Photochemical Degradation Research Articles

Research Updates on the Mechanism and Influencing Factors of the Photocatalytic Degradation of Perfluorooctanoic Acid (PFOA) in Water Environments.

Perfluorooctanoic acid is ubiquitous in water bodies and is detrimental to the health of organisms. Effectively removing perfluorooctanoic acid (PFOA), a persistent organic pollutant, has been a hot topic around the world. With traditional physical, chemical, and biological methods, it is difficult to effectively and completely remove PFOA, the costs are high, and it is easy to cause secondary pollution. There are difficulties in applying some technologies. Therefore, more efficient and green degradation technologies have been sought. Photochemical degradation has been shown to be a low-cost, efficient, and sustainable technique for PFOA removal from water. Photocatalytic degradation technology offers great potential and prospects for the efficient degradation of PFOA. Most studies on PFOA have been conducted under ideal laboratory conditions at concentrations that are higher than those detected in real wastewater. This paper summarizes the research status of the photo-oxidative degradation of PFOA, and it summarizes the mechanism and kinetics of PFOA degradation in different systems, as well as the influence of key factors on the photo-oxidative degradation and defluoridation process, such as system pH, photocatalyst concentration, etc. PFOA photodegradation technology's existing problems and future work directions are also presented. This review provides a useful reference for future research on PFOA pollution control technology.

Diffusion-Ordered Spectroscopy for Rapid and Facile Determination of Consumer Plastic Molecular Weight.

Molecular weight (MW) is a key control of plastic polymer properties and their fate in the environment. However, the primary tool used to determine plastic MW, gel permeation chromatography (GPC), has major limitations, such as low precision and accuracy, requirements for dedicated instrumentation, production of high volumes of hazardous waste, and large sample sizes. In this study, we describe, validate, and apply a diffusion-ordered spectroscopy (DOSY) method for polymer MW determinations, with a focus on applications for consumer plastics. Several experimental conditions were systematically optimized and tested to validate the DOSY method, including the selection of pulse sequences, the effect of sample concentration, cross-validation with multiple sets of external standards, and long-term instrumental stability. Validation was performed for a wide range of polymers, solvents, and temperatures, highlighting its potential for broad applicability. A preliminary screening of polystyrene and polyethylene terephthalate consumer products revealed widely varying MWs (up to two-fold) for products made of the same polymer type. A preliminary experiment was also conducted to track the decrease in polystyrene MW via photochemical chain scission reactions, finding a 20% reduction in MW after less than 1 week of irradiation. Collectively, our results demonstrate the potential for DOSY to provide high-throughput, accurate, and precise measures of polymer MW, as well as the evolution of polymer MW during environmental weathering processes, such as photochemical degradation. We conclude with a discussion of (i) the many advantages of DOSY compared to GPC, (ii) future developments to enhance the depth of information obtained from DOSY, and (iii) approaches to broaden the accessibility of this promising analytical method to the research community.

Photochemical degradation of fluorinated graphite stimulated by embedded nitrogen oxides

Layered fluorinated graphite material can become an efficient nanoreactor for photochemical reactions. In this work, we compared the photochemical behavior of partially fluorinated graphite (FG) and FG containing nitrogen oxides in the interlayer space (NOx@FG) under the action of a high-intense polychromatic photon beam from the synchrotron radiation source BESSY II. Analysis of the chemical and electronic states of the samples was performed using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. Density functional theory calculations were used to interpret and analyze the experimental data. It was found that nitrogen oxides promote the photo-induced degradation of the FG matrix, namely, its partial defluorination, formation of vacancies and doping with nitrogen, while the empty FG had a high photoresistance to synchrotron radiation. The results obtained can be used in the development of new approaches to the modification of graphene layers and in the creation of photostable materials for optical elements.

Photochemical degradation mechanisms and ecotoxicity of propranolol in natural water under simulated and natural sunlight irradiation

The widespread use of propranolol (PRO) has led to its detection in all types of natural water bodies, and it is hazardous to both aquatic organisms and humans. In this study, the photochemical transformation of PRO in the natural environment was investigated using both simulated and outdoor light experiments. The photodegradation of PRO was found to be faster in Pearl river water and the dissolved organic matter (DOM) solutions than that in pure water under sunlight irradiation. Quenching experiments show that the excited triplet states DOM (3DOM*) played a major role while ·OH and 1O2 played minor roles in PRO degradation. The secondary reaction rate constants of 3DOM* with PRO were determined to be (4.32 ∼ 6.38) × 108 M−1 s−1. DOM with high steady-state concentrations of the generated reactive species has higher photochemical reactivity for PRO photodegradation. Total of seven products were identified in in pure water, Pearl River water and three DOM solutions. The degradation of PRO can be mainly through hydroxyl addition, dehydration, naphthalene removal and isopropyl removal reactions. The reaction sites predicted by frontier electronic density calculations can further infer degradation pathways. The ecotoxicity of degradation products was found to be decreased relative to PRO through Ecological Structure Activity Relationship (ECOSAR) program.

Photochemical degradation pathways and near-complete defluorination of chlorinated polyfluoroalkyl substances

Chlorinated polyfluoroalkyl substances (Clx–PFAS) are an emerging class of pollutants worldwide. Here we demonstrate near-complete defluorination (that is, cleaving most C–F bonds) of diverse Clx–PFAS structures and the reaction mechanisms. First, we used ultraviolet/sulfite to degrade various carboxylic acids (n = 1, 2, 4 and 8 Cl–CnF2nCOO− and n = 1, 2 and 3 Cl–(CF2CFCl)nCF2COO−) and an ether sulfonic acid surfactant (F-53B, Cl–(CF2)6–O–(CF2)2SO3−). The initial reaction with a hydrated electron cleaved the C–Cl bond. The resulting fluorocarbon radicals (•CF2– on the terminal and –•CF– in the middle) yield C–H or C–SO3−, or form a dimer. In particular, we identified a novel reaction pathway with the unexpected HO• radical to cleave the C–C bond (for –•CF–) and yield –COO−. This pathway is critical for rapid and deep defluorination at 90–96% from carboxylic acids and 76% from F-53B. The following treatment with heat/persulfate at pH >12 achieved ~100% overall defluorination from carboxylic acids and 93% from F-53B without producing toxic ClO3− from Cl−. This study advances the understanding of PFAS transformation in engineering systems. It also suggests a synergy between molecular design and degradation technology towards sustainable management of fluorochemicals. The achievement of almost complete defluorination of chlorinated polyfluoroalkyl substances reveals insight into the degradation pathways of these persistent contaminants.

Multifunctional PVB nanocomposite wood coating by cellulose nanocrystal/ZnO nanofiller: Hydrophobic, water uptake, and UV-resistance properties

There has been a recent trend in wood conservation, involves studying new materials that are more efficient, as well as improving existing materials that have interesting features such as being less toxic, eco-friendly, reversible, and highly compatible with wood. One area of research has focused on the use of a new PVB nanocomposite wood coating with nanocrystalline cellulose/ZnO nanofibers. This coating has been found to provide protection against moisture and UV light.SEM images confirmed the presence of a homogeneous nanocomposite layer that adhered well to the wood surface and penetrated the inner surface. Comparison of wood treated with neat PVB and the new nanocomposites PVB/CNCs/ZnO after UV light aging revealed a significant reduction in ΔE by increasing the amount of ZnO. Additionally, adding content of CNCs nanoparticles in the nanocomposite matrix led to improvements in color changes. However, these changes were not noticeable when compared to the uncoated sample. ATR-FTIR spectrum analysis showed that samples with a high amount of ZnO and CNCs performed better against photochemical degradation. The findings suggest that the addition of nanocrystalline cellulose to ZnO and polymer composites is promising for the protection of wood against the destructive effects of UV light and humidity.

Role of Molecular Singlet Oxygen in Photochemical Degradation of NTO: DFT Study

NTO (5-nitro-1,2,4-triazol-3-one), an energetic material used in military applications, may be released to the environment and dissolved in surface water and groundwater due to its good water solubility. Singlet oxygen is an important reactive oxygen species produced in the aquatic environment under sunlight irradiation. A detailed investigation of the possible mechanism for NTO decomposition in water induced by singlet oxygen as one of the pathways for NTO environmental degradation was performed by a computational study at PCM(Pauling)/M06-2X/6-311++G(d,p) level. Decomposition of NTO was found to be a multistep process that may begin with singlet oxygen attachment to the carbon atom of the C═N double bond. The formed intermediate undergoes cycle opening, and nitrogen gas, nitrous acid, and carbon (IV) oxide elimination. Isocyanic acid, arisen transiently, hydrolyzes into ammonia and carbon (IV) oxide. The obtained results show a significant increase in reactivity of the anionic form of NTO as compared to its neutral form. The calculated activation energies and high exothermicity of the studied processes support the contribution of singlet oxygen to NTO degradation into low-weight inorganic compounds in the environment.

Mercury isotope clocks predict coastal residency and migration timing of hammerhead sharks

Abstract The management of migratory taxa relies on the knowledge of their movements. Among them, ontogenetic habitat shift, from nurseries to adult habitats, is a behavioural trait shared across marine taxa allowing resource partitioning between life stages and reducing predation risk. As this movement is consistent over time, characterizing its timing is critical to implement efficient management plans, notably in coastal areas to mitigate the impact of fisheries on juvenile stocks. In the Mexican Pacific, habitat use of the smooth hammerhead shark (Sphyrna zygaena) is poorly described, while the species is heavily harvested. Given the large uncertainties associated with the timing of out‐migration from coastal nursery grounds to offshore waters prior to reproductive maturity, a more precise assessment of smooth hammerhead shark movements is needed. Photochemical degradation of mercury imparts mass‐independent isotope fractionation (Δ199Hg) which can be used to discriminate between neonate coastal shallow habitats and the offshore deep foraging patterns of late juveniles. Here, we present the application of muscle Δ199Hg as molecular clocks to predict the timing of ontogenetic habitat shifts by smooth hammerhead sharks, based on their isotopic compositions at the initial and arrival habitats and on muscle isotopic turnover rate. We observed decreases in Δ199Hg values with shark body length, reflecting increasing reliance on offshore mesopelagic prey with age. Coastal residency estimates indicated that smooth hammerhead sharks utilize coastal resources for 2 years prior to offshore migration, suggesting a prolonged residency in these ecosystems. Policy implications. This study demonstrates how mercury stable isotopes and isotopic clocks can be implemented as a complementary tool for stock management by predicting the timing of animal migration—a key aspect in the conservation of marine taxa. In the Mexican Pacific, fishing pressure on shark species occurs in coastal habitats depleting juvenile stocks. Consequently, management decision support tools are imperative for effectively maintaining early life stage population levels over time. The finding that smooth hammerhead sharks extensively rely on highly fished habitats for 2 years after parturition supports the relevance of establishing a size limit in coastal fisheries and demonstrates how the current temporal shark fishing closure could lack efficiency for the species.

Validation of UV/persulfate as a PFAS treatment of industrial wastewater and environmental samples

The contamination of natural water and industrial wastewater with per- and polyfluoroalkyl substances (PFAS) occurs globally. Thus, proper technologies are required to reduce PFAS in the environment and mitigate the adverse effects of these pollutants on human health and the environment. This study used a 23 full factorial design to evaluate the importance of operating factors including the level of persulfate (PS), the initial concentration of PFAS, and the time to the photochemical degradation of PFAS via ultraviolet irradiation at 185/254 nm assisted with persulfate (PS/UV method) in spiked solution. The method was then applied to break down PFAS in industrial wastewater, landfill leachate and groundwater samples using the highest factor levels applied in the 23 full factorial design. The results showed that the three investigated factors played an important role in the degradation of PFAS. The highest PFAS degradation was 57 % perfluorobutanoic acid (PFBA), 80 % perfluorooctanoic acid (PFOA) and 60 % perfluorooctane sulfonate (PFOS) using 10 mg L−1 PFAS, 5 g L−1 PS for 4 h. The defluorination also increased in the presence of PS but decreased in the presence of potassium hydrogen phthalate, nitrates, and chlorides. The PS/UV method decreased the concentration of PFAS in wastewater samples by 20–25 % PFOS and 13–15 % perfluorohexane sulfonate (PFHxS). PFAS degradation in wastewater improved with increasing treatment time. Under the PS/UV treatment, the degradation of major PFAS in groundwater was 94 % 6–2 FTS, 75 % PFOA, 62 % PFOS and 61 % PFHxS. The removal of major compounds in landfill leachate reached up to 12 % PFHxA, 32 % PFPeA, 56 % PFOA and 43 % PFOS. Our study indicated matrix effects leading to decreased PFAS degradation in different contaminated waters. The level of PS should also be controlled to an optimal value because higher levels led to a decrease in treatment efficiency.

Photochemical degradation of perfluorooctanoic acid under UV irradiation in the presence of Fe (III)-saturated montmorillonite

Perfluorooctanoic acid (PFOA) has attracted worldwide attention owing to its widespread distribution and potential ecological risks. Developing low-cost, green-chemical and highly efficient treatment approaches is significant for treating PFOA caused environmental issues. Herein, we propose a feasible PFOA degradation strategy under UV irradiation by adding Fe (III)-saturated montmorillonite (Fe-MMT), and the Fe-MMT could be regenerated after reaction. In our system consisting of 1 g L−1 Fe-MMT and 24 μM PFOA, nearly 90 % initial PFOA could be decomposed within 48 h. The enhanced PFOA decomposition could be explained by the ligand-to-metal charge transfer mechanism based on the generated reactive oxygen species (ROSs) and the transformation of iron species in the MMT layers. Moreover, the special PFOA degradation pathway was revealed according to the intermediate identification and the density functional theory calculation. Further experiments demonstrated that even in the presence of co-existing natural organic natter (NOM) and inorganic ions, efficient PFOA removal could still be obtained in UV/Fe-MMT system. This study offers a green-chemical strategy for PFOA removal from contaminated waters.

Nanoplastics Weathering and Polycyclic Aromatic Hydrocarbon Mobilization.

Despite increasing efforts to recycle plastic materials, large quantities of plastics waste continue to accumulate in the oceans. Persistent mechanical and photochemical degradation of plastics in the oceans yields micro- and nanoscale plastic particles, which represent potential vectors for mobilizing hydrophobic carcinogens in an aqueous milieu. Yet, the fate and potential threats associated with plastics remain largely unexplored. Herein, we apply an accelerated weathering protocol to consumer plastics to characterize the effect of photochemical weathering on the size, morphology, and chemical composition of nanoplastics under defined conditions and validate that the photochemical degradation is consistent with plastics harvested from the Pacific Ocean. Machine learning algorithms trained with accelerated weathering data successfully classify weathered plastics from nature. We demonstrate that photodegradation of poly(ethylene terephthalate) (PET)-containing plastics produces enough CO2 to induce a mineralization process that results in the deposition of CaCO3 on nanoplastics. Finally, we determine that despite UV-radiation induced photochemical degradation and mineral deposition, nanoplastics retain their ability to sorb, mobilize, and increase bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in water and under simulated physiological gastric and intestinal conditions.

The grassland carbon cycle: Mechanisms, responses to global changes, and potential contribution to carbon neutrality.

Grassland is one of the largest terrestrial biomes, providing critical ecosystem services such as food production, biodiversity conservation, and climate change mitigation. Global climate change and land-use intensification have been causing grassland degradation and desertification worldwide. As one of the primary medium for ecosystem energy flow and biogeochemical cycling, grassland carbon (C) cycling is the most fundamental process for maintaining ecosystem services. In this review, we first summarize recent advances in our understanding of the mechanisms underpinning spatial and temporal patterns of the grassland C cycle, discuss the importance of grasslands in regulating inter- and intra-annual variations in global C fluxes, and explore the previously unappreciated complexity in abiotic processes controlling the grassland C balance, including soil inorganic C accumulation, photochemical and thermal degradation, and wind erosion. We also discuss how climate and land-use changes could alter the grassland C balance by modifying the water budget, nutrient cycling and additional plant and soil processes. Further, we examine why and how increasing aridity and improper land use may induce significant losses in grassland C stocks. Finally, we identify several priorities for future grassland C research, including improving understanding of abiotic processes in the grassland C cycle, strengthening monitoring of grassland C dynamics by integrating ground inventory, flux monitoring, and modern remote sensing techniques, and selecting appropriate plant species combinations with suitable traits and strong resistance to climate fluctuations, which would help design sustainable grassland restoration strategies in a changing climate.

Visible light-exposed lignin facilitates cellulose solubilization by lytic polysaccharide monooxygenases

Lytic polysaccharide monooxygenases (LPMOs) catalyze oxidative cleavage of crystalline polysaccharides such as cellulose and are crucial for the conversion of plant biomass in Nature and in industrial applications. Sunlight promotes microbial conversion of plant litter; this effect has been attributed to photochemical degradation of lignin, a major redox-active component of secondary plant cell walls that limits enzyme access to the cell wall carbohydrates. Here, we show that exposing lignin to visible light facilitates cellulose solubilization by promoting formation of H2O2 that fuels LPMO catalysis. Light-driven H2O2 formation is accompanied by oxidation of ring-conjugated olefins in the lignin, while LPMO-catalyzed oxidation of phenolic hydroxyls leads to the required priming reduction of the enzyme. The discovery that light-driven abiotic reactions in Nature can fuel H2O2-dependent redox enzymes involved in deconstructing lignocellulose may offer opportunities for bioprocessing and provides an enzymatic explanation for the known effect of visible light on biomass conversion.

Long-term photochemical stability of heteroaromatic dye-functionalised g-C3N4via covalent linkage for efficient photocatalytic hydrogen evolution

In this study, three typical D–π–A type heteroaromatic organic dyes containing carbazole (CBZ), phenothiazine (PTZ), and phenoxazine (POZ) moiety as electron donor cores and linked to g-C3N4 with amide covalent bonds were synthesized. Thereafter, we studied the long-term photochemical stability and degradation mechanism of the associated dye-sensitised g-C3N4 with covalent linkage or weak interaction. The results revealed that most of the dyes degraded and became unstable after absorption on g-C3N4 under light irradiation. Interestingly, after the target dyes were linked to g-C3N4 with amide covalent bonds, the photostability could be effectively promoted and improved to high levels of stability. For POZ-S dye covalent bond-linked sample g-C3N4/POZ-S, ∼90.5% percent of the dyes were reserved, whereas only ∼25.3% remained for the physically absorbed dye sample g-C3N4+POZ-S after 30 min of irradiation aging test. Moreover, the obtained g-C3N4/POZ-S sample exhibited enhanced H2 evolution activity with photocatalytic H2 production rates that were approximately 96- fold of that of pure g-C3N4. Then, we applied various instrumental analysis and DFT calculation to clarify the mechanism involved with dye photostability and degradation pathway. The typical decarboxylation process was confirmed, and such an unfavourable reaction process could be effectively inhibited if the target dye is linked to g-C3N4 with amide covalent bond instead of the weak interaction. Overall, the existed covalent bond is the key factor for enhancing both the photochemical stability and photocatalytic activity of organic dye-sensitised g-C3N4 for hydrogen evolution.

Experimental Study on Kinetics and Mechanism of Ciprofloxacin Degradation in Aqueous Phase Using Ag-TiO2/rGO/Halloysite Photocatalyst

In this study, Ag-TiO2/rGO/halloysite nanotubes were synthesised from natural sources using a simple method. The material was characterised by X-ray diffraction (XRD), Fourier-transform infrared (FTIR), Raman spectroscopy, BET, scanning electron microscopy (SEM) and UV-vis DRS techniques. The as-synthesised material has a sandwich-like shape, with the active phase distributed evenly over the rGO/HNT support. Compared to pure TiO2, the material has a lower band gap energy (~2.7 eV) and a suitable specific surface area (~80 m2/g), making it able to participate effectively in the photochemical degradation of pollutants. The catalyst showed exceptional activity in the degradation of CIP antibiotics in water, achieving a conversion of about 90% after 5 h of irradiation at an initial CIP concentration of 20 ppm. This efficiency was significantly higher than that of pure TiO2 and Ag-TiO2, which could prove the important effect of the support and silver doping. The results of the experiments show that the process follows a pseudo-first-order kinetic model in the case of (1%)Ag wt. and pseudo-second-order in the case of (3%)Ag wt., which could be explained by the aggregation of silver and the increasing role of chemisorption. Tests with radical scavengers showed that the •OH radical had the greatest effect on CIP decomposition, while •O2− had the least. The neutral pH value and the high degree of mineralisation (approx. 80%) confirm the potential of the material for use in wastewater treatment.

Photochemical Fingerprinting Is a Sensitive Probe for the Detection of Synthetic Cannabinoid Receptor Agonists; toward Robust Point-of-Care Detection.

With synthetic cannabinoid receptor agonist (SCRA) use still prevalent across Europe and structurally advanced generations emerging, it is imperative that drug detection methods advance in parallel. SCRAs are a chemically diverse and evolving group, which makes rapid detection challenging. We have previously shown that fluorescence spectral fingerprinting (FSF) has the potential to provide rapid assessment of SCRA presence directly from street material with minimal processing and in saliva. Enhancing the sensitivity and discriminatory ability of this approach has high potential to accelerate the delivery of a point-of-care technology that can be used confidently by a range of stakeholders, from medical to prison staff. We demonstrate that a range of structurally distinct SCRAs are photochemically active and give rise to distinct FSFs after irradiation. To explore this in detail, we have synthesized a model series of compounds which mimic specific structural features of AM-694. Our data show that FSFs are sensitive to chemically conservative changes, with evidence that this relates to shifts in the electronic structure and cross-conjugation. Crucially, we find that the photochemical degradation rate is sensitive to individual structures and gives rise to a specific major product, the mechanism and identification of which we elucidate through density-functional theory (DFT) and time-dependent DFT. We test the potential of our hybrid "photochemical fingerprinting" approach to discriminate SCRAs by demonstrating SCRA detection from a simulated smoking apparatus in saliva. Our study shows the potential of tracking photochemical reactivity via FSFs for enhanced discrimination of SCRAs, with successful integration into a portable device.

Rosmarinic and Glycyrrhetinic Acid-Modified Layered Double Hydroxides as Functional Additives for Poly(Lactic Acid)/Poly(Butylene Succinate) Blends.

Immobilizing natural antioxidant and biologically active molecules in layered double hydroxides (LDHs) is an excellent method to retain and release these substances in a controlled manner, as well as protect them from thermal and photochemical degradation. Herein, we describe the preparation of host-guest systems based on LDHs and rosmarinic and glycyrrhetinic acids, two molecules obtained from the extraction of herbs and licorice root, respectively, with antioxidant, antimicrobial, and anti-inflammatory properties. Intercalation between the lamellae of the mono-deprotonated anions of rosmarinic and glycyrrhetinic acid (RA and GA), alone or in the presence of an alkyl surfactant, allows for readily dispersible systems in biobased polymer matrices such as poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and a 60/40 wt./wt. PLA/PBS blend. The composites based on the PLA/PBS blend showed better interphase compatibility than the neat blend, correlated with increased adhesion at the interface and a decreased dispersed phase size. In addition, we proved that the active species migrate slowly from thin films of the composite materials in a hydroalcoholic solvent, confirming the optimization of the release process. Finally, both host-guest systems and polymeric composites showed antioxidant capacity and, in the case of the PLA composite containing LDH-RA, excellent inhibitory capacity against E. coli and S. aureus.

Visible light-activated photocatalytic activity of TiO2–crystal violet based superhydrophobic paint against VOCs in indoor air

Visible-light-activated photochemical degradation against VOCs in indoor air using TiO2 nanoparticles encapsulated crystal violet.

Hybrid MoS2/polymer nanoarrays for large-scale photon harvesting and enhanced molecular photo-bleaching

Header Two-dimensional (2D) Transition Metal Dichalcogenide semiconductors (TMDs) are a promising platform in view of developing a novel generation of optoelectronics devices and renewable photon to energy conversion technologies. However new ultra-compact photon harvesting schemes are urgently required to mitigate their poor photon absorption properties. In this work we propose a novel flat-optic solution where a few layers MoS2 film is conformally deposited on a large area (cm2) nanogrooved template. The subwavelength reshaping of the TMDs film induces the excitation of photonic Rayleigh Anomalies (RA). The latter promote a strong in-plane electromagnetic confinement and can be easily tuned over a broadband spectrum by tailoring the illumination conditions. As a demonstration of the potential of this large-area surface functionalization we employed the hybrid 2D nanopatterns as a photocatalyst in a prototype photobleaching reaction of Methylene Blue (MB) molecules. We demonstrate a strong enhancement of the photochemical MB degradation, well above a factor 2, by effectively tuning the RA mode in resonance to the molecular absorption band. Therefore, these findings pave the way to flat-optics photon harvesting schemes for boosting photoconversion efficiency in large-scale hybrid 2D-TMD/polymer layers, with a strong impact in applications ranging from waste-water remediation to new-generation photonics and renewable energy storage

Quantitative NMR spectroscopy reveals solvent effects in the photochemical degradation of thymoquinone

Thymoquinone, a monoterpene natural product isolated from Nigella sativa, has demonstrated potent antioxidant, cytotoxic, anticancer, and anti-inflammatory activity, making it a compound of great therapeutic potential and scientific interest. However, as a photochemically labile compound that can dimerize or decompose into other compounds upon irradiation, its clinical administration and synthetic modifications are greatly limited by its instability in the presence of light. Therefore, it is crucial to have a reliable way to quantify decreases in thymoquinone concentration as an indicator of photodegradation to provide insight into the chemical use of the compound. Here, we employed quantitative 1H nuclear magnetic resonance (NMR) spectroscopy as well as computational time-dependent density functional theory (TD-DFT) calculations to identify the effect of solvation on the photochemical degradation of thymoquinone under ultraviolet light (UV). We found that the rate of photochemical degradation of thymoquinone is highly solvent dependent, and that greatest photodegradation occurs in chloroform. The results presented here are informative for future solvent selection related to the isolation and experimental usage of the compound in solution.