Photolysis Process Research Articles

Glycosylated AIE‐active Red Light‐triggered Photocage with Precisely Tumor Targeting Capability for Synergistic Type I Photodynamic Therapy and CPT Chemotherapy

AbstractPhotocaging is an emerging protocol for precisely manipulating spatial and temporal behaviors over biological activity. However, the red/near‐infrared light‐triggered photolysis process of current photocage is largely singlet oxygen (1O2)‐dependent and lack of compatibility with other reactive oxygen species (ROS)‐activated techniques, which has proven to be the major bottleneck in achieving efficient and precise treatment. Herein, we reported a lactosylated photocage BT‐LRC by covalently incorporating camptothecin (CPT) into hybrid BODIPY‐TPE fluorophore via the superoxide anion radical (O2−⋅)‐cleavable thioketal bond for type I photodynamic therapy (PDT) and anticancer drug release. Amphiphilic BT‐LRC could be self‐assembled into aggregation‐induced emission (AIE)‐active nanoparticles (BT‐LRCs) owing to the regulation of carbohydrate‐carbohydrate interactions (CCIs) among neighboring lactose units in the nanoaggregates. BT‐LRCs could simultaneously generate abundant O2−⋅ through the aggregation modulated by lactose interactions, and DNA‐damaging agent CPT was subsequently and effectively released. Notably, the type I PDT and CPT chemotherapy collaboratively amplified the therapeutic efficacy in HepG2 cells and tumor‐bearing mice. Furthermore, the inherent AIE property of BT‐LRCs endowed the photocaged prodrug with superior bioimaging capability, which provided a powerful tool for real‐time tracking and finely tuning the PDT and photoactivated drug release behavior in tumor therapy.

Accelerated Indirect Photodegradation of Organic Pollutants at the Soil-Water Interface.

Indirect photolysis driven by photochemically produced reactive intermediates (PPRIs) is pivotal for the transformations and fates of pollutants in nature. While well-studied in bulk water, indirect photolysis processes at environmental interfaces remain largely unexplored. This study reveals a significant acceleration of indirect photodegradation of organic pollutants at the soil-water interface of wetlands. Organic pollutants experienced ubiquitously enhanced indirect photodegradation at the soil-water interfaces, with rates 1.41 ± 0.01 to 4.27 ± 0.03-fold higher than those in bulk water. This enhancement was observed across various natural and artificial wetlands, including coastal wetlands and rice paddies. In situ mapping indicated that soil-water interfaces act as hotspots, concentrating both organic pollutants and PPRIs by 9.30- and 4.27-folds, respectively. This synchronized colocation is the primary cause of the accelerated pollutant photolysis. Additionally, the contribution of each PPRI species to pollutant photolysis and a coupled transformation pathway at the soil-water interface significantly differed from those in bulk water. For instance, the contribution of singlet oxygen to metoxuron photolysis increased from 10.1% in bulk water to 44.4% at the soil-water interface. Our study highlights the rapid indirect photolysis of organic pollutants at the soil-water interfaces, offering new insights into the natural purification processes in wetlands as "Earth's kidneys."

Kinetic modelling of ozonation and photolytic ozonation of metronidazole removal from water

This work addresses the ozonation, photolysis, and photolytic ozonation of metronidazole (MTZ), a widely used antibiotic frequently detected in urban wastewater. A UVA source emitting radiation between 300 and 400 nm was utilized. The presence of scavengers such as t-butanol and sodium azide confirmed the role of hydroxyl radicals in both ozonation and photolysis processes. Conversely, singlet oxygen did not influence the photolytic processes. The average quantum yields of MTZ and ozone were determined to be 1.2 × 10−3 and 0.72 mol/Einstein, respectively, for the 300–400 nm wavelength range. In direct MTZ photolysis, a stoichiometric ratio of 0.34 mol of hydroxyl radicals formed per mol of photolyzed MTZ was observed. However, the effects of hydroxyl radicals on the MTZ photolytic rate were only significant after 45 min of reaction time. Using rate constant data from literature and quantum yields calculated in this study, a kinetic model for both MTZ ozonation and photolytic ozonation was proposed, enabling the prediction of MTZ conversion and degradation rates. This model includes three intermediate compounds that also consume ozone and hydroxyl radicals. The results show that experimental and calculated concentrations of MTZ are within an error margin of less than 14 % in all cases.

Toxicology of Dimethoate and its Degradation by Biological, Chemical, and Photolytic Process

Toxicology of Dimethoate and its Degradation by Biological, Chemical, and Photolytic Process

Aging of microplastics and its photo-catalytic degradation of coexisting tetracycline

Photodegradation processes play a crucial role in the transforming of antibiotics in aqueous environments, while photochemical aging influences the properties of microplastics (MPs). In this study, the efficacy of ultraviolet (UV) irradiation in eliminating tetracycline (TC) was examined. Especially, TC degradation was mediated by polyethylene microplastics (PE-MPs) was subjected to aging through UV exposure and a combination of UV and thermal-activated persulfate treatments. The effects of MPs concentration, salinity, and pH on TC degradation were investigated. The characteristics of aging PE-MPs and the corresponding active free radicals were analyzed to understand the mechanism of TC degradation. The results showed that the existence of PE-MPs significantly influenced TC degradation under photosensitized conditions. However, as the concentration of PE-MPs increased, the degradation rate initially increased and subsequently declined. TC degradation increased from approximately 35 % to 85 % when pH increased from 3 to 11 mediated by aged PE-MPs. Moreover, the TC degradation ability increased with increasing salinity, and a higher aging degree facilitated the photodegradation of TC, achieving a removal rate of 62 %. At the same time, free radical quenching confirmed that the singlet oxygen (1O2), hydroxyl radical (OH), and superoxide radical (O2·−) produced all involved in the photolysis process of TC mediated by PE-MPs, especially 1O2. The analysis of the degradation products of TC and prediction of its toxicity revealed that the ecological risk associated with the degradation solution diminished compared with that of the TC mother solution.

Synergistic effect of adsorption and photolysis on methylene blue removal by magnetic biochar derived from lignocellulosic biomass

In this study, magnetic biochar was synthesized by doping Fe3O4 onto the biochar surface followed by analysis of its properties. The efficiency of methylene blue (MB) removal through the combined processes of adsorption and photolysis was assessed. The presence of Fe3O4 on the biochar surface was confirmed using Raman spectroscopy and X-ray photoelectron spectroscopy. The magnetic biochar, after MB adsorption, showed a magnetism of 39.50 emu/g leading to a 97.07 % recovery rate. The specific surface area of biochar was higher (380.68 m2/g) than that of magnetic biochar (234.46 m2/g), and the maximum adsorption capacity of MB was higher in the biochar (0.03 mg/g) than that in magnetic biochar (0.02 mg/g) under the optimal conditions for MB adsorption. The MB adsorption experiments using biochar or magnetic biochar were optimally conducted under 10–20 mg/L MB concentration, 1 g biochar dosage, pH 12, 200 rpm rotation speed, 25 °C temperature, and 30 min duration. Under dark conditions, biochar had a higher MB removal rate, at 83.91 %, compared to magnetic biochar, at 78.30 %. Under visible light (λ > 425 nm), magnetic biochar effectively removed MB within 10 min, highlighting the synergistic effect of adsorption and photolysis. MB is physically and chemically adsorbed by the monolayer on the surface of EB and EMB according to adsorption behavior.

Stability Indicating Force Degradation Study of Nintedanib in Bulk and Pharmaceutical Dosage Form

Assay of the nintedanib drug substance can be determined using a newly designed and verified reverse-phase high-performance liquid chromatography (RP-HPLC) method, even when degradation products from forced degradation experiments are present. By using gradient elution, the mobile phase was a mixture of 70% acetonitrile and 30% water by volume. Acid, base, peroxide, thermal, and photolytic degradation were among the stress conditions that the product was subjected to. During the thermal and photolytic breakdown processes, no extra contaminants were detected. Using validation criteria such as specificity, linearity, limit of quantitation (LoQ), accuracy, precision, robustness, and ruggedness, the developed technique was validated in accordance with International Council for Harmonization (ICH) recommendations. At a concentration of 12.4 ng/mL, the LoQ value was attained. The results showed good linearity (r2 > 1.00) across doses ranging from 2 to 10 μg/mL. Verification of recovery was done by adding concentrated solutions of 5, 10, and 15 μg/mL. So, newly developed RP-HPLC technology can separate Nintedanib from its main degradation products, and it can also estimate the drug substance’s concentration.

A stability indicating method development and validation of a rapid and sensitive RP-HPLC method for Nintedanib and its application in quantification of nanostructured lipid carriers.

Nintedanib (NTB) is a multiple tyrosine kinase inhibitor, been investigated for many disease conditions like idiopathic pulmonary fibrosis (IPF), systemic sclerosis interstitial lung disease (SSc-ILD) and non-small cell lung cancer (NSCLC). NTB is available as oral capsule formulation, but its ability to detect degradants formed through oxidative, photolytic and hydrolytic processes makes it difficult to quantify. In the current work, a novel reversed-phase high-performance liquid chromatography (RP-HPLC) method was developed and validated. The developed method is simple, precise, reproducible, stable and accurate. The inherent stability of NTB was evaluated using the proposed analytical method approach and force degradation studies were carried out. NTB was separated chromatographically on the Shimadzu C 18 column as stationary phase (250 ×4.6 mm, 5 µm) using an isocratic elution method with 0.1% v/v triethyl amine (TEA) in HPLC grade water and acetonitrile (ACN) in the ratio 35:65% v/v. The mobile phase was pumped at a constant flow rate of 1.0 ml/min, and the eluent was detected at 390 nm wavelength. NTB was eluted at 6.77±0.00 min of retention time (t R) with a correlation coefficient of 0.999, the developed method was linear in the concentration range of 0.5 µg/ml to 4.5 µg/ml. The recovery rate was found to be in the range of 99.391±0.468% for 1.5 µg/ml concentration. Six replicate standards were determined to have an % RSD of 0.04. The formulation excipients didn't interfere with the determination of NTB, demonstrating the specificity of the developed method. The proposed approach of the analytical method developed can be used to quantify the amount of NTB present in bulk drugs and pharmaceutical formulations.

Integration of coagulation–flocculation and photolysis processes for treating reverse osmosis concentrate (ROC) of pharmaceutical wastewater management

ABSTRACT This study provides novel insights into optimizing the integral treatment process, contributing to ROC treatment strategies. A comprehensive treatment approach for reverse osmosis concentrate (ROC) from pharmaceutical wastewater was investigated using an integral system consisting of a coagulation-flocculation and photolysis process. Ferric chloride (FC) and poly-aluminum chloride (PAC) are examined as coagulants within the range (0.1–1) gL−1, focusing on turbidity, chemical oxygen demand (COD), and total organic carbon (TOC) removal. The findings show that the optimal FeCl3 dosage is 0.4 gL−1, achieving significant turbidity reduction to 1 NTU. PAC at 0.2 gL−1 is optimal, reducing turbidity to 1 NTU and exhibiting non-linear behavior in COD and TOC removal, introducing them as a starting point to the post-treatment. Photolysis of treated samples at pH 7 yields COD reductions of 60.5% for PAC and 79.5% for FC, with respective TOC reductions of 79.5% and 75.23% over 360 min. At (pH 3.5) showed a significant reduction in the COD and TOC of treated ROC. The FC coagulant could decrease the COD from 261 to 5 mgL−1 (98% COD removal) and the TOC from 143.9 to 5 mgL−1 (74.8% TOC removal). The FAC coagulant could decrease the COD from 675 to 39 mgL−1 (93% COD removal) and the TOC from 186 to 13.1 mgL−1 (69.7% TOC removal). The conventional oxidant (H2O2) at optimal dosages enhanced COD and TOC removal at pH 7, with treated PAC and FeCl3 achieving 81.8% and 97.2% COD reduction and 89% and 98% TOC reduction at 360 minutes. These results were supported by the cost analysis in which this system was cost effective manner. This system can offer a solution for the efficient treatment of other types of industrial wastewater and open the door to new applications for water reuse on a broad scale, contributing to global water sustainability.

Full spectroscopic model and trihybrid experimental-perturbative-variational line list for NH

ABSTRACT Imidogen (NH) is a reactive molecule whose presence in astrochemical environments is of interest due to its role in the formation of nitrogen-containing molecules and as a potential probe of nitrogen abundance. Spectroscopic NH monitoring is useful for Earth-based combustion and photolysis processes of ammonia and other nitrogen-containing species. NH is also relevant to ultracold molecular physics and plasma studies. To enable these diverse applications, high-quality molecular spectroscopic data are required. Here, a new line list with significant advantages over existing data is presented. Most notably, this line list models isotopologue spectroscopy and forbidden transitions (important for NH visible absorption), alongside some overall improvements to accuracy and completeness. This approach takes advantage of existing experimental data (from a previous MARVEL compilation) and perturbative line lists together with new MRCI ab initio electronic data. These are used to produce a novel variational spectroscopic model and trihybrid line list for the main 14N1H isotopologue, as well as isotopologue-extrapolated hybrid line lists for the 14N2H, 15N1H, and 15N2H isotopologues. The new 14N1H ExoMol-style trihybrid line list, kNigHt, comprises 4076 energy levels (1078 experimental) and 327 014 transitions up to 47 500 cm−1 (211 nm) between five low-lying electronic states (X 3Σ−, a 1Δ, b 1Σ+, A 3Π, and c 1Π). For most anticipated applications aside from far-infrared studies, this line list will be of sufficient quality; any improvements should focus on the b 1Σ+ energies, and the a 1Δ – A 3Π and b 1Σ+ – A 3Π spin–orbit couplings.

Epoxiconazole degradation in water samples: a comparative study of Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis processes.

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.

Rational design of CdS-enwrapped polypyrrole nanoparticles for wastewater treatment: removal of hazardous pollutants in aqueous solutions.

The modern world requires a chemical industry that can run at low production costs while producing high-quality products with minimal environmental impact. The development of environmentally friendly, cost-effective, and efficient wastewater treatment materials remains a majorproblem for the sustainable approach. We prepared nanoscale cadmium sulfide (CdS)-enwrapped polypyrrole (PPy) polymer composites for degradation of organic pollutants. The prepared CdS@PPy nanocomposites were characterized by powder X-ray diffraction, scanning electron microscope (SEM), field emission scanning electron microscope (FESEM), Fourier transform infrared spectroscopy (FTIR), and ultraviolet-visible(UV) absorption spectroscopy, indicating proper intercalation between CdS and PPy. Consequently, the catalytic efficiency of the synthesized hybrid nanocomposites was analyzed through the degradation of methylene blue (MB) and rhodamine B (Rh B) under visible light irradiation. The measured degradation efficiency of the dye solutions under the photolysis process is about 18% and 23% for MB and Rh B dye, respectively. Furthermore, the recycle test result concludes that the CdS@PPy composite exhibits 91% and 89% of MB and Rh B dye degradation efficiency even at the 4th cycle, respectively. The positive synergistic impact of CdS and PPymay be the result of effective photocatalytic degradation of MB and RhB.

Ecotoxicological strategies employing biochemical markers and organisms to monitor the efficacy of malathion photolysis treatment

The objective of this study was to assess the photolysis-mediated degradation of malathion in standard and commercial formulations, and to determine the toxicity of these degraded formulations. Degradation tests were carried out with 500 μg L−1 of malathion and repeated three times. The initial and residual toxicity was assessed by using Lactuca sativa seeds for phytotoxicity, Stegomyia aegypti larvae for acute toxicity, and Stegomyia aegypti mosquitoes (cultivated from the larval stage until emergence as mosquitoes) to evaluate the biochemical markers of sublethal concentrations. For the standard formulations the photolytic process efficiently reduced the initial concentration of malathion to levels below the regulatory limits however, the formation of byproducts was revealed by chromatography, which allowed for a more complete proposal of photolytic-mediated malathion degradation route. The degraded formulations inhibited the growth of L. sativa seeds, while only the untreated formulations showed larvicidal activity and mortality. Both formulations slightly inhibited acetylcholinesterase activity in S. aegypti mosquitoes, while the standard formulation decreased and the commercial formulation increased glutathione S-transferase activity. However, there were no significant differences for superoxide dismutase, esterase-α, esterase-β and lipid peroxidation. These findings indicate that in the absence of the target compound, the presence of byproducts can alter the enzymatic activity. In general, photolysis effectively degrade malathion lower than the legislation values; however, longer treatment times must be evaluated for the commercial formulation.

Investigation of the photolysis process of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) and polystyrene (PS) microplastics: Plastics aging effect, transformation products and toxicity assessment

Microplastics (MPs) and persistent pollutants (POPs) are new pollutants that are extensively studied worldwide. To fill the gaps that the degradation processes and mechanisms of polycyclic aromatic hydrocarbons (PAHs) on the surface of most MPs are still unclear, the photochemical transformation of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) MPs and polystyrene (PS) MPs in water were investigated and compared. The photolysis of BaA on the surface of PS in water proceeded easier than that on PVC within the 48 h irradiation period, with the pseudo-first-order rate constant of 0.0489 min−1 and 0.0181 min−1, respectively, which can be ascribed to the smaller particle size and more OH production of PS MPs. Due to the light competition between the chromophore and BaA as well as the light-shielding effect, aged MPs showed an inhibitory effect on the degradation of BaA compared with pristine MPs. For BaA/PVC MPs system, the degradation of BaA in real water was not significantly affected by coexisting ions and humic acid (HA) (p < 0.05), while slight inhibitory effect on the degradation of BaA appeared for PS MPs in different water matrices (UP: 86.97 %, YR: 84.47 %, PR: 81.42 % and HR: 83.21 %). According to the electron paramagnetic resonance (EPR) test, quenching experiment and probe experiment, the relative contribution of direct photolysis (PVC: 82.02 %; PS: 69.54 %) and indirect photolysis (PVC: 17.98 %; PS: 30.46 %) was confirmed. A total of 14 products were identified, and the product types were not affected by plastics aging. The results of the toxicity assessment indicated that although some intermediate products remained toxic to aquatic organisms, the toxicity of most products was lower than that of BaA. This study provides new insights into the environmental fate of PAHs and the role of MPs in the photolysis process of contaminants in surface water.

Evaluation and Modeling of Polylactide Photodegradation under Ultraviolet Irradiation: Bio-Based Polyester Photolysis Mechanism.

In our study, we investigated the accelerated aging process of PLA under 253.7 nm UV-C irradiation with the use of the GPC, NMR, FTIR, and DSC methods and formal kinetic analysis. The results of GPC and DSC indicated a significant degree of destructive changes in the PLA macromolecules, while spectroscopic methods NMR and FTIR showed maintenance of the PLA main structural elements even after a long time of UV exposure. In addition to that, the GPC method displayed the formation of a high molecular weight fraction starting from 24 h of irradiation, and an increase in its content after 144 h of irradiation. It has been shown for the first time that a distinctive feature of prolonged UV exposure is the occurrence of intra- and intermolecular radical recombination reactions, leading to the formation of a high molecular weight fraction of PLA decomposition products. This causes the observed slowdown of the photolysis process. It was concluded that photolysis of PLA is a complex physicochemical process, the mechanism of which depends on morphological changes in the solid phase of the polymer under UV radiation.

Turning harmful Mn2+ to treasure: In-situ formed ε-MnO2 for removing heavy metals from acid mine drainage

Acid mine drainage (AMD) contains high concentrations of heavy metals, causing serious environmental pollution. Current neutralization techniques fail to recover and utilize valuable heavy metals, and generate large quantities of hazardous sludge. Manganese (Mn) is generally present at high levels in AMD. Therefore, this paper proposed a technology to recover Mn from AMD, by adding KMnO4 to converting Mn into ε-MnO2. Ultra-Violet C (UVC) was used to photolyze the residual KMnO4. The study then evaluated the processes and mechanisms involved in the technology. The photolysis of KMnO4 in strong acidic conditions was determined, and new mechanisms were proposed. MnO2 produced by the photolysis process was formed through the reaction between Mn(III) and KMnO4. In the absence of KMnO4, Mn(III) underwent further photolysis and was reduced to Mn2+. The maximum adsorption capacities of in-situ formed ε-MnO2 for Pb2+, Cd2+, and Fe3+ were 449.80, 122.05, and 779.88 mg/g, respectively. Higher Mn-OH levels and MnO2 regeneration were crucial in improving adsorption performance. Proton exchange and inner-circle complexation were the main pathways for Pb2+ and Cd2+ adsorption by in-situ formed ε-MnO2. A phase transformation occurred when a substantial amount of Fe3+ was adsorbed, leading to the gradual transformation to MnFe binary oxides. When applying in-situ formed ε-MnO2 technology for actual AMD treatment, 98.62 % of Mn in AMD was recovered within 24 h in the presence of ε-MnO2 for possible further reuse in industries, with a final recovery of 0.76 kg/m3. Further, this technique removed other heavy metals and reduced the sludge volume by 20.99 % when used as a pre-treatment step for neutralization. These results demonstrated the broad potential of this treatment technology.

Wavelength dependency and photosensitizer effects in UV-LED photodegradation of iohexol

Iodinated X-ray contrast media (ICM) are ubiquitously present in water sources and challenging to eliminate using conventional processes, posing a significant risk to aquatic ecosystems. Ultraviolet light-emitting diodes (UV-LED) emerge as a promising technology for transforming micropollutants in water, boasting advantages such as diverse wavelengths, elimination of chemical additives, and no induction of microorganisms’ resistance to disinfectants. The research reveals that iohexol (IOX) degradation escalates as UV wavelength decreases, attributed to enhanced photon utilization efficiency. Pseudo-first-order rate constants (kobs) were determined as 3.70, 2.60, 1.31 and 0.65 cm2 J−1 at UV-LED wavelengths of 255, 265, 275 and 285 nm, respectively. The optical properties of dissolved organic matter (DOM) and anions undeniably influence the UV-LED photolysis process through photon competition and the generation of reactive substances. The influence of Cl− on IOX degradation was insignificant at UV-LED 255, but it promoted IOX degradation at 265, 275 and 285 nm. IOX degradation was accelerated by ClO2−, NO3−and HA due to the formation of various reactive species. In the presence of NO3−, the kobs of IOX followed the order: 265 > 255 > 275 > 285 nm. Photosensitizers altered the spectral dependence of IOX, and the intermediate photoactivity products were detected using electron spin resonance. The transformation pathways of IOX were determined through density functional theory calculations and experiments. Disinfection by-products (DBPs) yields of IOX during UV-LED irradiation decreased as the wavelength increased: 255 > 265 > 275 > 285 nm. The cytotoxicity index value decreased as the UV-LED wavelength increased from 255 to 285 nm. These findings are crucial for selecting the most efficient wavelength for UV-LED degradation of ICM and will benefit future water purification design.

Photolysis of dinotefuran in aqueous solution: Kinetics, influencing factors and photodegradation mechanism

The environmental behaviour of neonicotinoid insecticides (NNIs) is of momentous concern due to their frequent detection in aquatic environment and their biotoxicity for non-target organisms. Phototransformation is one of the most significant transformation processes, which is directly related to NNIs exposure and environmental risks. In this study, the photodegradation of dinotefuran (DIN, 1-Methyl-2-nitro-3-(tetrahydro-3-furanylmethyl)-guanidine), one of the most promising NNIs, was conducted under irritated light in the presence of Cl−, DOM along with the effect of pH and initial concentration. The findings demonstrated that in ultra-pure (UP) water, the photolysis rate constants (k) of DIN rose with increasing initial concentration. Whereas, in tap water, at varied pH levels, and in the presence of Cl-, the outcomes were reversed. At the same time, lower concentration of DOM promoted DIN photolysis processes due to the production of reactive oxygen species, while higher concentrations of DOM inhibited the photolysis by the predominance of light shielding effects. The singlet oxygen (1O2) was produced in the photolysis processes of DIN with Cl− and DOM, which was confirmed by electron spin resonance (EPR) analysis. Four main photolysis products and three intermediates were identified by UPLC-Q-Exactive Orbitrap MS analysis. The possible photodegradation pathways of DIN were proposed including the oxidation by 1O2, reduction and hydrolysis after the removal of nitro group from parent compounds. This study expanding our understanding of transformation behavior and fate of NNIs in the aquatic environment, which is essential for estimating their environmental risks.

Organic aerosol formation from 222 nm germicidal light: ozone-initiated vs. non-ozone pathways.

Germicidal ultraviolet lamps outputting 222 nm light (GUV222) have the potential to reduce the airborne spread of disease through effective inactivation of pathogens, while remaining safe for direct human exposure. However, recent studies have identified these lamps as a source of ozone and other secondary pollutants such as secondary organic aerosol (SOA), and the health effects of these pollutants must be balanced against the benefits of pathogen inactivation. While ozone reactions are likely to account for much of this secondary indoor air pollution, 222 nm light may initiate additional non-ozone chemical processes, including the formation of other oxidants and direct photolytic reactions, which are not as well understood. This work examines the impacts of GUV222 on SOA formation and composition by comparing limonene oxidation under GUV222 and O3-only control conditions in a laboratory chamber. Differences between these experiments enable us to distinguish patterns in aerosol formation driven by ozone chemistry from those driven by other photolytic processes. These experiments also examine the influence of the addition of NO2 and nitrous acid (HONO), and investigate SOA formation in sampled outdoor air. SOA composition and yield vary only slightly with respect to GUV222vs. ozone-only conditions; NO2 and HONO photolysis do not appreciably affect the observed chemistry. In contrast, we observe consistent new particle formation under high-fluence 222 nm light (45 μW cm-2) that differs substantially from ozone-only experiments. This observed new particle formation represents an additional reason to keep GUV222 fluence rates to the lowest effective levels.

Photoinduced cytotoxic activity of a rare ruthenium nitrosyl phenanthroline complex showing NO generation in human cells.

A new nitro-nitrosyl complex [RuNO(Phen)(NO2)2OH] (1) was synthesized and characterized by X-ray diffraction, where Phen = 1,10-phenanthroline. The complex was crystallized in two different modifications without (1) and with a solvent molecule of DMF (1a). The photolysis process together with the determination of the quantum yield of NO release was investigated in acetonitrile solution using a special flow-through system for the simultaneous registration of infrared (IR) and optical absorption (UV-vis) spectra under irradiation with 450 nm light. The quantum yield of photoinduced NO release was 4.0 ± 0.2%. DFT calculations showed that the main contribution to the absorption band at 450 nm is made by the HOMO/HOMO-1 → LUMO transitions, which are represented by the transfer of electron density from the -OH and -NO2 ligands to the orbitals located on the Ru-NO bond. The dark and photoinduced cytotoxicity of the complex was studied against the human breast adenocarcinoma (MCF-7) and lung carcinoma (A549) cell lines and human non-tumor lung fibroblasts (MRC5). The complex shows a low cytotoxicity on MCF-7 cells (ICdark50 = 90.6 ± 6.2 μM and ICirr.50 = 95.3 ± 11.4 μM) and a moderate dark cytotoxicity on A549 and MRC5 cells (ICdark50 = 33.4 ± 2.6 μM and ICdark50 = 62.6 ± 3.1 μM, respectively), which slightly increases after irradiation (ICirr.50 = 21.2 ± 3.3 μM and ICirr.50 = 47.2 ± 2.3 μM, respectively).