes are debated within the framework of the cooperative effect of the hydrogen bonding network and counter anions on the supramolecular formations observed. Furthermore, within the context of biological activity surveys, these compounds were reviewed against different types of bacteria to validate their efficiency, including both Gram-positive as well as Gram-negative bacteria. Enhanced behaviour towards Fusarium oxysporum f. sp. albedinis fungi, were detected for 1 and 4.

Coordination complexes constructed from pyrazole-acetamide and pyrazole-quinoxaline: effect of hydrogen bonding on the self-assembly process and antibacterial activity.

Two mononuclear coordination complexes of N-(2-aminophenyl)-2-(5-methyl-1H-pyrazol-3-yl)acetamide (L1), namely [Cd(L1)2Cl2] (C1) and [Cu(L1)2(C2H5OH)2](NO3)2 (C2) and one mononuclear complex [Fe(L2)2(H2O)2](NO3)2·2H2O (C3), obtained after in situ oxidation of L1, have been synthesized and characterized spectroscopically. As revealed by single-crystal X-ray diffraction, each coordination sphere made of two heterocycles is completed either by two chloride anions (in C1), two ethanol molecules (in C2) or two water molecules (in C3). The crystal packing analysis of C1, C2 and C3, revealed 1D and 2D supramolecular architectures, respectively, via various hydrogen bonding interactions, which are discussed in detail. Furthermore, evaluation in vitro of the ligands and their metal complexes for their antibacterial activity against Escherichia coli (ATCC 4157), Pseudomonas aeruginosa (ATCC 27853), Staphylococcus aureus (ATCC 25923) and Streptococcus fasciens (ATCC 29212) strains of bacteria, revealed outstanding results compared to chloramphenicol, a well-known antibiotic, with a normalized minimum inhibitory concentration as low as 5 µg mL-1.

Experimental and theoretical study for removal of trimethoprim from wastewater using organically modified silica with pyrazole-3-carbaldehyde bridged to copper ions.

BACKGROUND: Human and veterinary antibiotics are typically discharged as parent chemicals in urine or feces and are known to be released into the environment via wastewater treatment plants (WWTPs). Several research investigations have recently been conducted on the removal and bioremediation of pharmaceutical and personal care products (PPCPs) disposed of in wastewater. RESULTS: SiNP-Cu, a chelating matrix, was produced by delaying and slowing 1.5-dimethyl-1H-pyrazole-3-carbaldehyde on silica gel from functionalized with 3-aminopropyltrimethoxysilane. The prepared sorbent material was characterized using several techniques including BET surface area, FT-IR spectroscopy, Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and nitrogen adsorption-desorption isotherm. The pseudo-second-order model provided the best correlation due to the big match between the experimental and theoretical of different adsorption coefficients. The Langmuir and Freundlich adsorption models were used and the study showed a better match with the Freundlich model with a capacity of removal reached up to 420 mg g-1. The removal capacity was dependent on pH and increased by increasing pH. The removal percentage reached 91;5% at pH = 8. The adsorbent demonstrated a high percentage removal of TMP, reaching more than 94% when increased pH. The sample was simply regenerated by soaking it for a few minutes in 1 N HCl and drying it. The sorbent was repeated five times with no discernible decrease in removal capacity. The thermodynamic study also showed endothermic, increasing randomness and not spontaneous. The free energy was 2.71 kJ/mol at 320 K. The findings of the DFT B3LYP/6-31 + g (d, p) local reactivity descriptors revealed that nitrogen atoms and π-electrons of the benzene and pyrimidine rings in the TMP are responsible for the adsorption process with the SiNP surface. The negative values of the adsorption energies obtained by molecular dynamic simulation indicated the spontaneity of the adsorption process. CONCLUSION: The global reactivity indices prove that TMP is stable and it can be removed from wastewater using SiNP surface. The results of the local reactivity indices concluded that the active centers for the adsorption process are the nitrogen atoms and the π-electrons of the pyrimidine and benzene rings. Furthermore, the positive value of the maximum charge transfer number (ΔN) proves that TMP has a great tendency to donate electrons to SiNP surface during the process of adsorption.

A Highly Efficient Environmental-Friendly Adsorbent Based on Schiff Base for Removal of Cu(II) from Aqueous Solutions: A Combined Experimental and Theoretical Study.

Removal of heavy metals from drinking water sources and rivers is of strategic health importance and is essential for sustainable ecosystem development, in particular in polluted areas around the globe. In this work, new hybrid inorganic-organic material adsorbents made of ortho- (Si-o-OR) or para-Schiff base silica (Si-p-OR) were synthesized and characterized in depth. These hybrid adsorbents show a high selectivity to Cu(II), even in the presence of competing heavy metals (Zn(II), Cd(II), and Pb(II)), and also demonstrate great reusability after five adsorption-desorption cycles. Maximum sorption capacity for Cu(II) was found for Si-o-OR (79.36 mg g-1) and Si-p-OR (36.20 mg g-1) in no less than 25 min. Energy dispersive X-ray fluorescence and Fourier transform-infrared spectroscopy studies demonstrate that this uptake occurs due to a chelating effect, which allows these adsorbents to trap Cu(II) ions on their surfaces; this result is supported by a theoretical study for Si-o-OR. The new adsorbents were tested against real water samples extracted from two rivers from the Oriental region of Morocco.

Kinetics, thermodynamics, equilibrium, surface modelling, and atomic absorption analysis of selective Cu(ii) removal from aqueous solutions and rivers water using silica-2-(pyridin-2-ylmethoxy)ethan-1-ol hybrid material.

The removal of heavy metals is attracting considerable attention due to their undesirable effects on the environment. In this investigation, a new adsorbent based on silica functionalized with pyridin-2-ylmethanol (SiPy) was successfully synthesized to yield to a hybrid material. FTIR, SEM, TGA, and specific surface area analysis were used to characterize the structure and morphology of the SiPy hybrid material. Various heavy metal ions such as Cu(ii), Zn(ii), Cd(ii), and Pb(ii) were selected to examine the adsorption efficiency of the newly prepared adsorbent, optimized at varying solution pH, contact time, concentration, and temperature. The adsorbent SiPy displayed good adsorption capacity of 90.25, 75.38, 55.23, and 35.12 mg g-1 for Cu(ii), Zn(ii), Cd(ii), and Pb(ii), respectively, at 25 min and pH = 6. The adsorption behaviors of metal ions onto the SiPy adsorbent fitted well with the pseudo-second-order kinetic mode and the isotherm was better described by the Langmuir isotherm. The thermodynamic studies disclose spontaneous and endothermic adsorption process. Furthermore, the SiPy adsorbent retained good selectivity and regeneration properties after five adsorption-desorption cycles of Cu(ii). A computational investigation of the adsorption mechanism indicates that the N-pyridine, O-hydroxyl, and ether O-atoms play a predominant role during the capture of Cu(ii), Zn(ii), Cd(ii), and Pb(ii). This study proposes the SiPy adsorbent as an attractive material for the selective removal of Cu(ii) from real river water and real industrial wastewater.

Synthesis and cytotoxicity against tumor cells of pincer N-heterocyclic ligands and their transition metal complexes.

The complexes: [CoL2](ClO4)2 (1), [FeL2](ClO4)2 (2), [NiL2](ClO4)2 (3) and [MnLCl2] (4), with L = diethyl-1,1'-(pyridine-2,6-diyl)bis(5-methyl-1H-pyrazole-3-carboxylate), were synthesized and fully characterized. Structural analysis revealed two distinct patterns influenced by the counter ions where L acts as a tridentate chelating ligand. The in vitro antitumor activity of L and L' (diethyl 2,2'-(pyridine-2,6-diylbis(5-methyl-1H-pyrazole-3,1-diyl)) diacetate) as well as their metal complexes, was tested by the measurement of their cytostatic and cytotoxic properties towards the blood cancer mastocytoma cell line P815. We have also investigated their interactions with the antioxidant enzyme system. As a result, [MnL'Cl2] (1') exhibited the strongest activity compared to reference cis-platin with no cytotoxicity towards normal cells PBMCs (Peripheral Blood Mononuclear Cells). On the other hand, the antioxidant enzyme activity showed that the efficiency of metal complex 1' against P815 tumor cells was via the rise in the SOD activity and inhibition of CAT enzyme activity. This proof of concept study allows disclosure of a new class of molecules in cancer therapeutics.

Efficient and Environmentally Friendly Adsorbent Based on ß-Ketoenol-Pyrazole-Thiophene for Heavy-Metal Ion Removal from Aquatic Medium: A Combined Experimental and Theoretical Study.

A new sustainable and environmentally friendly adsorbent based on a ß-ketoenol-pyrazole-thiophene receptor grafted onto a silica surface was developed and applied to the removal of heavy-metal ions (Pb(II), Cu(II), Zn(II), and Cd(II)) from aquatic medium. The new material SiNPz-Th was well characterized and confirms the success of covalent binding of the receptor on the silica surface. The effect of environmental parameters on adsorption including pH, contact time, temperature, and the initial concentration were investigated. The maximum adsorption capacities of SiNPz-Th for Pb(II), Cu(II), Zn(II), and Cd(II) ions were 102.20, 76.42, 68.95, and 32.68 mg/g, respectively, at 30 min and pH = 6. The adsorption isotherms, kinetics, and thermodynamic process were investigated and showed efficiency and selectivity toward Pb(II) and good regeneration performance. Density functional theory, noncovalent-interaction, and quantum theory of atoms in molecules calculations were used to study and to gain a deeper understanding of both the adsorption mechanism and selectivity of metal ions onto the adsorbent. Accordingly, metal ions such as Pb(II), Cu(II), and Zn(II) were bidentate coordinated with the adsorbent by nitrogen and oxygen atoms of the Schiff base C=N and hydroxyl group -OH, respectively, to form stable complexes. Whereas Cd(II) was coordinated in a monodentate fashion with oxygen atom of the hydroxyl group. Furthermore, the affinity of SiNPz-Th toward the metal ions was decreased in the order of Pb(II) > Cu(II) > Zn(II) > Cd(II), in good agreement with the experimental results. All these results highlight that SiNPz-Th has good potential to be an advanced adsorbent for the removal of lead ions from real water.

Synthesis, Biochemical Characterization, and Theoretical Studies of Novel ß-Keto-enol Pyridine and Furan Derivatives as Potent Antifungal Agents.

In the present study, we report the design and synthesis of new derivatives of the ß-keto-enol grafted on pyridine and furan moieties (L 1 -L 11 ). Structures of compounds were fully confirmed by Fourier transform infrared spectroscopy (FT-IR), 1H NMR, 13C NMR, electrospray ionization/liquid chromatography-mass spectrometry (ESI/LC-MS), and elemental analysis. The compounds were screened for antifungal and antibacterial activities (Escherichia coli, Bacillus subtilis, and Micrococcus luteus). In vitro evaluation showed significant fungicidal activity for L 1 , L 4 , and L 5 against fungal strains (Fusarium oxysporum f.sp albedinis) compared to the reference standard. Especially, the exceptional activity has been demonstrated for L 1 with IC50 = 12.83 µg/mL. This compound and the reference benomyl molecule also showed a correlation between experimental antifungal activity and theoretical predictions by Petra/Osiris/Molinspiration (POM) calculations and molecular coupling against the Fgb1 protein. The highest inhibition of bacterial growth for L 1 is due to its strongest binding to the target protein. This report may stimulate the further synthesis of examples of this substance class for the development of new drugs.

Solvent induced supramolecular polymorphism in Cu(II) coordination complex built from 1,2,4-triazolo[1,5-a]pyrimidine: Crystal structures and anti-oxidant activity.

Two Cu(II) coordination complexes, C1 and C2 of the formula [Cu(4)2(H2O)2], have been prepared by reaction between CuCl2·2H2O and 7-ethoxycarbonylmethyl-5-methyl-1,2,4[1,5-a]pyrimidine (L) in a 1:2 M:L molar ratio. The L molecule decomposes during the reaction process into 7-carboxy-5-methyl-[1,2,4]-triazolo[1,5-a]pyrimidine (4) through an intermediate, ethyl 2,2-dihydroxy-2-(5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-yl)acetate (5), which has been isolated and its crystal structure determined by X-ray diffraction. The X-ray analysis of the single crystals of [Cu(4)2(H2O)2] obtained from the slow evaporation of EtOH and MeOH, separately, revealed the formation of "solvent induced" polymorphs C1 and C2, respectively. The primary supramolecular synthon for C1 and C2 are six membered ring, and square shaped hydrogen bonded architecture, respectively. The self-assembly of such synthons resulted in a two dimensional hydrogen bonded sheet supported by OH⋯O interactions. In addition, the antioxidant properties of the ligands and its complexes were evaluated in vitro using 1,1-diphenyl-2-picrylhydrazyl acid, 2,2'-azino-bis (3-ethylbenzothiazoline-6 sulfonic acid radical scavenging methods and ferric reducing antioxidant power.

Synthesis, Antimicrobial Screening, Homology Modeling, and Molecular Docking Studies of a New Series of Schiff Base Derivatives as Prospective Fungal Inhibitor Candidates.

Twelve new Schiff base derivatives have been prepared by the condensation reaction of different amino substituted compounds (aniline, pyridin-2-amine, o-toluidine, 2-nitrobenzenamine, 4-aminophenol, and 3-aminopropanol) and substituted aldehydes such as nicotinaldehyde, o,m,p-nitrobenzaldehyde, and picolinaldehyde in ethanol using acetic acid as a catalyst. The envisaged structures of the all the synthesized ligands have been confirmed on the basis of their spectral analysis FT-IR, mass spectroscopy, 1H- and 13C-NMR. In vitro screening of their antibacterial and antifungal potential against Escherichia coli bacterium and Fusarium oxysporum f.sp albedinis (F.o.a) fungus, respectively, revealed that all the ligands showed no significant antibacterial activity, whereas most of them displayed good antifungal activity. Homology modeling and docking analysis were performed to explain the antifungal effect of the most and least active compound against two F.o.a fungus proteins.

Removal and extraction efficiency of Quaternary ammonium herbicides paraquat (PQ) from aqueous solution by ketoenol-pyrazole receptor functionalized silica hybrid adsorbent (SiNPz).

Pesticides and herbicides have been used extensively in agricultural practices to control pests and increase crop yields. Paraquat (PQT2+, 1,1-dimethyl-4,4-dipyridinium chloride) is one of the herbicide that belois classified as bipyridines and is used over the world. The objective of this study is to use ketoenol-pyrazole receptor functionalized silica hybrid as adsorbent for removal PQT2+ from aqueous solution. The adsorbent was synthesized, and characterized using scanning electron microscopy (SEM), nuclear magnetic resonance (NMR), Thermal analysis and other techniques. Different experimental parameters such as the effect of the amount of adsorbent, solution pH and temperatures and contact times were studied. Pseudo-order kinetics models were studied, and our data followed a pseudo second order. Experimental data were analyzed for both Langmuir and Freundlich models and the data fitted well with the Langmuir isotherm model. To understand the mechanism of adsorption, thermodynamic parameters like standard enthalpy, standard Gibbs free energy, and standard entropy were studied. The study indicated that the process is spontaneous, exothermic in nature and follow physisorption mechanisms. The novelty of this study showed surface of pyrazol-enol-imine-substituted silica (SiNPz) has the ability to highlight the surface designed for efficient removal of PQT2+, from aqueous solutions more than other studies. The study also showed that ketoenol-pyrazole receptor can be regenerated in five cycles using HNO3 without affecting its adsorption capacity.

Highly Selective Removal of Pb(II) by a Pyridylpyrazole-ß-ketoenol Receptor Covalently Bonded onto the Silica Surface.

Efficient materials capable of capturing toxic metals from water are widely needed. Herein, a new pyridylpyrazole-ß-ketoenol receptor, X-ray diffraction analyzed, was covalently incorporated into the silica surface to produce solid and recyclable adsorbent particles. The new material, fully characterized, revealed extremely efficient removal of toxic metals from water, with a selectivity order of Pb(II) > Zn(II) > Cu(II) > Cd(II). The adsorption was exceptionally rapid at optimum pH and concentrations, showing Pb(II) removal of 93 mg g-1 within 5 min and maximum Pb(II) adsorption of 110 mg g-1 after only 20 min. Sorption isotherms agreed well with the Langmuir model suggesting a monolayer adsorption, whereas kinetics agreed with the pseudo-second-order model suggesting a chemisorption binding mechanism. Thermodynamics of adsorption were fitted with an endothermic and spontaneous process. The material, recyclable for at least five cycles, is therefore promising for the cleanup of water polluted by toxic metals, especially lead.

Novel ß-keto-enol Pyrazolic Compounds as Potent Antifungal Agents. Design, Synthesis, Crystal Structure, DFT, Homology Modeling, and Docking Studies.

A new family of promising inhibitors bearing ß-keto-enol functionality with greatly improved pharmacophore properties has been prepared. Herein, a series of novel derivatives of ß-keto-enol group embedded with pyrazolic moiety has been designed and synthesized via a one-step procedure using mixed Claisen condensation in the attempt to develop potential antifungal agents. The structures of the synthesized compounds were confirmed by elemental analysis, FT-IR, ESI/LC-MS, and 1H and 13C NMR. In addition, X-ray diffraction analysis (XRD) was used to determine the single crystal structure of compound 10. All of the new compounds have been evaluated for their in vitro antifungal and antibacterial activities. Interestingly, the results indicate that most of the compounds display notable antifungal activity close to that of the benomyl fungicide taken as the standard drug. For the most active compound and for benomyl, a correlation has been evidenced between the experimental antifungal activity and the theoretical predictions by DFT calculations and molecular docking against Fgb1 protein.

Removal of toxic heavy metals from river water samples using a porous silica surface modified with a new ß-ketoenolic host.

A new hybrid adsorbent material for the efficient removal of heavy metals from natural real water solutions (Moroccan river water samples) was prepared by the immobilization of a new conjugated ß-ketoenol-pyridine-furan ligand onto a silica matrix. The thermodynamical properties including pH, adsorption isotherms, competitive adsorption, selectivity and regeneration were studied to investigate the effect of ketoenol-pyridine-furan-silica (SiNL) on the removal of Zn(II), Pb(II), Cd(II) and Cu(II) from aqueous solutions. An increase in adsorption as a function of pH and fast adsorption was reached within 25 min. The maximum sorption capacities for Zn(II), Pb(II), Cd(II) and Cu(II) were 96.17, 47.07, 48.30 and 32.15 mg·g-1, respectively. Furthermore, the material proved to be very stable - its adsorption capacity remained greater than 98% even after five cycles of adsorption/desorption. Compared to literature results, this material can be considered a high-performing remediation adsorbent for the extraction of Zn(II) from natural real water solution.