Vanesa Muñoz

The Employment of a Removable Chitosan‐Derivatized Polymeric Sensitizer in the Photooxidation of Polyhydroxylated Water‐Pollutants

The known O2(1∆g)‐sensitizer system Chitosan bounded Rose Bengal (CH‐RB), with Rose Bengal (RB) immobilized by irreversible covalent bonding to the polymer Chitosan (CH), soluble in aquous acidic medium, was employed in the photodegradation of three tri‐hydroxy benzene water‐contaminants (THBs). The system sensitizes the O2(1∆g)‐mediated photodegradation of THBs by a process kinetically favored, as compared to that employing free RB dissolved in the same solvent. Additionally the free xanthene dye, degradable by O2(1∆g) through self‐sensitization upon prolonged light‐exposure, is considerably protected when bonded to CH‐polymer. The polymeric sensitizer, totally insoluble in neutral medium, can be removed from the solution after the photodegradative cycle by precipitation through a simple pH change. This fact constitutes an interesting aspect in the context of photoremediation of confined polluted waters. In other words, the sensitizing system could be useful for avoiding to dissolve dyestuffs in the polluted waters, in order to act as conventional sunlight‐absorbing dye‐sensitizers. In parallel the interaction CH ‐ O2(1∆g) in acidic solution was evaluated. The polymer quenches the oxidative species with a rate constant 2.4 × 108 M−1 s−1 being the process mostly attributable to a physical interaction. This fact promotes the photoprotection of the bonded dye in the CH‐RB polymer.

Scavenging of photogenerated ROS by Oxicams. Possible biological and environmental implications

The profusely employed drugs Piroxicam (Piro), Tenoxicam (Teno) and Meloxicam (Melo) belonging to the non-steroidal antiinflammatory drug (NSAID) family of the Oxicams (Oxis) were studied in the frame of two specific conditions: (a) their ROS scavenging ability, in relation to a possible biological antioxidant action and (b) their photodegradability under environmental conditions, in the context of Oxi-contaminated waters. Singlet molecular oxygen (O2((1)Δg)) and superoxide radical anion (O2(-)) were photogenerated through Riboflavin (Rf, vitamin B2)-photosensitization in aqueous and aqueous-methanolic solutions in the presence of Oxi concentrations in the range 50-500 μM. The visible-light absorber vitamin is currently present in all types of natural waters and constitutes the most frequent endogenous photosensitizer in mammals. Hence, it was employed in order to mimic both natural sceneries of interest. All three Oxis quench O2((1)Δg) with rate constants in the order of 10(8)M(-1)s(-1) showing a significant photodegradation efficiency given by a dominant reactive fashion for deactivation of the oxidative species. Although this is not a desirable property in the context of photoprotection upon prolonged photoirradiation, constitutes in fact a promissory aspect for the degradation NSAIDs, in waste waters. Indirect evidence indicates that Melo is also oxidized through a O2(-)-mediated component. The simultaneous presence of Piro plus tryptophan or tyrosine under Rf-photosensitizing conditions, which has taken the amino acids as photooxidizable model residues in a proteinaceous environment, indicates that the NSAID induces a protection of the biomolecules against photodynamic degradation.

Experimental procedure for the mechanical evaluation of oxide-carbon refractories by strain measurement

Experimental issues regarding the implementation of a methodology for obtaining strain-stress curves at high temperatures and in a controlled atmosphere of oxide-C refractories are presented. These curves give a detailed description of the material’s mechanical behavior that is not attainable using conventional tests. The method to measure the specimen strain by contact extensometry and the system to control the atmosphere by a gas flow are described. As an example, the experimental study of commercial Al2O3-MgO-C refractory bricks used in steel ladles at high temperature (1260 °C) in both air and N2 atmospheres is presented showing the valuable information obtained applying strain-stress measurements.

Effect of Cu2 +-complexation on the scavenging ability of chrysin towards photogenerated singlet molecular oxygen (O2(1Δg)). Possible biological implications

Visible-light irradiation of aqueous-ethanolic solutions of Riboflavin (Rf) in the individual presence of the flavone chrysin (Chr) and its complex with Cu(2+) ([Chr2Cu]; 2:1 L:M) generates singlet molecular oxygen O2((1)Δg), that concomitantly interact with both flavone derivatives. Overall (kt) and reactive (kr) rate constants in the order of 10(7)M(-1)s(-1) were determined for the process. Metal chelation greatly enhances the scavenging ability of [Chr2Cu] towards O2((1)Δg) through a mechanism dominated, in >80%, by the physical component. In this way, practically all O2((1)Δg) is deactivated by the complex without significant loss of the quencher. The isolated flavone quenches O2((1)Δg) in a prevailing reactive fashion. The very low value exhibited by [Chr2Cu] for the kr/kt ratio constitutes a positive quality for antioxidative protectors in biological media, where elevated local concentration and high reactivity of significant molecules make them initial targets for O2((1)Δg) aggression. Finally, two interesting properties in the field of free radicals scavenging by [Chr2Cu] must be mentioned. In first place metal chelation itself, in the obvious sense of free metal ion withdrawal from the oxidizable medium, prevents the initiation of a free radical-mediated oxidation processes through mechanisms of Fenton or lipid peroxidation. In addition, the incorporation of Cu adds to [Chr2Cu] the ability of a free radical scavenger, already described for similar Cu-chelate compounds. This collection of beneficial properties positions the complex as a remarkably promising bioprotector towards ROS-mediated oxidation. A quantification of the efficiency on the initial anti-oxidative effect exerted by Chr and [Chr2Cu] towards tryptophan was carried out. The amino acid is an archetypal molecular model, commonly employed to monitor oxidative degradation of proteinaceous media. It was efficiently photoprotected against O2((1)Δg)-mediated photooxidation by [Chr2Cu].

Chalcones as Analytical Reagents of Aluminum: Stability, Thermodynamic and Kinetic Study

Abstract Chalcones, a group of polyphenolic compounds, has been studied for a long time due to their biological properties and their ability as analytical reagents. In this work the stability and thermodynamic parameters concerning the fotmation in ethanolic medium of two chalcone–aluminium complexes (2′,3-dihydroxychalcone-Al(III) and 2′,4′,3-trihydroxychalcone-Al(III)) were studied and a kinetic study of the formation reaction was aslo performed. Both systems showed 1:1 L : M stoichiometry and stability constants at four temperatures were determined. Thermodynamic parameters indicate that both formation reactions are endothermic and driving force is entropic. Kinetic study revealed that 2′,4′,3-trihydroxychalcone-Al(III) formation is faster than 2′,3-dihydroxyclacone-Al(III), a factor which can be interesting when proposing new analytical reagents.