Speciation studies on the complex formation reactions of [Pd(N,N-diethyl-ethylendiamine)(H2O)2]2+ with some bio-relevant ligands and displacement reaction by mercaptoethylamine

Pd(deen)Cl2 and Pd(deen)(CBDCA) complexes, where deen=N,N-diethylethylenediamine and CBDCA=1,1-cyclobutanedicarboxylate, were synthesized and characterized by elemental analysis and spectroscopic techniques. The stoichiometry and stability of the complexes formed between various biologically relevant ligands (amino acids, peptides, DNA constituents and dicarboxylic acids) and [Pd(deen)(H2O)2]2+ were investigated at 25 °C and 0.1 M ionic strength. The speciation diagrams of the complexes formed in solutions are evaluated. The mode of coordination of glycylglycine is investigated by spectrophotometric measurements. The equilibrium constants for the displacement of coordinated ligands as inosine, glycine or methionine by mercaptoethylamine are calculated. The results are expected to contribute to the chemistry of antitumour agents.     

Graphite/Methanesulfonic Acid (GMA) as a New Reagent for Sulfonylation of Phenols and Thia‐Fries Rearrangement of Aryl Sulfonates to Sulfonylphenols

A new facile method for direct sulfonylation of phenols was developed. Graphite in methanesulfonic acid (GMA) was used to prepare sulfonylphenols by sulfonylation of phenol and naphthalene derivatives with p‐toluenesulfonic acid (=4‐methylbenzenesulfonic acid) (Table 1) and the thia‐Fries rearrangement of aryl sulfonates (Table 4). Mechanistic studies showed that the sulfonylation reaction of phenols in GMA occurred through an initial sulfonate formation followed by a thia‐Fries rearrangement of the aryl sulfonate by an intermolecular mechanism (Scheme 3).     

Copper(II)-selective fluorimetric bulk optode membrane based on a 1-hydroxy-9,10-anthraquinone derivative having two propenyl arms as a neutral fluorogenic ionophore

A new optical chemical sensor has been developed for the selective determination of copper(II) ions in aqueous solutions. The reversible sensing system was prepared by incorporating 1-hydrpxy-2-(prop-2'-enyl)-4-(prop-2'-enyloxy)-9,10-anthraquinone (AQ) as a neutral Cu2+-selective fluoroionophore in the plasticized PVC membrane with potassium tetrakis(p-chlorophenyl borate) as an anionic additive. The response of the sensor is based on the fluorescence quenching of AQ by Cu2+ ions. At a pH 5.5, the proposed sensor displays a calibration response for Cu2+ over a wide concentration rang of 1.0 x 10(-2) to 1.0 x 10(-6) M, with a relatively fast response of less than 40 s. In addition to high stability and reproducibility, the sensor shows a unique selectivity towards Cu2+ ion with respect to common co-existing cations. The proposed fluorescence optode was applied successfully to the determination of copper(II) in black tea samples.     

Influence of gamma radiation on morphology structure,electrochemical corrosion behavior and hardness of Ni–Cr based alloys

This study evaluates the effects of gamma radiation on structure, electrochemical corrosion behavior and Vickers hardness of commercial dental Nikkeli–Kromi–Polttosekoitus [Ni_65.2Cr_22.5Mo_9.5X_2.8 (X=Nb, Si, Fe and Mn)] alloy. The corrosion rate of Ni_65.2Cr_22.5Mo_9.5X_2.8 (X=Nb, Si, Fe and Mn) alloy with 0.5 M HCl is increased with increasing the exposure rate of gamma radiation. The corrosion resistance of Ni_65.2Cr_22.5Mo_9.5X_2.8 (X=Nb, Si, Fe and Mn) is varied and reaches a minimum value at 30 KGy. The corrosion potential value also is varied and reaches its highest value at 30 KGy. The Vickers hardness value of Ni_65.2Cr_22.5Mo_9.5X_2.8 (X=Nb, Si, Fe and Mn) alloy is decreased by increasing the gamma radiation dose. Also it is obvious from our results that the effects of gamma radiation at the surface are much higher as compared with deeper parts and the structure of the alloy is changed due to its exposure to gamma radiation.     

New 1,3,4‐Thiadiazole Derivatives: Synthesis,Characterization, and Antimicrobial Activity

In the present study, 2,5‐bis(mercapto‐acetichydrazide)‐1,3,4‐thiadiazole ( 1 ) was utilized by different reagents, namely, ethoxymethylene malononitrile, ethoxymethylene ethyl cyanoacetate, triethyl orthoformate, phenyl isothiocyanate, carbon disulfide, isatin, acetophenone, cyclohexanone, different aldehydes, and different anhydrides, to yield a new series of 2,5‐disubstituted‐1,3,4‐thiadiazoles 2 – 18 . The chemical structure of these products was characterized by the spectral data IR, ¹H‐NMR, ¹³C‐NMR, MS, and elemental analysis. All the synthesized compounds were screened for their antibacterial activity.     

Direct Amination and Synthesis of Fused N‐Substituted Isothiochromene Derivatives

Isothiochromene[3,4‐d] pyrimidine derivatives 2 , 3 , and 4a , b were synthesized from the reaction of 3‐amino‐1‐(pyridin‐4‐yl)‐5‐(pyridin‐4‐ylmethylene)‐5,6,7,8‐tetrahydro‐1H‐isothiochromene‐4‐carbonitrile 1 with acetic anhydride, formamide, urea, or thiourea in appropriate experimental conditions. Combination of 1 with carbon acid derivatives afforded isothiochromene [3,4‐b]pyridine 6 – 8 in good yield. A simple approach for N‐substituted fused isothiochromene derivatives has been explored. A POCl₃‐mediated direct amination of isothiochromene amide 2 with NH₂‐heterocycles, secondary amines, and carbohydrazides is described and compared with classical method, yielding 10 – 14 . The structures of the newly synthesized compounds were elucidated on the basis of elemental analysis, and spectral data.     

Synthesis of Some New Thiazolo[3,2‐a]pyrimidine Derivatives and Their Applications as Disperse Dyes

A series of novel thiazolo[3,2‐a]pyrimidine derivatives were synthesized by using β‐ketoanilides 1a–c as starting materials and as key intermediates for preparation of new pyrimidinecompounds 3a–e and fused heterocyclic pyrimidine derivatives 5a–c . The new compounds were transformed to disperse dyes 6a,b and 7 . The chemical structures were elucidated by spectroscopic and elemental analyses and found to be in good agreement with the proposed structures. The versatility of compounds 6a,b and 7 for textile dyeing as disperse dyes was reported. The synthesized dyes were applied to polyester fabrics by using high temperature dyeing method at 120°C. The dye uptake expressed as color strength (k/s) of the dyed samples has been measured. Moreover, the color strength was examined in detail. In addition, the position of color in CIELAB coordinates (L*, a*, b*, h, and C*) was assessed. The color fastness of the dyed samples gave excellent results for washing and rubbing; however, the light fastness was moderate. Raman spectra of dyed samples unequivocally excluded ring dyeing and found to match with the proposed structures.