Iron(III), nickel(II) and zinc(II) complexes based on acetophenone-S-methyl-thiosemicarbazone: synthesis,characterization, thermogravimetry,and a structural study

New complexes, [Fe(L)Cl], [Ni(L)], and [Zn(L)C₂H₅OH] (1–3), were synthesized by template reaction of 2-hydroxy-acetophenone-S-methyl-thiosemicarbazone with 2-hydroxy-benzaldehyde. The compounds were characterized by elemental analysis, magnetic measurements, FT-IR, ¹H NMR, UV–visible, and ESI–MS spectra. In these complexes, the ligand is coordinated to the metal ion as dinegatively charged tetradentate chelating agents via the N₂O₂ donor set. The iron(III) and zinc(II) complexes exhibit square pyramidal geometry whereas the nickel(II) complex has a square planar geometry. The crystal structure of 1, determined by X-ray diffraction method, indicates that 1 crystallizes in the monoclinic space group P21/c with Z = 4. Thermal decompositions of the compounds have been investigated using TGA in air.     

Synthesis of Novel Triazole Incorporated Thiazolone Motifs Having Promising Antityrosinase Activity through Green Nanocatalyst CuI-Fe3O4@SiO2 (TMS-EDTA)

In the present work, novel 5-((1-benzyl-1,2,3-triazol-4-yl)methoxybenzylidene)-2-(arylamino)thiazol-4-one thiazolone incorporated triazole derivatives have been designed as tyrosinase inhibitors. The compounds were synthesized through click reaction in good yield. Moreover, the antityrosinas activity of the synthesized derivatives was evaluated. In the search for establishing a click copper-catalyzed azide/alkyne cycloaddition (CuAAC) reaction under strict conditions, in terms of a novel air-stable, a recyclable and efficient magnetic catalyst was planned for new triazole derivatives as a well-organized copper iodide supported on the functionalized Fe₃O₄@SiO₂ core-shell (CuI/Fe₃O₄@SiO₂(TMS-EDTA) nanoparticles). The engineered nanocatalyst synthesized for the first time and characterized by different methods, including FT-IR spectroscopy, XRD, FESEM, EDX, TEM, TGA, and BET analysis. The excellent catalytic performance in ethanol with high surface area (351.7 m²g⁻¹) and short reaction time for diverse functional groups (120–200 min), no use of toxic solvents, reusability of the catalyst, and using eco-friendly conditions are the advantageous of this work. Moreover,the nanocatalyst can be used at least five times without any significant decrease in the yield of the reaction. The thiazolidine-triazole derivatives 9a , 9c , 9e , and 9 g showed promising tyrosinase inhibitory activity with IC₅₀ values in the range of 5.90–9.81 μM. The compounds were found to be considerably more potent tyrosinase inhibitors than the reference inhibitor kojic acid (IC₅₀ = 18.36 μM).     

Synthesis,structural characterization and DNA-binding studies of a new cobalt (II) complex: (HAcr)<Subscript>4</Subscript>[Co(Sal)<Subscript>3</Subscript>]

A new cobalt (II) coordination compound was synthesized using proton transfer mechanism. The reaction between CoCl₂·2H₂O, Salicylic acid (H₂Sal) and acridine (Acr) gave a new coordination compound formulated as (HAcr)₄[Co(Sal)₃], which was characterized by elemental analysis, NMR, IR and UV/Vis spectroscopies. The interaction of this complex with DNA has been investigated in vitro using UV absorption, fluorescence spectroscopy, viscosity measurements and gel electrophoresis methods. The intrinsic binding constant has been estimated to be 5.8 × 10⁵ M^?1 using UV absorption. The interaction of DNA–Co (II) complex caused quenching in fluorescence. The binding constant, the number of binding site and Stern–Volmer quenching constant have been calculated to be 7.7 × 10⁴ M^?1, 1.143 and 1.5 × 10⁴ Lmol^?1, respectively. The increase in the viscosity of DNA with increasing the concentration of the Co (II) complex and the observations of other experiments suggest that the cobalt (II) complex binds to DNA by partial intercalation binding mode. Furthermore, the interaction of DNA–Co (II) complex was confirmed using gel electrophoresis studies. Moreover, molecular docking technique predicted partial intercalation binding mode for the complex.     

The catalysis, synthesis and characterization of ferrocenylchalcone

Eight kinds of ferrocenylchalcone derivatives were synthesized by the reaction of acetylferrocene and aromatic aldehyde using solid as catalyst in the experiment. The influrence of the catalysts, the raw material molar ratios and reaction times on the yield of ferrocenylchalcone derivatives are discussed. The optimal conditions of synthesis reaction have been selected: the catalyst was KF/Al₂O₃, n(acetyl ferrocene)/n(formal dehyde) = 1:1.2. The structures of the products were characterized by melting point test, IR, ¹HNMR, ¹³CNMR and elemental analysis.     

Synthesis,characterization and comparative DNA interaction studies of new copper(II) and nickel(II) complexes containing mesalamine drug using molecular modeling and multispectroscopic methods

Complexes of copper(II) and nickel(II) containing the drug mesalamine (5-ASA) have been synthesized and characterized by FT-IR, mass and UV–vis spectra, elemental analysis, and theoretical methods. The binding interactions between mesalamine and its Cu(II) and Ni(II) complexes with calf thymus DNA (ct-DNA) were investigated using absorption, fluorescence emission and circular dichroism (CD) spectroscopies, and viscosity measurements. Absorption spectra of 5-ASA, Cu(II) and Ni(II) complexes showed hypochromism. The calculated binding constants (K_b) obtained from UV–vis absorption studies were 1.27 × 10³, 1.6 × 10³, and 1.2 × 10⁴ M^?1 for 5-ASA, Cu(II) and Ni(II) complexes, respectively. The compounds induced detectable changes in the CD spectra of ct-DNA (B → A structural transition, B → C structural transition and stabilization of the right-handed B form, for mesalamine, Cu(II) and Ni(II) complexes, respectively). The competitive binding experiments with Hoechst 33258 indicated that 5-ASA and copper complex could interact as groove binders. Furthermore, Ni complex had no effect on the fluorescence intensity and peak position of MB-DNA system. Finally, the results obtained from experimental and molecular modeling showed that complexes bind to DNA via minor-groove binding.     

Photodegradation of 2-nitrophenol catalyzed by CoO, CoS and CoO/CoS nanoparticles

The nanoparticles of CoO, CoS and CoO/CoS composite are synthesized using precipitation method. The X-ray diffraction, UV–Vis absorption spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy and FT-IR spectroscopy are used to characterize the prepared nanoparticles. The EDX analysis shows the formation of CoO_0.67S_0.33 composite. The XRD pattern indicates the hexagonal structure for nanocomposite. The formation of Co–O and Co–S bonds is confirmed by FT-IR spectra. The band-gap energies of 2.97, 3.06 and 2.91 eV are obtained from UV–Vis spectra of CoO, CoS and CoO/CoS nanoparticles, respectively. The results of photodegradation of 2-nitrophenol show that the photoreactivity order of nanocatalysts is CoO/CoS > CoO > CoS. The pseudo first-order kinetic rate constants of 6.4 × 10^?3, 4.3 × 10^?3 and 12.2 × 10^?3 min^?1 are obtained for CoO, CoS and CoO/CoS nanoparticles, respectively, at photodegradation reaction conditions of pH 10, 30 mg/L of 2-NP and 1.3 g/L of the catalyst. The proposed nanocomposite shows an acceptable reusability and stability against photocorrosion in four-cycle photodegradation experiments.     

Organometallic polymers. I. Synthesis of ferrocene-containing poly(phosphine oxides) and poly(phosphine sulfides)

Poly(phosphine oxides) and poly(phosphine sulfides) of ferrocene were synthesized in the melt phase. The resulting ferrocene polymers, linked by phosphorus bridges, were thermally stable and infusible solids, of low molecular weight (M?_n < 4000). Phenyldichlorophosphine, phenyldichlorophosphonate, and phenylphosphonothioic dichloride were copolymerized with ferrocene in the melt phase (80–110°C.) with ZnCl₂ as a catalyst. As the polymerization temperature was raised, cleavage of cyclopentadiene rings from iron became more pronounced, and cyclopentane-bridged polymers of ferrocene were produced in competition with the ferrocene–phosphorus polymers. The cleavage-polymerization process became predominant at 140°C. The structures of poly(phosphine oxides) (and sulfides) of ferrocene were verified by infrared and nuclear magnetic resonance spectroscopy.     

Preparation,characterization, DFT calculations and ethylene oligomerization studies of iron(II) complexes bearing 2-(1H-benzimidazol-2-yl)-phenol derivatives

Five 2-(1H-benzimidazol-2-yl)-phenol derivatives including 1H (HL₁), 5-chloro-(HL₂), 5-methyl-(HL₃), 5,6-dichloro-(HL₄), and 5,6-dimethyl-(HL₅) were synthesized by the reaction of their corresponding benzene-1,2-diamine precursors and 2-hydroxybenzaldehyde which subsequently was employed in complexation with Fe(II) to prepare complexes C1–C5, respectively. Indeed, in all complexes, the ligands were coordinated as bidentate, via the C=N nitrogen and hydroxy oxygen atom of benzimidazole moiety and phenol ring, respectively. The compounds were characterized by FTIR, UV–vis, ¹H- and ¹³C-NMR spectropscopy, ICP, and elemental analysis (C, H, and N). The purity of these compounds was determined by melting point (m.p )and TLC. The synthesized ligands and complexes were geometrically optimized by Gaussian09 software at B3LYP/TZVP level of theory and satisfactory theoretical–experimental agreement was achieved for analysis of IR data of the compounds. Catalytic behavior of the iron(II) complexes was investigated for ethylene reactivity. On activation with diethylaluminum chloride (Et₂AlCl), iron(II) complex (C4) showed the highest activity (1686 kg oligomers.mol^?1(Fe).h^?1) for ethylene oligomerization when it contains chlorine substituents and exhibits good selectivity for linear 1-butene. The steric and electronic effects of ligands were investigated in detail on the influence of their catalytic activities.     

Palladium(II) 9,10-phenanthrenequinone N-substituted thiosemicarbazone/semicarbazone complexes as efficient catalysts for N-arylation of imidazole

A series of palladium complexes, [PdCl(L_1–4)] (1–4) (L₁ = 9,10-phenanthrenequinone thiosemicarbazone, L₂ = 9,10-phenanthrenequinone methylthiosemicarbazone, L₃ = 9,10-phenanthrenequinone phenylthiosemicarbazone, and L₄ = 9,10-phenanthrenequinone semicarbazone), have been synthesized and characterized by elemental analyses, UV–vis, FT-IR, ¹H and ¹³C NMR, and ESI-Mass spectroscopic methods. The catalytic efficiency of the synthesized complexes was examined against N-arylation of imidazole. The system works well with the electron-rich, -neutral, and -deficient aryl halides to afford the products in good to excellent yields. Sterically congested aryl halides and heteroaryl halides have also been used as substrates to provide N-arylated heterocycles. In addition, this methodology can be applicable to other substrates with N-containing heterocycles.     

Synthesis and antifungal property of N-(aryl) and quaternary N-(aryl) chitosan derivatives against Botrytis cinerea

A series of N-(aryl) and their quaternary N-(aryl) chitosan derivatives were synthesized and evaluated for their antifungal activity against crop-threatening fungus Botrytis cinerea. Schiff bases were firstly synthesized by the reaction of chitosan with cinnamaldehyde, cuminaldehyde and 4-dimethylaminobenzaldehyde followed by reduction with sodium borohydride to form N-(aryl) chitosans. Quaternary N-(aryl) chitosans were then obtained by reaction of N-(aryl) chitosan compounds with ethyl iodide. The chemical structures were characterized by ¹H-NMR, FT-IR and UV spectroscopic techniques. The antifungal activity was evaluated in vitro against B. cinerea by mycelial growth inhibition method and in vivo by application of compounds to tomato plants prior to inoculation with fungal spores. In an in vitro experiment, all quaternized chitosans were more active than N-(aryl) chitosan derivatives and N,N,N-(diethylcinnamyl) chitosan (QC1) was the most potent (EC₅₀ = 1,147 mg/L) against mecelia however, N,N,N-(diethyl-p-dimethylaminobenzyl) chitosan (QC3) was the most potent (EC₅₀ = 334 mg/L) against spores. In an in vivo study, no disease incidence (0.0 %) was observed with QC1 and QC3 at 1,000 mg/L. Spray liquid chitosan enhanced total phenolics and guaiacol peroxidase in inoculated leaves.     

Preparation of Poly(amic acid) and Polyimide via Microwave-Assisted Polycondensation of Aromatic Dianhydrides and Diamines

Summary: A copolycondesation-type poly (amic acid) (PAA) was synthesized using pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) as dianhydride monomers, and 4,4′-oxydianiline (ODA) as a diamine monomer under microwave irradiation in dimethylformamide (DMF). PAA was then converted into a polyimide (PI) by an imidization. The structure and performance of the polymer were characterized by Fourier-transform infrared (FT-IR) spectroscopy, Proton nuclear magnetic resonance (¹H NMR) spectrometry, viscosity, X-ray diffraction (XRD), and thermogravimetric (TG) analyses. The results showed that under microwave irradiation, the intrinsic viscosity and the yield of PAA were increases, and the reaction time was shortened. The FT-IR spectra of the polymer revealed characteristic peaks for PI around 1778^– and 1723 cm^–1. TG curves indicated that the obtained PI began to lose weight at 535 °C, and its 10% thermal decomposition temperature under N₂ was 587 °C.     

Catalytic oxidation of NO over Mn–Co–Ce–Ox catalysts: effect of reaction conditions

Manganese–cobalt–cerium oxide (Mn–Co–Ce–Ox) catalysts were synthesized by the co-precipitation method and tested for activity in low-temperature catalytic oxidation of NO in the presence of excess O₂. With the best Mn–Co–Ce mixed-oxide catalyst, approximately 80 % NO conversion was achieved at 150 °C and a space velocity of 35,000 h^?1. The effect of reaction conditions (reaction temperature, volume fractions of NO and O₂, gas hourly space velocity (GHSV), and catalyst stability) was investigated. The optimum reaction temperature was 150 °C. Increasing the O₂ content above 3 % results in almost no improvement of NO oxidation. This catalyst enables highly effective removal of NO within a wide range of GHSV. Furthermore, the stability of the Me–Co–Ce–Ox catalyst was excellent; no noticeable decrease of NO conversion was observed in 40 h.     

Crystal structures and in vitro anticancer studies on new unsymmetrical copper(II) Schiff base complexes derived from meso-1,2-diphenyl-1,2-ethylenediamine: a comparison with related symmetrical ones

Two new unsymmetrical copper(II) Schiff base complexes, [CuLⁿ(py)]ClO₄ (n = 1, 2) in which Lⁿ represents a tridentate N₂O type Schiff base ligand, were synthesized. Lⁿs were derived from monocondensation of meso-1,2-diphenyl-1,2-ethylenediamine with salicylaldehyde or 3-methoxysalicylaldehyde. The reaction between [CuLⁿ(py)]ClO₄ and other salicylaldehyde derivatives resulted in new N₂O₂ unsymmetrical tetradentate Cu^II complexes, CuL^3–6. Crystal structures of [CuL¹(py)]ClO₄, CuL⁴, and CuL⁵ were obtained. These new complexes as well as a series of related symmetrical ones (i.e. CuL^7–12) were tested for their in vitro anticancer activity against human liver cancer cell line (Hep-G2) by MTT and apoptosis assay. All of the complexes showed considerable cytotoxic activity against tumor cell lines (IC₅₀ = 5.13–16.24 μg mL^?1). The symmetrical CuL⁷ was the most potent anticancer derivative (IC₅₀ = 5.13 μg mL^?1) compared to the control drug 5-FU (IC₅₀ = 5.4 μg mL^-1, p < 0.05). Flow cytometry experiments showed that the copper derivatives especially [CuL²(py)]ClO₄ and CuL⁷ induced more apoptosis on Hep-G2 tumor cell lines compared to 5-FU.     

Multichannel recognition of hydrogen sulphate anion by a Zn(II)–triazole–pyridine complex bearing a ferrocenyl pendant

Receptors ferrocene–triazole–pyridine triads assembled with Zn(II) or Cd(II) metal cations behave as chemosensor molecules for HSO₄ ^?  anions through electrochemical and optical channels: the redox peak of the ferrocene/ferrocenium redox couple is shifted cathodically by 72–53 mV, and a new absorption band appeared in the UV–vis spectrum upon complexation with the HSO₄ ^?  anion. Association constants, detection limits and stoichiometries of the recognition processes have been determined, whereas ¹H NMR experiments and density functional theory calculations are used to suggest the plausible binding mode taking place in the new supramolecular assembly formed.     

Synthesis of Substituted 4,4′-Oxy-bis(aminophenylglyoximes) and Their Polymeric Metal Complexes with Cu(II), Ni(II), and Co(II) Salts

4,4′-Bis(chloroacetyl)diphenyl ether (HL) was synthesized from chloroacetyl chloride and diphenyl ether in the presence of AlCl₃ as catalyst by Friedel-Crafts reaction. Subsequently, its keto oxime (H₂L) and glyoxime (H₄L) derivatives were also prepared. Then, five new substituted 4,4′-oxy-bis(aminophenyl-glyoximes) (H₄L_1–5) were synthesized from 4,4′-oxy-bis(chlorophenylglyoxime) and the corresponding amines. The Ni(II), Cu(II), and Co(II) complexes of these ligands were prepared. The structures of these ligands and their complexes were identified by FT-IR, ¹H NMR, and ICP-AES spectral data, elemental analyses, and magnetic measurements.     

Synthesis and characterization of poly[(4-vinylphenyl)dimethyl- silane]-b-polybutadiene-b-poly[(4-vinylphenyl)dimethylsilane] (PVPDMS-b-PBd-b-PVPDMS)

The novel functionalized triblock copolymers,poly[(4-vinylphenyl)dimethylsilane]-b-polybutadiene-b-poly[(4-vinylphenyl)-dimethylsilane] (PVPDMS-b-PBd-b-PVPDMS),were synthesized by anionic polymerization method using high vacuum technique. The hydrocarbon-soluble dilithium initiator synthesized from l,3-di[l-(methylphenyl)ethenyl]benzene(MPEB) was used to synthesize polybutadiene(PBd) precursors and the triblock copolymers in the presence of sec-BuOLi.The precursors and copolymers were characterized by size exclusion chromatography(SEC),~1HNMR and DSC techniques.     

Synthesis,crystal structures,and magnetic properties of three new iron(II) complexes with pyrrolyl-substituted triaryltriazoles

Three pyrrolyl-substituted triaryltriazoles, 3-(N-methyl-2-pyrrolyl)-4-(p-R-phenyl)-5-(2-pyridyl)-1,2,4-triazole (L¹: R = MeO; L²: R = Cl; L³: R = Br), and their mononuclear iron(II) complexes, trans-[Fe(L^1–3)₂(NCS)₂]?2MeOH (1: L¹; 2: L²; 3: L³), have been synthesized and characterized by elemental analysis, FT-IR, ESI-MS, and single-crystal X-ray crystallography. Crystallographic studies revealed that 1–3 are isomorphous and crystallize in the triclinic space group P-1. All the complexes have a similar octahedral [FeN₆] core with two trans-NCS^? ions. Each ligand adopts a chelating bidentate coordination mode via the pyridyl N and one N of the triazole. Intermolecular O–H?O hydrogen bonding and C–H?π interactions link the molecules of 1–3 to form a 1-D chain or 2-D framework. Variable-temperature magnetic susceptibility measurements indicated that all the complexes remained in a high-spin state from 1.8 to 300 K and had a weak antiferromagnetic interaction.     

Synthesis of nickel(II) complexes of isatin thiosemicarbazone derivatives: in vitro anti-cancer,DNA binding,and cleavage activities

Six new nickel(II) complexes of thiosemicarbazone Schiff base with isatin moiety [Ni(L1)₂–Ni(L6)₂] were synthesized through reaction of Ni(II) with (Z)-2-(2-oxoindolin-3-ylidene)-N-phenylhydrazinecarbothioamide (L1H), (Z)-2-(5-methyl-2-oxoindolin-3-ylidene)-N-phenylhydrazinecarbothioamide (L2H), (Z)-2-(5-fluoro-2-oxoindolin-3-ylidene)-N-phenylhydrazinecarbothioamide (L3H), (Z)-N-methyl-2-(5-nitro-2-oxoindolin-3-ylidene)hydrazinecarbothioamide (L4H), (Z)-N-methyl-2-(5-methyl-2-oxoindolin-3-ylidene)hydrazinecarbothioamide (L5H), and (Z)-N-ethyl-2-(5-methyl-2-oxoindolin-3-ylidene)hydrazinecarbothioamide (L6H). The structures of the Ni complexes were characterized through elemental analysis, infrared, and mass spectral data. The structure of the NiL2 complex was further characterized through single-crystal X-ray diffraction. The interaction of these complexes with calf thymus (CT-DNA) exhibited high intrinsic binding constants (K_b = 1.4 × 10⁵–2.4 × 10⁶ M^?1), which reflected their intercalative activity toward CT-DNA. This result was also confirmed by viscosity data. Electrophoresis studies revealed that these complexes could cleave the DNA through the oxidative pathway. The in vitro anti-proliferative study establishes the anticancer potency of these compounds against human colorectal carcinoma cell line.     

Eisen(II)-Verbindungen von Imidazolen

Iron(II) Compounds of Imidazoles The reaction of ferrocene and cyclopentadienyl dicarbonyl with imidazole, 2-methyl-, 2-ethyl- and 2-phenyl-imidazole yields iron(II) derivatives of these heterocyclic compounds, which have been investigated by thermogravimetry and Mössbauer spectroscopy. The derivative of the substituted imidazoles have the expected composition and contain fourfold coordinated iron. The reaction with unsubstituted imidazole yields the compound Fe(N₂C₃H₃) · 0,71 N₂C₃H₄ with fourfold as well as sixfold coordinated metal ions.     

Bulky organosilicon compounds based on sulfanyltetrazoles: their synthesis and in vitro antibacterial evaluation

The study introduces different organosilicon derivatives incorporating sulfanyltetrazole ring for biological applications. Initially, the sulfanyltetrazole derivatives and halo-analogues (Br, I) were synthesized. Later, selective reaction of tris(trimethylsilyl)methyllithium (TsiLi) in the presence (?46 and 0 °C) and absence (room temperature) of CS₂ with halo-sulfanyltetrazole derivatives yielded new multifunctional sulfanyltetrazole regioisomers with SH, C = S, ethynylthio and SiMe₃ groups, respectively. All the synthesized compounds were characterized by IR, ¹H-NMR, ¹³C-NMR spectra and elemental analysis data. The compounds were screened for their antibacterial activities against clinically important gram-positive and gram-negative bacteria using the spectrophotometric microdilution method. The preliminary screening indicated that the organosilicon derivatives incorporating SH and C = S (mercapto-silyl-thiones) and silyl-thioalkynes have antibacterial activities, whereas no antibacterial activity was observed on compounds containing (Me₃Si)₃C groups. Of the synthesized compounds, compound 5d showed the best activity against all the tested organisms (3.91–31.25 µg/mL).