TBHP/R4N+X– promoted hydroaroylation of dialkyl azodicarboxylates with methyl arenes,aldehydes, aryl methanols and arylmethyl chlorides

Efficient TBHP/R₄N⁺X^– promoted hydroaroylations of dialkyl azo-1,2-dicarboxylates with methyl arenes, aldehydes, aryl methanols and arylmethyl chlorides are described. These oxidation/oxygenation and hydroaroylation processes were carried out by tert-butyl hydroperoxide as terminal oxidant/oxygen source, and were catalyzed by tetrabutylammonium bromide and tricaprylmethylammonium chloride as the driving force. During this investigation, all these hydroaroylating sources were found to be highly efficient reagents without the need of any transition-metal.     

Immobilized triazine bis[mercapto amine] complexes of Pd(0) anchored nickel ferrite as a nanocatalyst for C–C coupling reaction

Immobilized triazine bis[mercapto amine] complexes of Pd(0) (NiFe₂O₄@TABMA-Pd(0)) was easily synthesized and applied as highly efficient and versatile nanocatalyst for the synthesis of various trans stilbenes with high performance for the Heck coupling reaction of several types of aryl halides under thermal conditions. In short reaction time, excellent yields of trans stilbene derivatives have been achieved using NiFe₂O₄@TABMA-Pd(0) catalyst.     

Improving of Anticancer Activity and Solubility of Cisplatin by Methylglycine and Methyl Amine Ligands Against Human Breast Adenocarcinoma Cell Line

Methylglycine, also known sarcosine, is dramatically used in drug molecules and its metal complexes can interact to DNA and also do cleavage. Hence, to study the influence of methylglycine ligand on biological behavior of metal complexes, two water-soluble platinum (II) complexes with the formula cis-[Pt(NH₃)₂(CH₃-gly)]NO₃ and cis-[Pt(NH₂-CH₃)₂(CH₃-gly)]NO₃ (where CH₃-gly is methylglycine) have been synthesized and characterized by spectroscopic methods, molar conductivity measurements, and elemental analyzes. The anticancer activity of synthesized complexes was tested against human breast adenocarcinoma cell line of MCF7 using MTT assay and results showed excellent anticancer activity with Cc₅₀ values of 126 and 292 μM after 24 h incubation time, for both complexes of cis-[Pt(NH₃)₂(CH₃gly)]NO₃ and cis-[Pt(NH₂-CH₃)₂(CH₃gly)]NO₃, respectively. Also, the interaction between Pt(II) complexes with calf thymus DNA was extensively studied by means of absorption spectroscopy, fluorescence titration spectra displacement with ethidium bromide (EtBr), and circular dichroism studied in Tris-buffer. The obtained spectroscopic results revealed that two complexes can bind to highly polymerized calf thymus DNA cooperatively and denature at micromolar concentrations. The fluorescence data indicate that quenching effect for cis-[Pt(NH₃)₂(CH₃gly)]NO₃ (K_sv?=?9.48 mM^?1) was higher than that of cis-[Pt(NH₂-CH₃)₂(CH₃gly)]NO₃ (K_sv?= 1.98 mM^?1). These results were also confirmed by circular dichrosim spectra. Consequently, docking data showed that cis-[Pt(NH₃)₂(CH₃gly)]NO₃ with more interaction energy binds on DNA via groove binding which is more compatible with experimental results.

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Graphical Abstract ? Two anticancer Pt(II) complexes, cis-[Pt(NH₃)₂(CH₃gly)]NO₃ and cis-[Pt(NH_2?CH₃)₂(CH₃gly)]NO₃, have been synthesized and interacted with calf thymus DNA. Improving solubility of these compounds reduce side effects and increase anticancer activity against human breast cell line. Modes of binding have been studied by electronic absorption, fluorescence, and CD measurements. Results show that both Pt(II) complexes can interact to DNA via groove binding.

     

M···π-conjugated complexes: simple materials with dramatic NLO features (M = Li,Na, K,and π = butadiene,cyclobutadiene, hexatriene,benzene)

Theoretical investigation of linear and nonlinear optical (NLO) properties in simple complexes consist of alkali metals and π-conjugated systems have been studied at MP2/6-311++G(2d,2p) computational level. Lithium, sodium, and potassium as alkali metals were chosen for interaction with some non-aromatic, aromatic and anti-aromatic systems. For better comparison of results, the π-systems were chosen with the same carbon number: butadiene as a non-aromatic in comparison with cyclobutadiene as an anti-aromatic and hexatriene as a non-aromatic in comparison with benzene as an aromatic system. Results revealed that gap energy of studied π-systems was decreased under the interacting with alkali metals. Furthermore all designed complexes were shown very good results in average polarizability (α) and first hyperpolarizability (β ₀) parameters. So these very simple dimer complexes could be introduced as promising innovative nonlinear optical materials.     

Electrochemical Oxidation of Nortriptyline and Its Voltammetric Sensing at a Carbon Ionic Liquid Electrode

The electrochemical oxidation of nortriptyline at a carbon ionic liquid electrode (CILE) was investigated. Nortriptyline is electrochemically inactive on conventional electrodes but CILE exhibited excellent electrocatalytic activity toward oxidation of nortriptyline with the well-defined anodic peak at 860 mV. This characteristic was attributed to the outstanding conductivity and electrocatalytic effect of the ionic liquid, 1-octylpyridinum hexaflourophosphate, used as a binder in the construction of the electrode. The influence of experimental parameters such as pH and sweep rate was also studied. The quantitative determination of nortriptyline was performed using differential pulse voltammetry technique. Under selected conditions the anodic peak current was linear to nortriptyline concentration in the ranges of 4.8 × 10^–6 to 2.4 × 10^–5 M and 2.4 × 10^–5 to 6.4 × 10^–5 M, with correlation coefficients of 0.9992 and 09949, respectively. The detection limit was 3 × 10^–7 M.     

New complexes of Ni(II) and Cu(II) with tridentate ONO Schiff base ligand: synthesis,crystal structures,electrochemical and theoretical investigation

In this research, we prepared a new series of the Cu(II) (1) and Ni(II) (2) metal complexes of a tridentate Schiff base ligand, (E)-2-(5-bromo-2-hydroxybenzylideneamino) phenol (H₂L). These complexes were characterized by elemental analysis, FT-IR, UV–Vis, and ¹H-NMR spectroscopy. The crystal structures of (1) and (2) were determined by X-ray diffraction studies. The single crystal X-ray diffraction analyses revealed that copper(II) cation is five-coordinated and the coordination polyhedron is a slightly distorted square pyramid. Nickel(II), on the other hand, is four-coordinated, and has a regular, square planar geometry. Further discussed were the electrochemical reduction of these complexes. We also analyzed the nature of the metal–ligand bond in the complexes through NBO and EDA analysis. Besides, vibrational sample magnetometer (VSM) revealed complex (1) was ferromagnetic.     

Copper-catalysed synthesis of 3,5-disubstituted isoxazoles enabled by pyridinyl benzimidazol (PBI) as a bidentate <Emphasis Type="Italic">N</Emphasis>-chelating ligand under mild conditions

In this paper, we introduced pyridinyl benzimidazol (PBI) as an easy-to-handle and bidentate N-chelating ligand that promote clean synthesis of 3,5-disubstituted isoxazoles in the presence of copper acetate as catalyst. This catalytic approach initiates with the hydroxyamination of aldehydes followed by chlorination and then generation of nitrile oxide which subsequently undergoes click-type [3 + 2]-dipolar cycloaddition with alkynes to give isoxazoles. This method provides an alternative green process to construct isoxazole derivatives.     

Vapor–liquid equilibria of binary tri-potassium citrate + water and ternary polypropylene oxide 400 + tri-potassium citrate + water systems from isopiestic measurements over a range of temperatures

Water activity measurements have been carried out on the aqueous solutions of both tri-potassium citrate (K₃Cit) and polypropylene oxide (PPO) 400 + K₃Cit over a range of temperatures at atmospheric pressure. The data obtained is used to calculate the vapor pressure as a function of temperature and concentration. The effect of temperature on the constant water activity lines of aqueous PPO + K₃Cit systems has been studied and it was found that, at higher temperatures the higher concentration of polymer is in equilibrium with a certain concentration of the salt. Also it was found that the vapor pressure depression for an aqueous PPO + K₃Cit system is more than the sum of those for the corresponding binary solutions. The experimental water activities have been correlated successfully with the segment-based local composition Wilson model. The agreement between the correlation and the experimental data is good.     

Synthesis of New (Pyrimido[4,5-e][1,3,4] thiadiazin-7-yl)hydrazine Derivatives

New (pyrimido[4,5-e][1,3,4]thiadiazin-7-yl)hydrazines were synthesized via the cyclocondensation of alkyl-2-phenylhydrazinecarbodithioates as bidentate nucleophiles with 5-bromo-2,4-dichloro-6-methylpyrimidine as an electrophile and further replacement of chlorine atom on the seven number position of pyrimido[4,5-e][1,3,4]thiadiazin by hydrazine in boiling ethanol.