Microwave-assisted one-pot multicomponent synthesis of indole derived fluorometric probe for detection of Co2+ ions

Cobalt (Co2+) is an essential constituent in the human body while excessive exposure leads to severe systemic toxic reactions which highlight the importance of developing effective methods to detect Co2+ ions. A simple and highly efficient fluorescence enhanced turn OFF-ON chemosensor was synthesized to detect the paramagnetic Co2+. The ligand, N-((1H-indol-3-yl)(phenyl)methyl)aniline (L), was synthesized in 92% yield by means of hydrated ferric chloride catalyzed one -pot multicomponent microwave irradiation in the presence of Indole, benzaldehyde, and aniline as reactants. The major green principles of waste prevention, high atom economy (94.3%), green solvent, higher energy efficiency, and catalysis were the highlights of the ligand synthesis. The ligand exhibited remarkable fluorescence enhancement with Co2+ and a turn ON ratio of over 160-fold in MeOH/H2O (at pH 3.5) solution at an excitation wavelength of 369 nm in the Ultra-Violet range. The detection limit of L- Co2+ was 2.2 μM. The excitation and the emission spectra indicated stoke’s shift of 93 nm which supports the fluorescence enhancement observed in L- Co2+ with respect to the free ligand. The Job’s plot indicated fluorometric sensing of Co2+ ascribed to the complex formation with a stoichiometric ratio of 2:1 (L- Co2+). Furthermore, the high linearity (r2 =0.992) observed in the Benesi Hildebrand plot in a wide concentration range of 0.5−80 μM confirmed the above stoichiometric ratio. The association constant (Ka) for the L-Co2+ was determined to be 8.382 ×1 04 M−1 ± 5.8 ×103M−1.The prepared Co2+ fluorometric probe indicated long-term stability in −18 ℃ up to 45 days. Furthermore, the presence of Fe2+ and Fe3+ in the medium with Co2+ exhibited an interference effect in the fluorescence intensities. Upon further concentration studies, it was evident that the interference of Fe2+ and Fe3+ starts around 10.00 μM and rises exponentially. Keywords: MCR, Green synthesis, Fluorescent Chemo-sensor, Turn OFF-ON, Cobalt (II), indole derivatives

FeIII in a high-spin state in bis(5-bromosalicylaldehyde 4-ethylthiosemicarbazonato-κ3 O,N 1,S)ferrate(III) nitrate monohydrate, the first example of such a cationic FeIII complex unit

The synthesis and crystal structure (100 K) of the title compound, [Fe(C10H11BrN3OS)2]NO3·H2O, is reported. The asymmetric unit consists of an octahedral [FeIII(HL)2]+ cation, where HL − is H-5-Br-thsa-Et or 5-bromosalicylaldehyde 4-ethylthiosemicarbazonate(1−) {systematic name: 4-bromo-2-[(4-ethylthiosemicarbazidoidene)methyl]phenolate}, a nitrate anion and a noncoordinated water molecule. Each HL − ligand binds via the thione S, the imine N and the phenolate O atom, resulting in an FeIIIS2N2O2 chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis and the N atoms in trans positions. This [Fe(HL)2](anion)·H2O compound contains the first known cationic FeIII entity containing two salicylaldehyde thiosemicarbazone derivatives. The FeIII ion is in the high-spin state at 100 K. In addition, a comparative IR spectroscopic study of the free ligand and the ferric complex is presented, demonstrating that such an analysis provides a quick identification of the degree of deprotonation and the coordination mode of the ligand in this class of metal compounds. The variable-temperature magnetic susceptibility measurements (5–320 K) are consistent with the presence of a high-spin FeIII ion with a zero-field splitting D = 0.439 (1) cm−1.

Synthesis and Characterization of Novel Copper(II)-Sunitinib Complex: Molecular Docking, DFT Studies, Hirshfeld Analysis and Cytotoxicity Studies

The main goal of this work was to report the synthesis, characterization, and cytotoxicity study of a novel copper(II)-sunitinib complex, CuSun. It has been synthesized and characterized in solid state and in solution by different methods (such as DFT, FTIR, Raman, UV-vis, EPR, NMR, etc.). The solid-state molecular structure of trichlorosunitinibcopper(II), where sunitinib: N-[2-(diethylamino)ethyl]-5-[(Z)-(5-fluoro-2-oxo-1H-indol-3-ylidene)methyl]-2,4-dimethyl-1H-pyrrole-3-carboxamide, for short Cu(Sun)Cl3, was determined by X-ray diffraction. It crystallizes in the triclinic space group P-1 with a = 7.9061(5) Å, b = 12.412(1) Å, c = 13.7005(8) Å, α = 105.021(6)°, β = 106.744(5)°, γ = 91.749(5)°, and Z = 2 molecules per unit cell. Also, we have found π-π interactions and classic and non-classic H-bonds in the crystal structure by using Hirshfeld surface analysis. In the speciation studies, the complex has dissociated in protonated sunitinib and chlorocomplex of copper(II), according to 1HNMR, EPR, UV-vis and conductimetric analysis. Molecular docking of the complex in both, ATP binding site and allosteric site of VEGFR2 have shown no improvement in comparison to the free ligand. Besides, cytotoxicity assay on HepG2 cell line shows similar activity for complex and ligand in the range between 1–25 μM supporting the data obtained from studies in solution.

Schiff bases and their metal complexes with biologically compatible metal ions; biological importance, recent trends and future hopes

Schiff bases are in the field of medicinal and material chemistry for a long time. There are several advancements from time to time towards facile synthesis and potential applications. As medicines they have been applied as organic molecules as well as their metal complexes. The activities of metal complexes have been found to increase due to increase lipophilicity in comparison to the corresponding free ligand. Besides simple coordination compounds they have been applied as ionic liquid (IL)- supported and IL-tagged species with far enhanced efficiency. Among metal complexes recent advancement deals with photodynamic therapy to treat a number of tumors with fewer side effects. Schiff bases are efficient ligands and their complexes with almost all metal ions are reported. This mini-review article deals with complexes of Schiff bases with biologically compatible metal ions, Co(II), Cu(II), Zn(II), Pd(II), Ag(I), Pt(II) and their potential uses to combat cancerous cells. Strong hopes are associated with photodynamic therapy and IL-tagged and IL-supported Schiff bases and their complexes.

Crystal structure, Hirshfeld surface analysis and DFT studies of tetrakis(μ-3-nitrobenzoato-κ2 O 1:O 1′)bis[(N,N-dimethylformamide-κO)copper(II)] dimethylformamide disolvate

The title compound, [Cu2(C7H4NO4)4(C3H7NO)2]·(C3H7NO)2, is a binuclear copper(II) complex located on an inversion center midway between the two copper(II) cations. The asymmetric unit consists of one CuII cation, two 3-nitrobenzoato ligands, and two dimethylformamide (DMF) molecules, one of which coordinates to the CuII cation and one is a solvate molecule. The carboxylate groups of the ligands bridge two CuII cations with a Cu—Cu distance of 2.6554 (6) Å, completing a distorted octahedral O5Cu coordination environment. The dihedral angles between the carboxylate and the aromatic ring planes of the two independent ligands are different from one another, viz. 5.2 (3) and 23.9 (3)°. The three-dimensional structure is consolidated by weak C—H...O interactions and stabilized by π–π stacking interactions between the aromatic rings. The complex and the free ligand were further characterized by Fourier-transform infrared spectroscopy (FT–IR), and the energies of the frontier molecular orbitals of the complex were determined by DFT calculations at the B3LYP/def2-TZVP level of theory.

Synthesis, Characterization and Antibacterial Activity Study of Cobalt(II), Nickel(II), Copper(II), Palladium(II), Cadmium(II) and Platinum(IV) Complexes with 4-Amino-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazole-3-thione

New transition metal complexes of cobalt(II), nickel(II), copper(II), palladium(II), cadmium(II), and platinum(IV) with bidentate ligand 4-amino-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazole-3-thiol were synthesized and characterized by microelemental analyses (CHNS), Fourier-transform infrared (FT-IR), UV-Visible spectra, molar conductance, magnetic susceptibility and thermal analyses (TG-DSC). The ligand was synthesized by ring closure of potassium-2-(3,4,5-trimethoxybenzoyl) hydrazine carbodithioate with an excess amount of hydrazine, and then was acidified using hydrochloric acid. The ligand was used as Lewis bases to prepare metal complexes through the reaction of ratio (1:2) metal:ligand. The ligand was characterized by 1H-NMR and 13C-NMR and the previously described methods to identify the complexes. The results obtained from spectra and elemental analyses indicated the tetrahedral geometry around Cd(II) ion, square-planar for Cu(II) and Pd(II), and octahedral geometry around Co(II), Ni(II), and Pt(IV). All the metal complexes showed significant antibacterial activity in comparison with the free ligand. The antibacterial test of the platinum(IV) complex showed higher activity than other metal complexes against bacteria Staphylococcus aureus (G-positive) and Escherichia coli (G-negative).

Polyazulene-Based Materials for Heavy Metal Ion Detection. 3. (E)-5-((6-t-Butyl-4,8-dimethylazulen-1-yl) diazenyl)-1H-tetrazole-Based Modified Electrodes

A recently synthesized azulene-tetrazole molecular receptor is proposed in this paper to continue the series of azulene substituted compounds that have been developed to build polyazulene-based materials for heavy metal (HM) ion detection. This study focuses on characterization of (E)-5-((6-t-butyl-4,8-dimethylazulen-1-yl) diazenyl)-1H-tetrazole (L) by electrochemical techniques in view of its use for designing electrochemical sensors for HM ion complexation. The character of redox processes was proved by cyclic, differential pulse, and rotating disk electrode voltammetry. An in-depth thermodynamic study of the complexation properties of the free ligand with Pb(II) and Cd(II) from aqueous solutions was performed, and the stoichiometry and stability constant values were determined. Chemically modified electrodes (CMEs) based on L (L-CMEs) prepared by controlled potential electrolysis (CPE) at different applied potentials and charges were characterized by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Their surface morphology was examined by scanning electron microscopy (SEM). The complexing properties of L-CMEs were investigated towards the detection of HM ions by anodic stripping and compared to the stability constants of the complexes in solution. Voltametric curves showed well-defined peaks for Pb (II), Cd (II), Cu (II) and Hg (II), but the responses differ from each other and vary depending on the ion concentrations in the accumulation solutions. The best results were obtained for Pb(II) and Cd(II) ions. The results obtained for Pb(II) are promising and can be used for its analysis in water solutions (detection limit of about 10−9 M).

Synthesis, Characterization, Fluorescence and Antimicrobial studies of Cu(II), Co(II), Ni(II), Zn(II) and Cd(II) complexes derived from Schiff’s base (E)-2-(5-chloro-2-hydroxybenzylidene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide

A series of Cu(II), Co(II), Ni(II), Zn(II) and Cd(II) complexes of (E)-2-(5-chloro-2-hydroxybenzylidene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (HL) with ONO donor ligand was synthesized. The ligand (HL) was prepared by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 5-chloro-2-hydroxybenzaldehyde. The HL and its metal complexes have been characterized using elemental analysis and various spectral techniques such as, FTIR, 1H and 13C NMR, Mass, UV–Visible, ESR, thermal analysis (TGA), magnetic moment, conductivity and powder-XRD. The Powder XRD pattern indicates hexagonal or tetragonal system for HL and its metal complexes. The fluorescence studies exhibits strong emission in the range of 400-500 nm for HL. Further in comparison the HL, Zn(II) and Cd(II) complexes showed enhanced emission whereas Cu(II), Co(II) and Ni(II) showed poor emission. The antimicrobial activities of the HL and its metal complexes were studied by minimum inhibitory concentration (MIC) method wherein the metal complexes showed better activity as compare to free ligand.

Spectroscopic Elucidation of Some Complexes of Vanillin Semicarbazone

3-Phenyl-4-methoxybenzaldehyde undergoes condensation with semicarbazide hydrochloride to form a Schiff-base i.e. 3-phenyl-4-methoxybenzaldehyde semicarbazone (abbreviated as MBS). It undergoes complexation with Vanadium(II), Manganese(II), and Copper(II). The comparison of FTIR-spectra of complexes with that of free ligand helps ascertain the coordination points of ligand through the nitrogen of –CH=N– group and oxygen of group. The axial ligands have been varied by chloride, acetate and nitrate ions. The UV/Visible and ESR spectra of complexes predicts their tetragonally distorted octahedral (D4h) symmetry. The tetragonal distortion parameter (Dt) is observed maximum for chloride while it is minimum for nitrate along z-axis. Both vanillin and semicarbazide are established biologically active compounds and hence their biological activities may be enhanced by their complexation and than a versatile field may be developed for further exploration.