Degradation of tartrazine by Oxone® in the presence of cobalt based catalyst supported on pillared montmorillonite - Efficient technology even in extreme conditions.

The catalytic degradation of hazardous organic contaminants in industrial wastewater is a promising technology. Reactions of tartrazine, the synthetic yellow azo dye, with Oxone® in the presence of catalyst in strong acidic condition (pH 2), were detected by using UV-Vis spectroscopy. In order to extend the applicability profile of Co-supported Al-pillared montmorillonite catalyst an investigation of Oxone® induced reactions were performed in extreme acidic environment. The products of the reactions were identified by liquid chromatography-mass spectrometry (LC-MS). Along with the catalytic decomposition of tartrazine induced by radical attack (confirmed as unique reaction path under neutral and alkaline conditions), the formation of tartrazine derivatives by reaction of nucleophilic addition was also detected. The presence of derivatives under acidic conditions slowed down the hydrolysis of tartrazine diazo bond in comparison to the reactions in neutral environment. Nevertheless, the reaction in acidic conditions (pH 2) is faster than the one conducted in alkaline conditions (pH 11). Theoretical calculations were used to complete and clarify the mechanisms of tartrazine derivatization and degradation, as well as to predict the UV-Vis spectra of compounds which could serve as predictors of certain reaction phases. ECOSAR program, used to estimate toxicological profile of compounds to aquatic animals, indicated an increase in the harmfulness of the compounds identified by LC-MS as degradation products from the reaction conducted for 240min. It could be concluded that an intensification of the process parameters (higher concentration of Oxone®, higher catalyst loading, increased reaction time, etc.) is needed in order to obtain only biodegradable products.

A novel approach in revealing mechanisms and particular step predictors of pH dependent tartrazine catalytic degradation in presence of Oxone®.

The degradation of tartrazine in the presence of cobalt activated Oxone® (potassium peroxymonosulfate) was investigated at different initial pH values. Aluminum pillared clay had the role of a support for catalytically active cobalt oxide species. The degradation of tartrazine and the formation of a mixture of degradation products were monitored using the Ultraviolet-Visible (UV-Vis) spectroscopy and gas chromatography-mass spectrometry (GC-MS). The exact qualitative composition of this mixture and the determination of the most probable mechanism of degradation (the primary goal) were obtained using GC-MS. Besides, the main reaction pathway (reaction with SO4˙- radical anion) and secondary pathways were proposed depending on the pH value. At pH = 6 the reaction with HO˙ radical was proposed. At pH = 11 decarboxilation was suggested as the first step of the secondary proposed reaction pathway. The combination of results acquired from the deconvolution of UV-Vis spectra and the theoretical UV-Vis spectra of degradation products, whose occurrence was predicted by quantum-chemical calculations, was proven to be beneficial for the identification of tartrazine degradation products and for defining UV-Vis predictors of particular degradation steps. An additional contribution of this paper, from the reactivity aspect, was the establishment of the critical structural demand for the radical degradation of any diazo compound. The existence of a hydrogen atom bound to a diazo group was found to be the essential prerequisite for the radical cleavage of diazo compounds.

Equilibrium and kinetics study on hexavalent chromium adsorption onto diethylene triamine grafted glycidyl methacrylate based copolymers.

Two porous and one non-porous crosslinked poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [abbreviated PGME] were prepared by suspension copolymerization and functionalized with diethylene triamine [abbreviated PGME-deta]. Samples were characterized by elemental analysis, mercury porosimetry, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and transmission electron microscopy. Kinetics of Cr(VI) sorption by PGME-deta were investigated in batch static experiments, in the temperature range 25-70°C. Sorption was rapid, with the uptake capacity higher than 80% after 30 min. Sorption behavior and rate-controlling mechanisms were analyzed using five kinetic models (pseudo-first order, pseudo-second order, Elovich, intraparticle diffusion and Bangham model). Kinetic studies showed that Cr(VI) adsorption adhered to the pseudo-second-order model, with definite influence of pore diffusion. Equilibrium data was tested with Langmuir, Freundlich and Tempkin adsorption isotherm models. Langmuir model was the most suitable indicating homogeneous distribution of active sites on PGME-deta and monolayer sorption. The maximum adsorption capacity from the Langmuir model, Q(max), at pH 1.8 and 25°C was 143 mg g(-1) for PGME2-deta (sample with the highest amino group concentration) while at 70°C Q(max) reached the high value of 198 mg g(-1). Thermodynamic parameters revealed spontaneous and endothermic nature of Cr(VI) adsorption onto PGME-deta.

Porosity of different dental luting cements.

OBJECTIVE: The aim of this in vitro study was to compare open porosity and pore size distribution of different types of luting cements (zinc phosphate and polycarboxylate produced by Harvard Cement, Great Britain, glass-ionomer product GC Fuji I, GC Corporation, Japan, and Panavia F, resin based composite cement, Kurraray Co. Ltd. Japan) using mercury intrusion porosimetry and use it as an additional parameter for ranging the quality of cements used in prosthetics. METHOD: Samples were hand mixed in accordance with the manufacturer's instructions and formed in cylindrical test specimens. Density of samples was determined using a pycnometer while porous structure was estimated using high pressure mercury intrusion porosimeter enabling estimation of pore diameters in interval 7.5-15,000 nm. RESULTS: The polycarboxylate cement posses the highest porosity and specific pore volume among investigated cements. By comparison of the results obtained for zinc phosphate and glass-ionomer cement, it can be observed that according to some textural properties zinc phosphate cement is better choice (smaller specific pore volume and absence of macropores larger than 1 microm) while according to other textural properties the glass-ionomer has advantage (smaller porosity). The resin based composite cement poses the most desired porous structure for prosthetic application among the investigated cements (the lowest porosity and specific pore volume and all identified pores are smaller than 20 nm). SIGNIFICANCE: Based on results of this study, it is possible to estimate the efficiency of luting cements to protect the interior of tooth from penetration of oral fluids, bacteria and bacterial toxins into unprotected dentine.