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.

State-of-the-Art of Eggshell Waste in Materials Science: Recent Advances in Catalysis, Pharmaceutical Applications, and Mechanochemistry.

Eggshell waste is among the most abundant waste materials coming from food processing technologies. Despite the unique properties that both its components (eggshell, ES, and eggshell membrane, ESM) possess, it is very often discarded without further use. This review article aims to summarize the recent reports utilizing eggshell waste for very diverse purposes, stressing the need to use a mechanochemical approach to broaden its applications. The most studied field with regards to the potential use of eggshell waste is catalysis. Upon proper treatment, it can be used for turning waste oils into biodiesel and moreover, the catalytic effect of eggshell-based material in organic synthesis is also very beneficial. In inorganic chemistry, the eggshell membrane is very often used as a templating agent for nanoparticles production. Such composites are suitable for application in photocatalysis. These bionanocomposites are also capable of heavy metal ions reduction and can be also used for the ozonation process. The eggshell and its membrane are applicable in electrochemistry as well. Due to the high protein content and the presence of functional groups on the surface, ESM can be easily converted to a high-performance electrode material. Finally, both ES and ESM are suitable for medical applications, as the former can be used as an inexpensive Ca2+ source for the development of medications, particles for drug delivery, organic matrix/mineral nanocomposites as potential tissue scaffolds, food supplements and the latter for the treatment of joint diseases, in reparative medicine and vascular graft producing. For the majority of the above-mentioned applications, the pretreatment of the eggshell waste is necessary. Among other options, the mechanochemical pretreatment has found an inevitable place. Since the publication of the last review paper devoted to the mechanochemical treatment of eggshell waste, a few new works have appeared, which are reviewed here to underline the sustainable character of the proposed methodology. The mechanochemical treatment of eggshell is capable of producing the nanoscale material which can be further used for bioceramics synthesis, dehalogenation processes, wastewater treatment, preparation of hydrophobic filters, lithium-ion batteries, dental materials, and in the building industry as cement.