Crystallographic report: Bis{µ‐[O‐cyclopentyl(4‐methoxyphenyl)dithiophosphonato]1κ:S,2κ:S‐[O‐cyclopentyl(4‐methoxyphenyl)dithiophosphonato]‐1κ2S,S′}dicadmium(II)

The centrosymmetric title compound, [Cd₂{CH₃OC₆H₄P(OC₅H₉)S₂}₄], features an eight‐membered [? Cd? S? P? S? ]₂ ring owing to the presence of bridging dithiolate ligands. Tetrahedral coordination geometries for cadmium are completed by chelating ligands. Copyright © 2004 John Wiley & Sons, Ltd.     

Adsorption of acid dyes from aqueous solutions onto acid-activated bentonite

The adsorption of two dyes, namely, Acid Red 57 (AR57) and Acid Blue 294 (AB294), onto acid-activated bentonite in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. Acidic pH was favorable for the adsorption of these dyes. The surface characterization of acid-activated bentonite was performed using the FTIR technique. The pseudo-first-order and pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamic data fitted the pseudo-second-order kinetic model well and also followed the intraparticle diffusion model up to 90 min, but diffusion is not the only rate controlling step. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The Freundlich model agrees very well with experimental data. The activation energies of adsorption were also evaluated for the adsorption of AR57 and AB294 onto activated bentonite.     

Preconcentration and separation of copper(II), cadmium(II) and chromium(III) in a syringe filled with 3-aminopropyltriethoxysilane supported on silica gel

In this study, a syringe was filled with silica gel loaded with 3-aminopropyltriethoxysilane, for the separation and preconcentration of copper, cadmium and chromium prior to their determination by graphite furnace atomic absorption spectrometry (GFAAS) in seawater. For this purpose, a syringe was filled with 0.5 g of modified silica gel and the sample solution was drawn into the syringe and ejected back again. The analyte elements were quantitatively retained at pH 5. Then, the elements sorbed by the silica gel were eluted with 2.0 M of HCl and determined by GFAAS. At optimum conditions, the recovery of Cu, Cd and Cr were 96-98%. Detection limits (3delta) were 6.6, 7.5 and 6.0 micro g L(-1) for Cu, Cd and Cr, respectively. The elements could be concentrated by drawing and discharging several portions of sample successively but eluting only once. Cu, Cd and Cr added to a seawater sample were quantitatively recovered (>95%) in the range of the 95% confidence level. The method proposed in this paper was compared with a column technique. Optimum experimental conditions, reproducibility, precision and recoveries of both techniques are the same, but the syringe technique is much faster, easier and more practical than the column technique. It is a portable system and allows one to make the sorption process in the source of sample. In addition, the risk of contamination is less than in the column technique.     

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

In situ photoelastic‐modulated Fourier transform infrared reflection absorption spectroscopy has been applied for the investigation of interfacial stability of organothiol and organosilane monolayer films on nanocrystalline zinc oxide thin films. It has been shown that for octadecyltriethoxysilane films, exposure to high water activities results in physisorption of water in the cross‐linked film. This high water activity at the interface leads to a reversible wet de‐adhesion of the interfacial silanol groups from the ZnO surface. However, the organothiol seems to form a denser monolayer and a stable by S–Zn bond that is resistant to the competition with adsorbed water. The reversible attachment for cross‐linked organosilanol films has been demonstrated for the first time by means of an in situ spectroscopic method on model ZnO surfaces. Copyright © 2016 John Wiley & Sons, Ltd.     

The investigation of complexation properties and synthesis of the (salen and salophen)-bridged Fe/Cr(III) capped complexes of novel Schiff bases

This article describes synthesis of novel Schiff base and its complexation properties with Fe(III) and Cr(III). Firstly 1,3,5-tris (formylphenoxymethyl)benzene (1, TRIPOD) with tris aldehyde groups were synthesized using the 1,3,5-trisbromomethylbenzene and 4-hydroxybezaldehyde. The compound 1 was converted to the Schiff base derivative (2, TCPIM-TRIPOD) with p-aminobenzoic acid. The prepared TCPIM-TRIPOD were reacted with four new trinuclear Fe(III) and Cr(III) complexes involving tetradenta Schiff bases N,N-bis(salicylidene)ethylenediamine-(salenH₂) or bis(salicylidene)-o-phenylenediamine-(salophenH₂) and characterized by means of elemental analysis carrying out infrared spectroscopy (IR), thermogravimetric analysis (TG), nuclear magnetic resonance (¹H-NMR), elemental analysis and magnetic susceptibility measurement. The complexes can also be characterized as low-spin distorted octahedral Fe(III) and Cr(III) bridged by carboxylic acids. The tricarboxylic acids play a role as bridges for weak antiferromagnetic intramolecular exchange.     

Measurements of radon concentration in drinking water samples from Kastamonu (Turkey)

Concentration of (222)Rn was determined in selected natural spring and tap water samples collected during spring and summer seasons from Kastamonu, Turkey. The aim of this work was to produce a map of the radon concentrations in water sources of the province and to determine any potential radiological risk for the local population. Radon measurements were performed by an AlphaGUARD radon gas analyser. The average radon concentrations were found to vary from 0.39±0.02 to 12.73±0.39?Bq?l(-1) for natural springs and from 0.36±0.04 to 9.29±0.45?Bq?l(-1) for tap water in spring, from 0.50±0.09 to 19.21±1.00?Bq?l(-1) for natural springs and from 0.31±0.03 to 13.14±0.38?Bq?l(-1) for tap water in summer. Furthermore, the results are compared with international recommendations and concentrations reported for other countries. Doses resulting from the consumption of these waters were calculated. The effective dose equivalents due to the intake of the (222)Rn present in these waters are expected to range from 0.93 to 32.54?μSv?y(-1) in summer and from 0.80 to 49.09?μSv?y(-1) in spring.     

Role of the n+1 amino acid residue on the deamidation of asparagine in pentapeptides

Deamidation plays an important role in biochemical phenomena such as aging. The role of the n + 1 residue on the deamidation of asparagine (asparagine being the nth residue) in three pentapeptide chains (GGNGG, GGNMG and GGNIG) has been analysed with hybrid computational tools. Potentials of mean force at 300 K were calculated from the MD/replica exchange simulations using weighted histogram analysis (WHAM) in explicit water. The snapshots were clustered taking into account the requirements of the plausible deamidation mechanisms, as such the tautomerisation of the asparagine side chain as initial step has been confirmed, based on the proximity of water to the deamidation site. The ultimate goal being to gain an insight on the peptide backbone N-H acidity, quantum mechanical calculations have been carried out. For this purpose, the distribution of Φ/Ψ, Φ₂/Ψ and end-to-end distances deduced from the WHAM diagrams have been considered and a total of 110 structures have been sampled. These neutral pentapeptides as well as their corresponding anions have been optimised (B3LYP/6-31++G(d,p)) in implicit water in order to gain an insight on the peptide backbone N-H acidity. In this study, we have shown that the open conformations of the neutrals and the anions, which display a β sheet like structure are well populated and their pK_as rank in the same order as the deamidating half-lives, that is the peptides that deaminate fastest can more readily access conformations that are more acidic.