Synthesis and antitumor activity of new silver(I)-N-heterocyclic carbene complexes

Abstract

In this study, two novel benzimidazole-based N-heterocyclic carbene ligands (1a-b) and their silver(I) complexes (2a-b) were synthesized. All new compounds were characterized by FT-IR, LC-MS, ¹H NMR, and ¹³C NMR spectroscopies. The in vitro antitumor activities of NHC ligands (1a-b) and their silver(I) complexes (2a-b) against DU-145 human prostate cancer cells, MDA-MB-231 and MCF-7 human breast cancer cells and L-929 (normal cells adipose from mouse) were also determined using MTT analysis for 24?h, 48?h, and 72?h. The results showed that while NHC ligands did not have in vitro antitumor activity on MCF-7, MDA-MB-231 and DU-145 cells, Ag(I)-NHC complexes have in vitro antitumor activities. The in vitro antitumor activity of 2a was found to be lower than that of 2b. Ag(I)-NHC complexes were observed to have higher IC₅₀ values for non-cancerous cell lines than cancer cells.     

Compatibility of binary systems of poly(methyl methacrylate), poly(vinyl chloride) and poly(vinyl acetate)

The influence of the thermal treatment on the stability in time of the dispersion degree of films containing binary polymer mixtures, poly(vinyl chloride)/poly(methyl methacrylate), poly(vinyl chloride)/poly(vinyl acetate) and poly(vinyl acetate)/poly(methyl methacrylate), was studied by thermogravimetry and optical microscopy with phase contrast. The dispersion degree depends particularly on the composition of the polymer mixture and can be improved by thermal treatment at temperatures above the glass temperatures of both homopolymers. It seems that this thermal treatment yields exclusively metastable structures with a general tendency to phase separation in a short time after thermal treatment, the heterogeneity mixtures (as film) being more pronounced.     

Candida zeylanoides as whole-cell biocatalyst to perform asymmetric bioreduction of benzophenone derivatives

Abstract

Candida zeylanoides P1 was investigated as whole cell biocatalyst for the bioreduction of biaryl prochiral ketones into chiral carbinols, which can be used as pharmaceutical intermediate. Bioreduction of different biaryl ketones was carried out to their corresponding chiral biaryl carbinols such as (S)-(4-chlorophenyl) (phenyl) methanol (2a), which can be used in the synthesis of L-cloperastine drug, with antitussive, antiepidemic activity and bronchial musculature relaxant characteristics, in gram scale, enantiopure form (>99%) and excellent yields. The selectivity of C. zeylanoides P1 in enantioselective reduction of biaryl ketones was not affected by the steric and electronic effects of substrates. The current method demonstrates an encouraging green chemistry approach for the production of biaryl secondary chiral alcohols of pharmaceutical importance in mild, inexpensive and environmentally friendly process. The present study has many benefits since this yeast biocatalyst were successfully applied bioreduction of structurally bulky prochiral substrates, which cannot be reducted by chemical catalysis.     

Thermal degradation of poly(ethyl methacrylate) and its copolymer with poly(ethyl acrylate)

The thermal degradation behaviour of poly(ethyl methacrylate) homopolymers and poly(ethyl methacrylate) and poly(ethyl acrylate) copolymers synthesized by using the benzoyl peroxide-di-methyl aniline redox pair at different temperatures (18–35C) was investigated. Contrary to some reports in the literature, the thermal degradation of PEMA was observed to take place in multi steps. These are assigned to be loss of labile end groups, side chain scission, anhydride formation and main chain degradation steps. Dominating chemical formations at the end of these steps were characterized by FTIR spectroscopy.The homopolymer samples synthesized at 18C showed a greater thermal stability against degradation. Copolymerization with small amounts of ethyl acrylate was observed to impart thermal stability to PEMA by stabilizing mainly the end groups against degradations.     

Synthesis and characterization of new macrocyclic Schiff base derived from 2,6-diaminopyridine and 1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane and its Cu(II), Ni(II), Pb(II), Co(III) and La(III) complexes

A new macrocyclic ligand, 1,3,5-triaza-2,4:7,8:16,17-tribenzo-9,12,15-trioxacyclooktadeca-1,5-dien (L) was synthesized by reaction of 2,6-diaminopyridine and 1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane. Then, its Cu(II), Ni(II), Pb(II), Co(III) and La(III) complexes were synthesized by template effect by reaction of 2,6-diaminopyridine and 1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane and Cu(NO₃)₂ · 3H₂O, Ni(NO₃)₂ · 6H₂O, Pb(NO₃)₂, Co(NO₃)₂ · 6H₂O, La(NO₃)₃ · 6H₂O, respectively. The ligand and its metal complexes have been characterized by elemental analysis, IR, ¹H and ¹³C NMR, UV–Vis spectra, magnetic susceptibility, thermal gravimetric analysis, conductivity measurements, mass spectra and cyclic voltammetry. All complexes are diamagnetic and Cu(II) complex is binuclear. The Co(II) was oxidized to Co(III). The comparative electrochemical studies show that the nickel complex exhibited a quasi-reversible one-electron reduction process while copper and cobalt complexes gave irreversible reduction processes in DMSO solution.     

Determination of metal ions by capillary electrophoresis using pre-column complexation with 1,10-phenanthroline

The capillary electrophoretic separation of Fe(II), Cu(II) and Zn(II) ions in an acidic buffer solution (pH 2.5) by complexation with 1,10-phenanthroline is investigated. As 1,10-phenanthroline is a neutral ligand, the positively charged metal complexes formed migrate in the same direction as the EOF, providing a rapid separation of metal ions in acidic buffers. The method was applied to the determination of metal ions in vitamin tablets. Received: 5 January 1998 / Revised: 27 March 1998 / Accepted: 15 May 1998     

Determination of Trace Amounts of Copper in Tap Water Samples with a Calix[4]arene Modified Carbon Paste Electrode by Differential Pulse Anodic Stripping Voltammetry

A calix[4]arene modified carbon paste electrode was used for trace determination of copper. The study of the preconcentration of copper as well as the other heavy metal ions at the modified electrode, with subsequent measurement by differential pulse anodic stripping voltammetry (DPASV), indicates the efficient open‐circuit accumulation of the analytes onto the electrode. Many parameters such as the composition of the paste, pH, preconcentration time and stirring rate influence the response of the measurement. The procedure was optimized for copper determination. For a 10‐minute preconcentration time at pH 6.5–7.5, the detection limit (LOD) was 1.1 μg L^?1. The optimized method was successfully applied to the determination of copper in tap water sample by means of standard addition procedure. The copper content of the sample was comparable with the result obtained with AAS method.     

Adsorption of Acid Dyes from Aqueous Solutions by Calcined Alunite and Granular Activated Carbon

Dyestuff production units and dyeing units have always had a pressing need for techniques that allow economical pretreatment for color in the effluent. The effectiveness of adsorption for dye removal from wastewaters had made it an ideal alternative to other expensive treatment options. This paper deals with an investigation on alunite, existing wide reserves in Türkiye and in the world, for dye removal. Calcined alunite was utilized for this study and its performance evaluated against that of granular activated carbon (GAC). The use of calcined alunite for the removal of Acid Blue 40 and Acid Yellow 17 (AB 40 and AY 17) from aqueous solution at different calcination temperature and time, particle size, pH, agitation time and dye concentration has been investigated. The adsorption followed by Langmuir and Freundlich isotherms. The process follows first order adsorption rate expression and the rate constant was found to be 7.65 × 10^–2 and 5.74 × 10^–2 min^–1 for adsorption of AB 40 and AY 17 on calcined alunite, and 8.41 × 10^–2 and 10.04 × 10^–2 min^–1 for adsorption of AB 40 and AY 17 on GAC, respectively. The equilibrium saturation adsorption capacities were 212.8 mg dye/g calcined alunite and 151.5 mg dye/g calcined alunite for AB 40 and AY 17, respectively. The adsorption capacities were found to be 57.47 mg and 133.3 mg dye per g of GAC for AB 40 and AY 17, respectively. The results indicate that, for the removal of acid dye, calcined alunite was most effective adsorbent, although comparable dye removals were exhibited by GAC.     

Chemical effects on L shell fluorescence yields of Ba, La and Ce compounds

Chemical effects on the average L shell fluorescence yields (v_L) for Ba, La and Ce compounds were investigated. Samples were excited by gamma-rays with 59.5 keV energy photons from a ²⁴¹Am radioisotope source. L X-rays emitted by samples were counted by a Si(Li) detector with a resolution 155 eV at 5.9 keV. Chemical effects on the average L shell fluorescence yield (v _L) for Ba, La and Ce compounds were observed. The values are compared with theoretical and experimental ones for the pure elements.     

Synthesis of Schiff bases by condensation of hetarylcarboxaldehydes withp-phenetidine

Summary Treatment of quinolinecarboxaldehydes and their derivatives withp-ethoxyaniline yields in a one-step reaction a series of new Schiff bases in 47–73% yield. The products [quinoline-2-, 6-methylquinoline-2-, quinoline-4-, quinoline-8-, and acridine-9-N-(p-ethoxyphenyl)formimidoyl], have been fully characterized.

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Synthese von Schiffschen Basen durch Kondensation von Hetarylaldehyden mitp-Phenetidin

Zusammenfassung Umsetzung von Chinolinaldehyden und deren Derivaten mitp-Ethoxyanilin liefert in einer Einstufenreaktion neue Schiffsche Basen in 47–73%iger Ausbeute. Alle Produkte [Chinolin-2-, 6-Methylchinolin-2-, Chinolin-4-, Chinolin-8- und Acridin-9-N-(p-ethoxyphenyl)formimidoyl] wurden voll charakterisiert.