Rice husk-based pyrogenic carbonaceous material efficiently promoted peroxymonosulfate activation toward the non-radical pathway for the degradation of pharmaceuticals in water.

Pristine pyrogenic carbonaceous material (BRH) obtained from rice husk and modified with FeCl3 (BRH-FeCl3) were prepared and explored as carbocatalysts for the activation of peroxymonosulfate (PMS) to degrade a model pharmaceutical (acetaminophen, ACE) in water. The BRH-FeCl3/PMS system removed the pharmaceutical faster than the BRH/PMS. This is explained because in BRH-FeCl3, compared to BRH, the modification (iron played a role as a structuring agent mainly) increased the average pore diameter and the presence of functional groups such as -COO-, -Si-O-, or oxygen vacancies, which allowed to remove the pollutant through an adsorption process and significant carbocatalytic degradation. BRH-FeCl3 was reusable during four cycles and had a higher efficiency for activating PMS than another inorganic peroxide (peroxydisulfate, PDS). The effects of BRH-FeCl3 and PMS concentrations were evaluated and optimized through an experimental design, maximizing the ACE degradation. In the optimized system, a non-radical pathway (i.e., the action of singlet oxygen, from the interaction of PMS with defects and/or -COO-/-Si-O- moieties on the BRH-FeCl3) was found. The BRH-FeCl3/PMS system generated only one primary degradation product that was more susceptible to biodegradation and less active against living organisms than ACE. Also, the BRH-FeCl3/PMS system induced partial removals of chemical oxygen demand and dissolved organic carbon. Furthermore, the carbocatalytic system eliminated ACE in a wide pH range and in simulated urine, having a low-moderate electric energy consumption, indicating the feasibility of the carbocatalytic process to treat water polluted with pharmaceuticals.

Experimental data on synthesis and characterization of chiral dinuclear manganese (II-II) compounds as biomimetic models of the active center of catalase.

Dinuclear manganese (II- III) compounds, which are potential models of the active center of catalase, were synthetized. This type of metalloenzymes presents biological importance due to three factors: they are redox catalyst centres, they are able to carry out hydrolytic reactions and they participate in activated processes via Lewis acids. Structurally, their active centre is composed by dinuclear manganese compounds, linked to nitrogen and oxygen donor atoms. An octahedral geometry around the metal ions were found, with acetate, hydroxy and aquo ligands; which can work as molecule bridges between them. The acid medium favours the electronic transfer between Mn3+ - Mn2+ as redox centre at 1.559 V and the consequent oxidation of hydrogen peroxide or organic molecules. The work also reports the data of two chiral novel compounds, [Mn2(S,S(+)Hcpse)4(NaClO4)2(NaOH)(CH4O)]n·[(C2H6O)2]n·[(CH4O)2]n and its respective enantioisomer, in which µ-oxo being as bridge metal centre. The X-ray structural was obtained as well as the optical and magnetic properties using Circular Dichroism, Electronic Paramagnetic Resonance, Magnetic Susceptibility and X-ray photoelectron spectroscopy.