A woman in her 70s had onychomycosis that was treated with topical luliconazole solution. Her nails changed color to yellow due to the treatment and exposure to sunlight. Avoidance of sunlight and continuous application of luliconazole resolved the discoloration and were effective for the treatment of onychomycosis one year after the first visit.

Recycling of plastic waste from electrical and electronic equipment (EEE), containing brominated flame retardants (BFR) remains difficult due to the increasingly stringent regulations on their handling and recovery. This report deals with photodegradation in a low-pressure reactor applying UV-visible light on Decabromodiphenyl ether (DBDE or BDE-209) randomly dispersed in commercially available Poly(acrylonitrile-butadiene-styrene) (ABS) and Poly(carbonate) (PC). The aim of this study is to investigate the possibility of decomposing a BFR in plastic waste from EEE while maintaining the specifications of the polymeric materials in order to allow for their recycling. The photodegradation of the extracted BFR was monitored using infrared spectroscopy and gas chromatography coupled with mass spectroscopy. DBDE underwent rapid photodegradation during the first minutes of exposure to UV-visible light and reached degradation yields superior to 90% after 15 min of irradiation. The evaluation of polymer properties (ABS and PC) after irradiation revealed superficial crosslinking effects, which were slightly accelerated in the presence of DBDE. However, the use of a low-pressure reactor avoids large photooxidation and allowed to maintain the thermal and structural properties of the virgin polymers.

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.

OBJECTIVE: Oxidation is one of the most common degradation pathways for active pharmaceutical ingredients (APIs) in pharmaceutical formulations, mostly involving 1-electron processes via peroxy radicals and 2-electron processes by peroxides. In liquid pharmaceutical formulations, several factors can impact oxidative instabilities including pH, excipient impurities, headspace oxygen, and the potential for photo-oxidation. Photo-oxidation can be particularly challenging to characterize given the number of oxidative mechanisms which can occur. This was observed during formulation development of a new chemical entity, MK-1454, where a degradation peak was observed during photostability studies which was not previously observed during peroxide and peroxyradical forced stress studies.
METHODS: To gain a fundamental understanding of reactive oxygen species generation and its role in degradation of MK-1454, experiments were performed with materials which either generate or measure reactive oxygen species including organic hydroperoxides, singlet oxygen, and superoxide to fundamentally understand a photodegradation mechanism which was observed in the original formulation. LC-MS experiments further elucidated the structure and mechanism of this observed degradation pathway.
RESULTS: A clear relationship between the decrease in dissolved oxygen after light exposure and the loss of MK-1454 was established. The data indicate that singlet oxygen is the most likely contributor of a particular photodegradation product. The singlet oxygen was generated by the inactive ingredients in the formulation, and LC-MS confirm this as the most likely pathway.
CONCLUSIONS: This work highlights the importance of understanding photochemical degradation of APIs in solution formulations and provides approaches which can better elucidate those mechanisms and thereby control strategies.

Environmental emission of pharmaceutical pollutants notably causes the contamination of aquatic ecosystems and drinking water. Typically, reduction of these pollutants in the environment is mostly managed by ameliorated wastewater treatments. Here, we report a method for the eco-design of drugs through the introduction within the molecular structure of a sensitive chemical group responsive to water treatments. The new drugs are thus programmed to fragment more easily and quickly than the original drugs. In this \"retro catabolic drug design\" strategy, methotrexate was used as drug model and an ether analog displaying a similar pharmacological profile was selected. Using photo-irradiation experiments at 254 nm, a representative drinking water treatment process, the identified transformation products were predominantly obtained from the expected molecular scission. Moreover, a faster kinetics of degradation was measured for the ether analog as compared to methotrexate and its transformation products were far less cytotoxic.

Pesticide deposits post-treatment and before diffusing inside the plants are exposed to sunlight. Many of them degrade into a variety of photoproducts that may be harmful to living beings through accidental ingestion. The addition of ultraviolet light absorbers to the pesticide formulations is an attractive strategy to prevent photodegradation of the pesticides. Water-soluble quaternary ammonium ultraviolet light absorbers (QAUVAs) were synthesized from 2,4-dihydroxy benzophenones (BP-1) and their structures were confirmed by 1H NMR, 13C NMR, UV, and FTIR. A cost-saving approach for the photoprotection of disulfoton insecticide using these QAUVAs is presented. All the four QAUVAs exhibit excellent UV screening effect. The insecticide disulfoton was recovered in much higher amounts (22.27 ~ 25.64% higher than control) when it was irradiated in the presence of QAUVAs in comparison with the amount of recovery of pesticide exposed in absence of them.

In this work, a complementary ultraviolet-visible (UV-VIS) spectroscopy and photoluminescence (PL) study on melatonin (MEL) hydrolysis in the presence of alkaline aqueous solutions and the photodegradation of MEL is reported. The UV-VIS spectrum of MEL is characterized by an absorption band with a peak at 278 nm. This peak shifts to 272 nm simultaneously with an increase in the band absorbance at 329 nm in the presence of an NaOH solution. The isosbestic point localized at 308 nm indicates the generation of some chemical compounds in addition to MEL and NaOH. The MEL PL spectrum is characterized by a band at 365 nm. There is a gradual decrease in the MEL PL intensity as the alkaline solution concentration added at the drug solution is increased. In the case of the MEL samples interacting with an alkaline solution, a new photoluminescence excitation (PLE) band at 335 nm appears when the exposure time to UV light reaches 310 min. A down-shift in the MEL PLE band, from 321 to 311 nm, as a consequence of the presence of excipients, is also shown. These changes are explained in reference to the MEL hydrolytic products.

Contamination of the environment by toxic pesticides has become of great concern in agricultural countries. Chlorpyrifos (CP) is among the pesticides most commonly detected in the environment owing to its wide agricultural applications. The aim of this study was to compare potential changes in the toxicity of CP after irradiation. To this end, photolysis of CP was conducted under simulated sunlight, and neurotoxicity assessment was carried out at CP of 20 and 50 μg L-1 and its corresponding irradiated mixture solutions which contain a mixture of identified intermediates using the nematode, Caenorhabditis elegans as a model organism. Photodegradation of 20 μg L-1 CP for 1 h produced no obvious reduction of physiological damage, and more serious effects on animal movement were detected after exposure of the animals to a solution of 50 μg L-1 for 1 h irradiation compared with unirradiated solution. GABAergic and cholinergic neurons were selectively vulnerable to CP exposure, and maximal neuropathological alterations were observed after 1 h irradiation of the CP solutions in coherence with the behavioral impairment. The generation of photoproducts was considered to be responsible for the enhanced disturbance on those biological processes. This work provided useful information on the toxicological assessments of chemicals that were produced during the environmental transformation of pesticides.

Pharmaceuticals are a group of ubiquitous emerging pollutants, many of which have been shown to undergo efficient photolysis in the environment. Photochemically produced reactive intermediates (PPRIs) sensitized by the pharmaceuticals in sunlit natural waters may induce photodegradation of coexisting compounds. In this study, the roles of coexisting contaminants on the phototransformation of pharmaceuticals were unveiled with the fibrate drugs gemfibrozil (GMF), fenofibrate (FNF), and fenofibric acid (FNFA) as model compounds. GMF undergoes initial concentration dependent photodegradation due to the involvement of singlet oxygen (1O2) initiated self-sensitized photolysis, and undergoes pH dependent photodegradation due to dissociation and hydroxyl radical (OH) generation. The decarboxylated intermediates of GMF and coexisting FNFA significantly accelerated the photodegradation of GMF. The promotional effects of the decarboxylated intermediates are attributed to generation of PPRIs, e.g. 1O2, superoxide (O2-), that subsequently react with GMF. Besides, FNFA can also promote the photodegradation of GMF through the electron transfer reaction from ground state GMF to excited state FNFA, leading to the formation of decarboxylated intermediates. The formed intermediates can subsequently also facilitate GMF photodegradation. The results presented here provided valuable novel insights into the effects of coexisting contaminants on the photodegradation of pharmaceuticals in polluted waters.

The use of ultraviolet light in photoreactors for wastewater treatment has become popular as an alternative of known chemical oxidative substances. UV LED light represents cheaper, robust, and versatile alternative to traditional UV lamps. In this study, it was designed and evaluated a photoreactor with an approach of chemical fluid dynamics (CFD) and experimental validation. The evaluation consisted of (1) CFD velocity profile analysis, (2) characterization of the average light distribution with potassium ferrioxalate actinometry, (3) degradation of a typical recalcitrant metallic cyanocomplex Fe(CN)63-, and (4) scavenger effect analysis in the photodegradation using potassium persulfate. Actinometrical essay concluded that the system was able to receive 1.93 μE/s. The reactor operated under turbulent regime and best result for Fe(CN)63- degradation was obtained at 4 h of operation, using 5-W UV-A LEDs, with pH ~ 7 and 10 mM de S2O82-. Baffled photoreactor demonstrated to be useful for this type of illumination and wastewater treatment.