Photocatalytic evaluation and characterization of TiO2-riboflavin phosphate film: analysis of reactive oxygen species.

The effect of Riboflavin-5'-phosphate (RFPO4) sensitization on photocatalytic properties of TiO2 film was studied. RFPO4 was adsorbed on film surface to investigate the photophysical properties of TiO2 upon blue-light photoexcitation. The film was characterized through scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, and diffuse reflectance spectroscopy. The efficiency of the TiO2/RFPO4 film was tested for pollutant elimination in aqueous media in a visible-light-driven system. The phenol paradigmatic model was employed in an aqueous solution as a contaminant target. TiO2/RFPO4 sensitized photodegradation of phenol, which produces catechol, hydroquinone, and benzophenone, was monitored by absorption spectroscopy and HPLC. The results indicated that phenol degradation with TiO2/RFPO4 film was due to the photogeneration of two reactive oxygen species, singlet molecular oxygen (O2(1Δg)) and superoxide radical anion (O2·-) identified through specific detection techniques. The presence of O2(1Δg) is reported here for the first time as generated from a sensitized TiO2 film upon visible-light photoirradiation. Based on the photophysical determinations, a photocatalytic mechanism for TiO2/RFPO4 was established.

A novel eco-friendly polymeric photosensitizer based on chitosan and flavin mononucleotide.

Flavin mononucleotide (FMN) is a dye belonging to the flavin family. These dyes produce photosensitized degradation of organic compounds via reaction with the excited states of the dye or with reactive oxygen species photogenerated from the triplet of the dye. This article presents a new polymeric dye (FMN-CS) composed of the photosensitizer FMN covalently bonded to chitosan polysaccharide (CS). FMN-CS obtained has a molecular weight of 230 × 103 g mol-1 and a deacetylation degree of 74.8%. The polymeric dye is an environmentally friendly polymer with spectroscopic and physicochemical properties similar to those of FMN and CS, respectively. Moreover, under sunlight, it is capable of generating 1O2 with a quantum yield of 0.31. FMN-CS, like CS, is insoluble in basic media. This allows easy recovery of the polymeric dye once the photosensitized process has been carried out and makes FMN-CS a suitable photosensitizer for the degradation of pollutants in contaminated waters. To evaluate whether FMN-CS may be used for pollutant degradation, the photosensitized degradation of two trihydroxybenzenes by FMN-CS was studied.

Oregano Essential Oil Interactions with Photogenerated Singlet Molecular Oxygen.

Essential oils are a mixture of volatile compounds, products of the secondary metabolism of plants. Once extracted, they can be deteriorated losing their organoleptic and therapeutic properties due to various environmental factors, being light exposure in aerobic conditions the main cause. In this work, the oregano essential oil extraction and characterization from Origanum vulgare plants grown in the experimental field of the FTU-UNSL and its photodegradation in MeOH:H2 O 60:40 v/v solvent were studied. Characterization by EIMS and NIST Mass Spectrometry indicates the main compounds of oregano essential oil, quantified in the extracted oil by GC-MS, are carvacrol (7.14%) and thymol (47.37%). Degradation of essential oil and its two major components can be caused by reactive oxygen species photogenerated from endogenous sensitizers as riboflavin. Our results suggest degradation occurs involving singlet molecular oxygen. Interaction of carvacrol and thymol with singlet oxygen is mainly a physical process, while essential oil has an important reactive component, which indicates there might be other constituents which could contribute to reactive photoprotection. The effect of simultaneous presence of oregano essential oil and tryptophan amino acid-used as a photooxidizable model under riboflavin-photosensitizing conditions-was studied in order to evaluate the possible photoprotection exerted by the essential oil.

The activity of propolis in the scavenging of vitamin B2-photogenerated ROS.

OBJECTIVES: The study was focused on the activity of propolis from Amaicha del Valle, Argentina (ProAV) as a promoter and scavenger of Riboflavin (Rf)--photogenerated reactive oxygen species (ROS). METHODS: Through a kinetic and mechanistic study, employing stationary and time-resolved photochemical and electrochemical techniques, the protecting activity of ProAV was investigated. RESULTS: In the absence of light and Rf, ProAV exerted a relatively efficient inhibitory effect on 1,1-diphenyl-2-picrylhydrazyl radicals and acts as a protector of artificially promoted linoleic acid oxidation. Under aerobic visible-light-irradiation conditions, in the presence of Rf as the only light-absorber species, a complex picture of competitive processes takes place, starting with the quenching of singlet and triplet electronically excited states of Rf by ProAV. The species O2(1 g), O2(•-), H2O2, and OH(•) are generated and interact with ProAV. DISCUSSION: ProAV behaves as an efficient ROS scavenger. It is scarcely photo-oxidized by interaction with the mentioned ROS. Quantitative results indicate that ProAV is even more resistant to photo-oxidation than the recognized antioxidant trolox. Two dihydroxychalcones, mostly present in the ProAV composition, are responsible for the protecting activity of the propolis.

Stability of flavonoids in the presence of riboflavin-photogenerated reactive oxygen species: a kinetic and mechanistic study on quercetin, morin and rutin.

Kinetic and mechanistic aspects on the stability of the flavones (FL) quercetin (Que), morin (Mor) and rutin (Rut), in methanolic solution and in the presence of reactive oxygen species (ROS) generated by visible light-promoted riboflavin (Rf, vitamin B(2)) photoirradiation were studied. The system was chosen as a model for the evaluation of the in vivo protective effect of biological targets by the flavones. The overall picture includes the vitamin as an endogenous natural photosensitizer. A systematic study on the effect of ROS on FL photostability shows that under work conditions Que is oxidized by singlet molecular oxygen (O(2)((1)Delta(g))), superoxide radical anion (O(2)(-)) and hydrogen peroxide; Mor is degraded by O(2)((1)Delta(g)) and O(2)(-) whereas Rut only reacts with O(2)((1)Delta(g)). Que and Rut, with an extremely poor overall rate constant, are mainly physical quenchers of O(2)((1)Delta(g)). Mor, with O(2)((1)Delta(g))-interception ability slightly lower than the recognized synthetic antioxidant trolox (Tx), behaves as a typical sacrificial scavenger provided that ca 80% of the collisions with O(2)((1)Delta(g)) cause its own degradation, whereas this parameter reaches around 50% in the case of Tx.