BACKGROUND: Stilbenoid extracts, such as those originating from grapevine by-products (e.g. canes), are of interest for use as biopesticides in vineyard owing to their antimicrobial activities. However, stilbenoids are unstable in the environment, especially under light. This study aimed to chemically characterize the effect of UV light on stilbenoids present in a grapevine cane extract (CE), and to evaluate the antimicrobial activities against two major grapevine pathogens (Plasmopara viticola and Botrytis cinerea) of grapevine extracts exposed to UV.
RESULTS: Treatment with UV (365 nm) on a grapevine CE led to degradation of stilbenoids (up to 71% after 1 h). The stilbenoid stability depended on their chemical structure: only those possessing CC, as trans-resveratrol and trans-ε-viniferin, were affected with first their isomerization and secondly their oxidation/cyclization. As a consequence, UV-exposed extracts (UV-CEs) showed reduced antimicrobial activities against the two pathogens (mycelium and spores). For instance, regarding P. viticola, an UV-CE exposed during 4 h showed an almost total loss of its activity on oomycete development and a 2.4-fold inhibition of zoospore mobility in comparison to CE. For B. cinerea, the inhibition capacity of the same UV-CE was reduced by only 1.1-fold on mycelial development and by 3.2-fold on conidial germination compared to CE.
CONCLUSIONS: UV light triggered modifications on the structure of bioactive stilbenoids, resulting in losses of their antimicrobial activities. Photoprotection of stilbenoids has to be considered in the perspective of using them in vineyards as biopesticides. © 2024 The Author(s). Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Timolol (TIM) is a non-selective ß-adrenergic receptor antagonist used orally for the treatment of hypertension and heart attacks, and topically for treating glaucoma; lately, it has also been used in some specific dermatological problems. In the present study, its photodegradation and potential risk of phototoxicity were examined using chemical, in silico and in vitro methods. The UV/VIS irradiated solutions of TIM at pH 1-13 were subjected to LC-UV and UPLC-HRMS/MS analyses showing pseudo first-order kinetics of degradation and several degradation products. The structures of these photodegradants were elucidated by fragmentation path analysis based on high resolution (HR) fragmentation mass spectra, and then used for toxicity evaluation using OSIRIS Property Explorer and Toxtree. Potential risk of phototoxicity was also studied using chemical tests for detecting ROS under UV/VIS irradiation and in vitro tests on BALB/c 3T3 mouse fibroblasts (MTT, NRU and Live/Dead tests). TIM was shown to be potentially phototoxic because of its UV/VIS absorptive properties and generation ROS during irradiation. As was observed in the MTT and NRU tests, the co-treatment of fibroblasts with TIM and UV/VIS light inhibited cell viability, especially when concentrations of the drug were higher than 50 µg/mL.

Antibiotic contamination has a significant negative impact on China, one of the largest producers and consumers of antibiotics worldwide. In this study, a three-dimensional flower-like structure of CoFe-LDHs was used to efficiently degrade tetracycline (TC) in a system triggered by peroxymonosulfate (PMS) and exposed to visible light. After exploring the effects of different metal ratios, catalyst dosage, initial TC concentrations, and pH, the optimal reaction conditions were determined. In comparison to pure CoFe-LDHs, the TC elimination rate was dramatically increased by the addition of the PMS. The strong environmental resistance, excellent stability and reusability, and universal flexibility were shown. The quenching experiments and electron spin resonance detection showed that the creation of reactive oxygen species was facilitated by the synergistic transmission of electrons between the active bimetallic components. Further, photogenerated holes was the dominant oxidizing species, which contributed more to the degradation of TC. The potential degradation pathways and intermediate toxicity of TC were suggested. This work offers a new method dominated by photogenerated holes for efficiently removing TC effluent.

A wide range of contaminants of emerging concern (CECs) are known to photodegrade in the surface layers of natural waters and wastewater systems. Computer programs such as GCSolar, ABIWAS, APEX, EXAMS and WASP model the direct photolysis rates and half-lives of CECs, usually as a function of the solar irradiance, water molar light extinction, chemical molar light absorption and reaction quantum yield. These programs have been used extensively for studies in natural water systems in the northern hemisphere. However, their applicability to wastewater treatment systems such as waste stabilisation ponds and/or southern hemisphere conditions is not well studied. Here we present a comparative review of the major software used and their potential applicability to predicting direct photolysis rates and half-lives in wastewater. The newer equivalent monochromatic wavelength, approach, which enables the approximation of polychromatic photodegradation via a monochromatic wavelength is also discussed. Current software appears to be less suitable for modelling photodegradation in wastewater systems in the southern hemisphere than the northern hemisphere as their internal databases are based on data from natural waters in the northern hemisphere. This may be because there have been few attempts to model CEC photolysis in wastewater systems, particularly in the southern hemisphere. This indicates that either new software needs to be developed, or these programs need to be updated with data on wastewater matrices and/or the southern hemisphere. We anticipate this review will promote the adaptation of these programs as tools to further the understanding CEC photodegradation in wastewater treatment plants.

Citalopram (CIT) is a commonly prescribed medication for depression. However, the photodegradation mechanism of CIT has not yet been fully analyzed. Therefore, the photodegradation process of CIT in water is studied by density functional theory and time-dependent density functional theory. The calculated results show that during the indirect photodegradation process, the indirect photodegradation of CIT with ·OH occurs via OH-addition and F-substitution. The minimum activation energy of C10 site was 0.4 kcal/mol. All OH-addition and F-substitution reactions are exothermic. The reaction of 1O2 with CIT includes the substitution of 1O2 for F and an addition reaction at the C14 site. The Ea value of this process is 1.7 kcal/mol, which is the lowest activation energy required for the reaction of 1O2 with CIT. C-C/C-N/C-F cleavage is involved in the direct photodegradation process. In the direct photodegradation of CIT, the activation energy of the C7-C16 cleavage reaction was the lowest, which was 12.5 kcal/mol. Analysis of the Ea values found that OH-addition and F-substitution, the substitution of 1O2 for F and addition at the C14 site, as well as the cleavage reactions of C6-F/C7-C16/C17-C18/C18-N/C19-N/C20-N are the main pathways of photodegradation of CIT.

Excessive usage and unrestricted discharge of antibiotics in the environment lead to their accumulation in the ecosystem due to their highly stable and non-biodegradation nature. Photodegradation of four most consumed antibiotics such as amoxicillin, azithromycin, cefixime, and ciprofloxacin were studied using Cu2O-TiO2 nanotubes. Cytotoxicity evaluation of the native and transformed products was conducted on the RAW 264.7 cell lines. Photocatalyst loading (0.1-2.0 g/L), pH (5, 7 and 9), initial antibiotic load (50-1000 μg/mL) and cuprous oxide percentage (5, 10 and 20) were optimized for efficient photodegradation of antibiotics. Quenching experiments to evaluate the mechanism of photodegradation with hydroxyl and superoxide radicals were found the most reactive species of the selected antibiotics. Complete degradation of selected antibiotics was achieved in 90 min with 1.5 g/L of 10% Cu2O-TiO2 nanotubes with initial antibiotic concentration (100 μg/mL) at neutral pH of water matrix. The photocatalyst showed high chemical stability and reusability up to five consecutive cycles. Zeta potential studies confirms the high stability and activity of 10% C-TAC (Cuprous oxide doped Titanium dioxide nanotubes for Applied Catalysis) in the tested pH conditions. Photoluminescence and Electrochemical Impedance Spectroscopy data speculates that 10% C-TAC photocatalyst have efficient photoexcitation in the visible light for photodegradation of antibiotics samples. Inhibitory concentration (IC50) interpretation from the toxicity analysis of native antibiotics concluded that ciprofloxacin was the most toxic antibiotic among the selected antibiotics. Cytotoxicity percentage of transformed products showed r: -0.985, p: 0.01 (negative correlation) with the degradation percentage revealing the efficient degradation of selected antibiotics with no toxic by-products.

Mechanism of direct UV photolysis of nalidixic acid (NA), a model quinolone antibiotic, was revealed using a combination of steady-state photolysis coupled with high resolution LC-MS and DFT quantum-chemical calculations. Both quantum yields of photodegradation and detailed identification of final products were performed for the first time for two main forms of NA: neutral and anionic. The quantum yield of NA photodegradation is 0.024 and 0.0032 for the neutral and anionic forms in the presence of dissolved oxygen and 0.016/0.0032 in deoxygenated solutions, respectively. The main process is photoionization with the formation of a cation radical, which undergoes transformation into three different neutral radicals and further into final photoproducts. It is shown that the triplet state does not play a role in the photolysis of this compound. The main products of photolysis are the products of the loss of carboxyl, methyl and ethyl groups in the NA molecule, as well as the dehydrogenation of the ethyl group. The results obtained may be important for understanding the fate of pyridine herbicides in the processes of disinfection by UV and in natural waters under the action of sunlight.

This work reports the preliminary results of the development of composite self-assembling membranes obtained by the combination of reduced graphene oxide (rGO) with commercial Degussa P25 titanium dioxide (TiO2). The purpose is to demonstrate the possibility of combining, in the same self-standing material, the capability to treat wastewater containing both inorganic and organic pollutants by exploiting the established ability of rGO to capture metal ions together with that of TiO2 to degrade organic substances. Moreover, this study also investigates the potential photocatalytic properties of tionite (TIO), to demonstrate the feasibility of replacing commercial TiO2 with such waste-derived TiO2-containing material, fulfilling a circular economy approach. Thus, rGO-TiO2 and rGO-TIO composite membranes, 1:1 by weight, were prepared and characterized by SEM-EDX, XRD, thermogravimetry, as well as by Raman and UV-Vis spectroscopies to verify the effective and homogeneous integration of the two components. Then, they were tested towards 3-mg L-1 aqueous synthetic solutions of Fe3+ and Cu2+ ions to evaluate their metal adsorption ability, with values of the order of 0.1-0.2 mmol gmembrane-1, comparable or even slightly higher than those of pristine rGO. Finally, the ability of the composites to degrade a common organic pesticide, i.e., Imidacloprid®, was assessed in preliminary photocatalysis experiments, in which maximum degradation efficiencies of 25% (after 3 h) for rGO-TiO2 and of 21% (after 1 h) for rGO-TIO were found. The result of tionite-containing membranes is particularly promising and worthy of further investigation, given that the anatase content of tionite is roughly 1/6 of the one in commercial TiO2.

One of the main concerns in using natural materials in construction, such as bamboo, regards their durability. Ultra violet (UV)irradiation is claimed as a damaging agent; therefore, it is important to study its effect. Several studies have shown that bamboo components such as lignin are subjected to photochemical degradation, but it is not well understood how this affects the mechanical properties of bamboo. The aim of this paper is to explore the correlation between photodegradation and bamboo mechanical performance. Bamboo samples were exposed to accelerated UV ageing for different times (from 6 to 360 h) and then subjected to a four-point bending test. Since one of the ways to stabilize bamboo is to thermally treat it, the tests were conducted on natural untreated bamboo and treated bamboo with a traditional flame treatment. Modifications of the chemical features of the material were analyzed with Fourier Trasform Infra Red (FTIR) spectroscopy, while modifications of the morphological features were analyzed byEnvironmental Scanning Electron Microscopy ESEM and optical microscopy observations. The results show that the bending behavior of bamboo is not compromised by UV exposure up to 360 h. In fact, although a progressive degradation of lignin is reported and cracks in the fiber walls are highlighted from micrographs, no effects were found on the fiber length.

Dissolved organic matter (DOM) plays a pivotal role in the biogeochemical cycles of elements and the regulation of forest ecosystem functions. However, studies on the regional and seasonal characteristics of DOM in cold-temperate montane forests are still not comprehensive. In this study, samples of water, soil, and sediment from different sites in the forest drainage basin were collected, and their DOM was characterized by an excitation-emission matrix and parallel factor analysis (EEM-PARAFAC). The results showed that terrestrial-sourced humic-like substances were the dominant DOM in the studied reservoir and inflowing rivers. The quality and quantity of DOM exhibited spatiotemporal variations with the influence of terrain and monsoonal precipitation. The average concentration of dissolved organic carbon (DOC) in the wet season was 11.62 mg/L, which was higher than that in the dry season (8.18 mg/L). Higher humification index (HIX) values were observed in the wet season and upstream water than in the dry season and reservoir water. Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) was used to further develop a molecular-level understanding of the in situ degradation process of DOM. The results indicated that photodegradation rather than biodegradation may play a dominant role in the in situ degradation of terrestrial-sourced humic-like substances under natural conditions. The biodegradability of DOM was enhanced after the in situ degradation process. Additionally, a significant decrease in the precursors of disinfectant byproducts in DOM was observed after in situ degradation. To our knowledge, this is the first study of the sources, characteristics, and in situ degradation of DOM in a reservoir in a cold-temperate forest. These findings help better understand the quality, quantity, and biogeochemical process of DOM in the studied reservoir and may contribute to the selection of drinking water treatment technologies for water supply.