Synthesis and characterization, novel across adjacent ring formed phthalocyanine

Novel mononuclear Zn(ii) 4, Co(ii) 5 and Cu(ii) 6 metallophthalocyanines have been synthesized from 4,4'(ethane-1,1-p-phenol-2,2-p-phenoxy)phthalonitrile 3, which can be obtained by the reaction of 4-nitrophthalonitrile 1 with 1,1,2,2-tetrakis(p-hydroxy-phenyl)-ethane 2. The target water-soluble derivatives of 7-9 were acquired from a boiling suspension of the compounds in aqueous 20% KOH solution. The synthesized complexes have been characterized by UV-vis, IR, (1)H NMR and MALDI-TOF-mass spectroscopies. In addition, the geometric and electronic structures of 2-6 were investigated by ab initio/DFT quantum mechanical calculations using the Gaussian 03 program with HF theory at the B3LYP/3-21G level. The redox properties of the complexes 4-6 were examined by cyclic voltammetry on platinum in DMSO/TBAP. These complexes displayed one-electron metallophthalocyanine-based and multi-electron hydroxyphenyl-based redox processes. The effect of temperature on the d.c. conductivity and impedance spectra of spin coated films of compounds were investigated at the temperatures between 300-452 K and in the frequency range of 40-105 Hz. Thermally activated conductivity dependence on temperature was observed for all compounds. A.c. results indicated that conduction mechanism can be explained by classical hopping barriers mechanism for all films.     

Modification of polydivinylbenzene microspheres by a hydrobromination/click-chemistry protocol and their protein-adsorption properties

Hydrophobic- and/or hydrophilic-polymer-grafted PDVB microspheres are synthesized by the combination of hydrobromination and click-chemistry processes. The modified-PDVB microspheres and the intermediates at various stages of synthesis are characterized using GPC, 1H NMR and FTIR spectroscopy and TGA analysis. Use of the microspheres as a support matrix for reversible protein immobilization via adsorption is investigated. The system parameters such as the adsorption conditions (i.e., enzyme concentration, medium pH) and desorption are studied and evaluated with regards to the biocatalytic activity and adsorption capacity.     

Development of a CD‐MEKC method for investigating the metabolism of tamoxifen by flavin‐containing monooxygenases and the inhibitory effects of methimazole,nicotine and DMXAA

A selective and low‐cost CD‐MEKC method under acidic conditions was developed for investigating the N‐oxygenation of tamoxifen (TAM) by flavin‐containing monooxygenases (FMOs). The inhibitory effects of methimazole (MMI), nicotine and 5,6‐dimethylxanthenone‐4‐acetic acid (DMXAA) on the given FMO reaction were also evaluated; 100 mM phosphate buffer (pH 8.6) was used for performing the enzymatic reaction and the separation of TAM and its metabolite tamoxifen N‐oxide (TNO) was obtained with a BGE consisting of 100 mM phosphoric acid solution adjusted to pH 2.5 with triethanolamine containing 50 mM sodium taurodeoxycholate, 20 mM carboxymethyl β‐CD and 20% ACN. The proposed method was applied for the kinetics study of FMO1 using TAM as a substrate probe. A Michaelis–Menten constant (K_m) of 164.1 μM was estimated from the corrected peak area of the product, TNO. The calculated value of the maximum reaction velocity (V_max) was 3.61 μmol/min/μmol FMO1; 50% inhibitory concentration and inhibition constant (K_i) of MMI, the most common alternate substrate FMO inhibitor, were evaluated and the inhibitory effects of two other important FMO substrates, nicotine and DMXAA, a novel anti‐tumour agent, were investigated.