Novel Schiff Base Derived from Amino Pyrene: Synthesis, Characterization, Crystal Structure Determination, and Anticancer Applications of the Ligand and Its Metal Complexes.

In this study, we report the cytotoxicity of a newly synthesized Schiff base HL ((E)-2-ethoxy-6((pyren-1-ylimino)methyl)phenol) and its derived metal complexes (Zn(II), Cu(II), Co(II), Cr(III), and Fe(III)) along with their structural characterizations by means of elemental analysis, magnetic moment, molar conductance, IR, UV-Vis, ESR, and mass spectrometry. The single X-ray diffraction of the HL shows that it exists in the phenol-imine form in its solid state. The NMR and IR data indicate that the bidentate binding of the Schiff base ligand with the metal center occurs during complexation through the azomethine nitrogen atom and the hydroxyl group oxygen atom of the 3-ethoxy salicylaldehyde. The electronic spectra and magnetic measurements indicate that the Co(II) complex has a tetrahedral geometry and that the Cr(III) and Fe(III) complexes have a distorted octahedral geometry. The ESR and electronic spectra suggest that the Cu(II) complex has a distorted tetrahedral geometry. The cytotoxic effects of the HL and all of the metal complexes were studied using human breast cancer (MCF-7) cells. The Cu(II) and Zn(II) complexes exhibited the highest activity against the tested cell line, with IC50 values of 5.66 and 12.74 µg/mL, respectively, and their activity was higher than that of the fluorouracil cancer drug against the MCF-7 cells (18.05 µg/mL).

Experimental and Computational Studies of Azo Dye-Modified Luminol Oligomers: Potential Application in Lithium Ion Sensing.

With a view to design novel conjugated oligomers via a facile technique for its possible application in sensors, the present work reports oligomerization of Bismarck Brown (BB) dye with luminol. The structure was confirmed via IR studies, while the electronic transitions were confirmed by UV-visible studies. Morphological studies were carried out via SEM. Computational studies were carried out using the DFT method with a B3LYP 6-311G(d) basis set to investigate the optimized geometry, band gap, and vibrational and electronic transitions data. The HOMO-LUMO energies showed significant reduction in the band gap upon increasing the content of BB dye. The computational IR and UV spectra were noticed to be in close agreement with the experimental results. Spectrophotometric determination of Li ion was attempted using lithium chloride and a lithium carbonate drug commonly used in the treatment of bipolar disorder. The detection limit was noticed to be as low as 5.1 × 10-6 M, which could be used to design a Li ion sensor.

Energy and reactivity profile and proton affinity analysis of rimegepant with special reference to its potential activity against SARS-CoV-2 virus proteins using molecular dynamics.

Rimegepant is a new medicine developed for the management of chronic headache due to migraine. This manuscript is an attempt to study the various structural, physical, and chemical properties of the molecules. The molecule was optimized using B3LYP functional with 6-311G + (2d,p) basis set. Excited state properties of the compound were studied using CAM-B3LYP functional with same basis sets using IEFPCM model in methanol for the implicit solvent atmosphere. The various electronic descriptors helped to identify the reactivity behavior and stability. The compound is found to possess good nonlinear optical properties in the gas phase. The various intramolecular electronic delocalizations and non-covalent interactions were analyzed and explained. As the compound contain several heterocyclic nitrogen atoms, they have potential proton abstraction features, which was analyzed energetically. The most important result from this study is from the molecular docking analysis which indicates that rimegepant binds irreversibly with three established SARS-CoV-2 proteins with ID 6LU7, 6M03, and 6W63 with docking scores - 9.2988, - 8.3629, and - 9.5421 kcal/mol respectively. Further assessment of docked complexes with molecular dynamics simulations revealed that hydrophobic interactions, water bridges, and π-π interactions play a significant role in stabilizing the ligand within the binding region of respective proteins. MMGBSA-free energies further demonstrated that rimegepant is more stable when complexed with 6LU7 among the selected PDB models. As the pharmacology and pharmacokinetics of this molecule are already established, rimegepant can be considered as an ideal candidate with potential for use in the treatment of COVID patients after clinical studies.

Synthesis and characterization of chitosan-supported Fe2O3 nanohybrids for rapid sonophotocatalytic degradation of 2,4,6-trichlorophenol.

The present study reports the design of heterogeneous photocatalytic system using Fe2O3 with chitosan (CS) as a matrix for the sonophotocatalytic degradation of 2,4,6-trichlorophenol (2,4,6-TCP). CS was chosen as a polymer matrix as it is abundant in nature, eco-friendly, and can be easily processed into microparticles, nanofibers, as well as nanoparticles and shows the tendency of adhesion towards a vast range of solid substrates besides serving as a chelating agent toward metallic oxides. The nanohybrids were characterized via Fourier transformation infrared spectrum (FT-IR), X-ray diffraction (XRD), scanning electron microscopy coupled with electron dispersive spectrum (SEM-EDS), thermogravimetric analysis (TGA), and UV-visible diffuse reflectance (UV-Vis-DRS) analyses. Infrared spectroscopy (IR) studies confirmed synergistic interaction between Fe2O3 and CS. The XRD measurements confirmed the crystalline morphology while SEM revealed formation of rod-like structures. The TGA studies confirmed higher thermal stability of CS/Fe2O3 as compared to pure CS. The optical band gap for CS and CS/Fe2O3 was calculated to be 3 eV and 2.25 eV, respectively, from diffuse reflectance spectral (DRS) studies. Rapid photocatalytic degradation of 2,4,6-TCP was observed under UV light irradiation in presence of CS and CS/Fe2O3 nanohybrids which revealed 83.19% and 95.20% degradation within a short span of 60 min. The degraded fragments were identified using liquid chromatography-mass spectrometry (LC-MS). The present study on the development of ecofriendly nanohybrid photocatalyst is expected to provide experimental basis for the future development of CS-based photocatalysts which can be easily processed into membranes/filters for the industrial scale degradation of toxic organic pollutants.

Synergistic Effect of NiLDH@YZ Hybrid and Mechanochemical Agitation on Glaser Homocoupling Reaction.

Herein, we report the synthesis of nickel-layered double hydroxide amalgamated Y-zeolite (NiLDH@YZ) hybrids and the evaluation of the synergistic effect of various NiLDH@YZ catalysts and mechanochemical agitation on Glaser homocoupling reactions. Nitrogen adsorption-desorption experiments were carried out to estimate the surface area and porosity of NiLDH@YZ hybrids. The basicity and acidity of these hybrids were determined by CO2 -TPD and NH3 -TPD experiments respectively and this portrayed good acid-base bifunctional feature of the catalysts. The NiLDH@YZ-catalyzed mechanochemical Glaser coupling reaction achieved best yield of 83 % for the 0.5NiLDH@0.5YZ hybrid after 60 min of agitation, which revealed the highest acid-base bifunctional feature compared to all the investigated catalysts. The developed catalyst has proven itself as a robust and effective candidate that can successfully be employed up to four catalytic cycles without significant loss in catalytic activity, under optimized reaction conditions. This work demonstrated a new strategy for C-C bond formation enabled by the synergy between mechanochemistry and heterogeneous catalysis.

Highly efficient degradation of metronidazole drug using CaFe2O4/PNA nanohybrids as metal-organic catalysts under microwave irradiation.

Catalytic degradation based on microwave irradiation is an emerging technique which promises prompt and efficient catalytic degradation of organic pollutants. Calcium ferrite (CaFe2O4), poly(1-napththylamine) (PNA), and PNA/CaFe2O4 nanohybrids were synthesized via microwave-assisted technique. The properties of the as-prepared CaFe2O4, PNA, and PNA/CaFe2O4 nanohybrids were characterized by the thermogravimetric analysis (TGA), FTIR, XRD, SEM, and ultraviolet-visible spectrophotometry (UV-vis) analyses. The formation of inorganic-organic hybrids was confirmed by the FTIR and XRD studies. Loading of PNA was confirmed to be 8%, 16%, 32%, and 40% in CaFe2O4 which was established by TGA studies and the thermal stability was found to follow the order: CaFe2O4 > 8-PNA/CaFe2O4 > 16-PNA/CaFe2O4 > 32-PNA/CaFe2O4 > 40-PNA/CaFe2O4 > PNA. CaFe2O4 and PNA revealed band gap values of 3.42 eV and 2.60 eV respectively while for the PNA/CaFe2O4 nanohybrids, the values were found to be ranging between 2.46 and 3.00 eV. The PNA modified CaFe2O4 nanohybrids showed higher degradation efficiency towards metronidazole (MTZ) drug as compared with PNA and pure CaFe2O4. MTZ drug showed around 94% degradation within 21 min of microwave irradiation using 40-PNA/CaFe2O4 as catalyst. The enhanced catalytic activity was attributed to the high surface area of the nanohybrid catalyst as well as improved microwave catalytic activity of PNA. The reactive species responsible for degradation were confirmed by scavenger studies which formation of ·OH and O2·- radicals. Recyclability tests showed that the 40-PNA/CaFe2O4 nanohybrid exhibited 86% degradation of MTZ (90 mg/l) even after the third cycle, which reflected higher reusability of the catalyst. The MTZ fragments were identified using liquid chromatography-mass spectrometry (LC-MS).

Synthesis of nanohybrids of polycarbazole with α-MnO2 derived from Brassica oleracea: a comparison of photocatalytic degradation of an antibiotic drug under microwave and UV irradiation.

The present work describes the synthesis of α-MnO2 nanorods using a natural extract of Brassica oleracea (cabbage) and the formulation of its nanohybrids with polycarbazole, i.e., α-MnO2/PCz. Synergistic interaction between PCz and MnO2 is revealed from infrared spectroscopy (IR) studies while the composition is determined by X-ray photoelectron spectroscopy (XPS). The formation of α-MnO2 nanorods is confirmed via high-resolution transmission electron microscopy (HRTEM). The indirect bandgap of α-MnO2 is reported as 2.5 eV while for the nanohybrids it is found to be ranging between 2.3 and 2.5 eV. Results show that 91% and 89% of degradation is achieved within 30 min and 90 min under the microwave and UV irradiation respectively. Hydroxyl radicals (•OH) and superoxide (•O2-) radicals are responsible for photocatalytic degradation of the drug Bactrim DS which is confirmed by radical scavenging experiments. The nanohybrids show promising catalytic activity under UV as well as microwave irradiation.

Scope of organometallic compounds based on transition metal-arene systems as anticancer agents: starting from the classical paradigm to targeting multiple strategies.

The advent of the clinically approved drug cisplatin started a new era in the design of metallodrugs for cancer chemotherapy. However, to date, there has not been much success in this field due to the persistence of some side effects and multi-drug resistance of cancer cells. In recent years, there has been increasing interest in the design of metal chemotherapeutics using organometallic complexes due to their good stability and unique properties in comparison to normal coordination complexes. Their intermediate properties between that of traditional inorganic and organic materials provide researchers with a new platform for the development of more promising cancer therapeutics. Classical metal-based drugs exert their therapeutic potential by targeting only DNA, but in the case of organometallic complexes, their molecular target is quite distinct to avoid drug resistance by cancer cells. Some organometallic drugs act by targeting a protein or inhibition of enzymes such as thioredoxin reductase (TrRx), while some target mitochondria and endoplasmic reticulum. In this review, we mainly discuss organometallic complexes of Ru, Ti, Au, Fe and Os and their mechanisms of action and how new approaches improve their therapeutic potential towards various cancer phenotypes. Herein, we discuss the role of structure-reactivity relationships in enhancing the anticancer potential of drugs for the benefit of humans both in vitro and in vivo. Besides, we also include in vivo tumor models that mimic human physiology to accelerate the development of more efficient clinical organometallic chemotherapeutics.

Development of a near infrared novel bioimaging agent via co-oligomerization of Congo red with aniline and o-phenylenediamine: experimental and theoretical studies.

With a view to study the effect of insertion of a multifunctional dye moiety on the photo physical properties of conducting polymers, the present paper reports for the first time the homopolymerization and co-oligomerization of Congo red (CR) dye with aniline and o-phenylenediamine. The co-oligomerization was established by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (1H-NMR), and ultraviolet-visible (UV-vis) spectroscopy while the morphology was examined using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The theoretical as well as experimental data of 1H-NMR as well as IR studies confirmed the co-oligomer formation while ultraviolet-visible spectroscopy studies revealed a dynamic change in the optical properties upon variation of co-oligomer composition. X-ray diffraction studies established a crystalline morphology of oligomers. Live cell confocal imaging studies revealed that the co-oligomers could be effectively used in NIR imaging.

A highly conductive thin film composite based on silver nanoparticles and malic acid for selective electrochemical sensing of trichloroacetic acid.

A highly conductive thin film composite based on silver nanoparticles (AgNPs) and malic acid (MA) was deposited on glassy carbon electrode (GCE) for the selective and sensitive electrochemical sensing of trichloroacetic acid (TCA). The casting solution containing MA functionalized AgNPs was employed as a precursor for the thermal deposition of the AgNPs integrated MA thin film composite onto the GCE surface. The uniform coverage of AgNPs within the thin film composite at GCE was obtained by field emission scanning electron microscopy (FESEM). A significantly high charge transfer resistance of the modified electrode (85.7â€¯Ω for AgNPs-MA/GCE in 2 mM [Fe(CN)6]3-/4- at a bias of +0.235 V as compared to bare GCE (38.01 Ω) verified the optimum coating of AgNPs-MA composite at the surface of the electrode. The AgNPs-MA composite deposited GCE revealed substantial electrocatalytic activity toward TCA reduction with significantly enhanced reduction current. The novel electrode manifested a linear square wave voltammetric (SWV) response over the concentration ranges of 0.1-2 (R2 = 0.9953) and 4-100 µM (R2 = 0.9969) with a limit of detection (LOD) and limit of quantification (LOQ) of 30 nM and 92.5 nM, respectively. The modified electrode exhibited an excellent long-term stability (30 days) with the retention of >95% of initial current. The selectivity of the proposed electrode for the determination of TCA was examined in the presence of dichloroacetic acid (DCA) and monochloroacetic acid (MCA) with the retention of high recovery percentages.

Synthesis of copper/nickel nanoparticles using newly synthesized Schiff-base metals complexes and their cytotoxicity/catalytic activities.

Transition metal complexes compounds with Schiff bases ligand representing an important class of compounds that could be used to develop new metal-based anticancer agents and as precursors of metal NPs. Herein, 2,3-bis-[(3-ethoxy-2-hydroxybenzylidene)amino]but-2-enedinitrile Schiff base ligand and its corresponding copper/nickel complexes were synthesized. Also, we reported a facile and rapid method for synthesis nickel/copper nanoparticles based on thermal reduction of their complexes. Free ligand, its metal complexes and metals nanoparticles have been characterized based on elemental analysis, transmission electron microscopy, powder X-ray diffraction, magnetic measurements and by various spectroscopic (UV-vis, FT-IR, (1)H NMR, GC-MS) techniques. Additionally, the in vitro cytotoxic activity of free ligand and its complexes compounds were assessed against two cancer cell lines (HeLa and MCF-7 cells)and one healthy cell line (HEK293 cell). The copper complex was found to be active against these cancer cell lines at very low LD50 than the free ligand, while nickel complex did not show any anticancer activity against these cell lines. Also, the antibacterial activity of as-prepared copper nanoparticles were screened against Escherichia coli, which demonstrated minimum inhibitory concentration and minimum bactericidal concentration values lower than those values of the commercial Cu NPs as well as the previous reported values. Moreover, the synthesized nickel nanoparticles demonstrated remarkable catalytic performance toward hydrogenation of nitrobenzene that producing clean aniline with high selectivity (98%). This reactivity could be attributed to the high degree of dispersion of Ni nanoparticles.

Synthesis of new microbial pesticide metal complexes derived from coumarin-imine ligand.

A series of metal complexes of zinc(II), cadmium(II), copper(II), nickel(II) and palladium(II) have been synthesized from coumarin-imine ligand, 8-[(1E)-1-(2-aminophenyliminio)ethyl]-2-oxo-2H-chromen-7-olate, [HL]. The structures of the complexes were proposed in the light of their spectroscopic, molar conductance, magnetic and thermal studies. The ligand coordinated in a tridentate manner through the azomethine nitrogen, the phenolic oxygen and the amine nitrogen and all complexes were non-electrolytes with different geometrical arrangements around the central metal ion. Photoluminescence data unambiguously showed remarkable fluorescence enhancement to Zn(2+) over other cations. The antimicrobial screening tests revealed that copper(II) complex exhibited the highest potency and its minimum inhibitory concentration on the enzymatic activities of the tested microbial species was determined. No toxin productivity was detected for all tested toxigenic species upon the exposure of copper complex.

2-Amino-3-[(E)-(2-hy-droxy-3-methyl-benzyl-idene)amino]-but-2-ene-dinitrile.

The title compound, C(12)H(10)N(4)O, is a Schiff base obtained from the condensation of diamino-maleonitrile and 2-hy-droxy-3-methyl-benzaldehyde. The mol-ecule is roughly planar, with an r.m.s. deviation of 0.0354 Å, and adopts the phenol-imine tautomeric form. An intra-molecular O-H⋯N hydrogen bond involving the O-H group and the azomethine N atom generates an S(6) ring. In the crystal, there are two N-H⋯N hydrogen bonds.

7-[(3,5-Di-tert-butyl-2-hy-droxy-benzyl-idene)amino]-4-methyl-2H-chromen-2-one.

The title compound, C(25)H(29)NO(3), is a Schiff base derivative of coumarin 120. There are two structurally similar but crystallographically independent mol-ecules in the asymmetric unit. Both mol-ecules exist in E configurations with respect to the C=N double bonds. The dihedral angles between the coumarin and 3,5-di-tert-butyl-2-hy-droxy-benzyl-idene ring planes are 4.62 (7) and 14.62 (7)° for the two mol-ecules. Intra-molecular O-H⋯N hydrogen bonding involving the O-H groups and the azomethine N atoms generate S(6) rings. In the crystal structure, independent mol-ecules are linked by C-H⋯π inter-actions, with groups of four mol-ecules stacked along the c axis.