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Epoxiconazole (EPO) is classified as a persistent organic pollutant due to its ability to persist in the environment for prolonged periods. Its degradation is pivotal in mitigating its environmental impact. This investigation focuses on assessing the degradation of EPO using various methodologies, namely Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis, conducted in both Milli-Q water and groundwater. These experiments encompassed evaluations at both the standard pH typically used in photo-Fenton reactions and the natural pH levels inherent to the respective aqueous environments. Additionally, EPO degradation products were analyzed after a 60-min reaction. Notably, in systems utilizing groundwater, the inclusion of additional iron was unnecessary, as the naturally occurring iron content in the groundwater facilitated the intended processes. Specifically, in Milli-Q water, solar photo-Fenton demonstrated an EPO degradation efficiency of 97%. Furthermore, the substitution of Milli-Q water with groundwater in Fenton-like processes did not significantly affect the efficacy of EPO degradation. These findings underscore the potential of solar photo-Fenton as an economically viable and environmentally sustainable strategy for EPO degradation.

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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.

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The application of photocatalysis for organic synthesis, both in the laboratory and on an industrial scale, will depend on the achieving of good yields and the ease with which it can be applied. Selective irradiation of the photocatalyst with LED light has made it possible to activate the reactions easily, without the need for UV or heat filters. However, a common problem is the need to separate the photocatalyst from the reaction products through extraction and chromatography isolation processes. These procedures make it difficult to recover and reuse the catalyst, which is not compatible with scale-up applications. Photocatalysts attached to heterogeneous supports resulted in an alternative, which facilitates their removal and reuse. In this study, we use chromatographic silica gel as a low-cost heterogeneous support to bind photosensitizers such as Riboflavin or Eosin Y. The modified silica gel was analyzed by FTIR-ATR and diffuse reflectance UV-visible spectroscopy, thermogravimetric analysis, and optical microscopy. These hybrid materials have a suitable size for easy separation by decantation and were found to be photoactive against two photooxidation reactions. These easy-to-handle materials open the door to effective applications for photoinduced organic synthesis methods at medium to large scale.

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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.

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The proherbicide Isoxaflutole (IXF) hydrolyzes spontaneously to diketonitrile (DKN) a phytotoxic compound with herbicidal activity. In this work, the sensitized degradation of IXF using Riboflavin (Rf), a typical environmentally friendly sensitizer, Fenton and photo-Fenton processes has been studied. The results indicate that only the photo-Fenton process produces a significant degradation of the IXF. Photolysis experiments of IXF sensitized by Riboflavin is not a meaningful process, IXF quenches the Rf excited triplet (3 Rf*) state with a quenching rate constant of 1.5 · 107  m-1  s-1 and no reaction is observed with the species O2 (1 Δg ) or O 2 · - generated from 3 Rf*. The Fenton reaction produces no changes in the IXF concentration. While the photo-Fenton process of the IXF, under typical conditions, it produces a degradation of 99% and a mineralization to CO2 and H2 O of 88%. A rate constant value of 1.0 × 109  m-1  s-1 was determined for the reaction between IXF and HO˙. The photo-Fenton process degradation products were identified by UHPLC-MS/MS analysis.

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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.

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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 × 10(8) 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.

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The objectives of the present study were to determine the in vitro efficacy of chitosan (0.5, 1.0, 2.0 and 3.0mg/mL) under different water availabilities (0.995, 0.99, 0.98, 0.96 and 0.93) at 25°C on lag phase, growth rate and fumonisin production by isolates of Fusarium verticillioides and Fusarium proliferatum. The presence of chitosan affected growth and fumonisin production, and this effect was dependent on the dose and aW treatment used. The presence of chitosan increased the lag phase, and reduced the growth rate of both Fusarium species significantly at all concentrations used, especially at 0.93 aW. Also, significant reduction of fumonisin production was observed in both Fusarium species at all conditions assayed. The present study has shown the combined effects of chitosan and aW on growth and fumonisin production by the two most important Fusarium species present on maize. Low molecular weight (Mw) chitosan with more than 70% of degree of deacetylation (DD) at 0.5mg/mL was able to significantly reduce growth rate and fumonisin production on maize-based media, with maximum levels of reduction in both parameters obtained at the highest doses used. As fumonisins are unavoidable contaminants in food and feed chains, their presence needs to be reduced to minimize their effects on human and animal health and to diminish the annual market loss through rejected maize. In this scenario post-harvest use of chitosan could be an important alternative treatment.

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Kinetic and mechanistic aspects of the photochemical and microbiological degradation of the herbicide Maleic Hydrazide (MH) have been studied. Riboflavin (Rf, vitamin B2) was employed as a main photosensitizer whereas Humic Acid (HA) was included as a second sensitizer in order to more closely simulate natural environmental conditions. MH quenches excited singlet and triplet states of Rf, with rate constants close to the diffusion limit. The herbicide and dissolved molecular oxygen competitively quench triplet excited Rf. As a consequence the reactive oxygen species (ROS), superoxide radical anion (O2(-·)), hydrogen peroxide (H2O2) and singlet molecular oxygen (O2((1)Δg)) are produced by electron- and energy-transfer processes, respectively, as demonstrated by auxiliary experiments employing selective auxiliary quenchers and the exclusive O2((1)Δg) generator Rose Bengal (RB). As a global result, the photodegradation of Rf is retarded, whereas MH is degraded by the generated ROS. The bacteria Pseudomonas aeruginosa (Ps) and Bacillus subtilis (Bs), recognized as contaminants surface-water and soil and microbial antagonists of phytopathogenic, were used in the microbiological experiments. Results of the individual incubation of both bacteria in in the presence of MH indicate a stimulation on the Ps growth, implying the biodegradation of the herbicide, whereas MH only exerted a bacteriostatic effect on Bs.

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The aim of this study was to evaluate the efficacy of ferulic acid (1, 10, 20 and 25 mM) at different water activity (aw) values (0.99, 0.98, 0.96 and 0.93) at 25 °C on growth and fumonisin production by Fusarium verticillioides and Fusarium proliferatum on maize based media. For both Fusarium species, the lag phase significantly decreased (p ≤ 0.001), and the growth rates increased (p ≤ 0.001) at the lowest ferulic acid concentration used (1mM), regardless of the aw. However, high doses of ferulic acid (10 to 25 mM) significantly reduced (p ≤ 0.001) the growth rate of both Fusarium species, regardless of the a(w). In general, growth rate inhibition increased as ferulic acid doses increased and as media aw decreased. Fumonisin production profiles of both Fusarium species showed that low ferulic acid concentrations (1-10mM) significantly increased (p ≤ 0.001) toxin production, regardless of the aw. High doses of ferulic acid (20-25 mM) reduced fumonisin production, in comparison with the controls, by both Fusarium species but they were not statistically significant in most cases. The results show that the use of ferulic acid as a post-harvest strategy to reduce mycotoxin accumulation on maize needs to be discussed.

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