Intrareticular Exciton Effects Regulate Photocatalytic Activity in Donor-Acceptor Olefin-Linked Covalent Organic Frameworks.

Olefin-linked covalent organic frameworks (OL-COFs) show great promise for visible-light-driven photocatalysis. Manipulating atomic-level donor-acceptor interactions in OL-COFs is key to understanding their exciton effects in this system. Here, three OL-COFs are presented with orthorhombic lattice structures, synthesized via Knoevenagel polycondensation reaction of terephthalaldehyde and tetratopic monomers featuring phenyl, benzo[c][1,2,5]oxadiazole, and benzo[c][1,2,5]thiadiazole moieties. These OL-COFs feature tunable donor-acceptor interactions, making them ideal for studying exciton effects in olefin-linked systems. Comprehensive analyses, including temperature-dependent photoluminescence spectra, ultrafast spectroscopy, and theoretical calculations, reveal that stronger donor-acceptor interactions lead to reduced exciton binding energy (Eb), accelerated exciton dissociation, and longer-lived photogenerated charges, thereby enhancing photocatalytic performance. Notably, The TMO-BDA COF, with the lowest Eb, demonstrates superior photocatalytic activity in one-pot sequential organic transformation and excellent catalytic performance in gram-scale reactions, highlighting its potential for practical applications. This work provides valuable insights into regulating the exciton effect at the molecular level in OL-COFs, offering pathways to enhance photocatalytic efficiency.

Photo-oxidation of Micro- and Nanoplastics: Physical, Chemical, and Biological Effects in Environments.

Micro- and nanoplastics (MNPs) are attracting increasing attention due to their persistence and potential ecological risks. This review critically summarizes the effects of photo-oxidation on the physical, chemical, and biological behaviors of MNPs in aquatic and terrestrial environments. The core of this paper explores how photo-oxidation-induced surface property changes in MNPs affect their adsorption toward contaminants, the stability and mobility of MNPs in water and porous media, as well as the transport of pollutants such as organic pollutants (OPs) and heavy metals (HMs). It then reviews the photochemical processes of MNPs with coexisting constituents, highlighting critical factors affecting the photo-oxidation of MNPs, and the contribution of MNPs to the phototransformation of other contaminants. The distinct biological effects and mechanism of aged MNPs are pointed out, in terms of the toxicity to aquatic organisms, biofilm formation, planktonic microbial growth, and soil and sediment microbial community and function. Furthermore, the research gaps and perspectives are put forward, regarding the underlying interaction mechanisms of MNPs with coexisting natural constituents and pollutants under photo-oxidation conditions, the combined effects of photo-oxidation and natural constituents on the fate of MNPs, and the microbiological effect of photoaged MNPs, especially the biotransformation of pollutants.

Environmental Markers of Plastics and Microplastics.

The slow reaction rates to chemical and photochemical degradation are well-known properties of plastics. However, large plastic surfaces exposed to environmental conditions release particles and compounds that affect ecosystems and human health. The aim of this work was to identify compounds associated with the degradation of polyethylene (PE), polystyrene (PS), and polyvinyl chloride (PVC) microplastics (markers) on silica and sand and evaluate their use to screen microplastics on natural sand. Products were identified by using targeted and untargeted LC-HRMS analysis. All polymers underwent chemical oxidation on silica. PE released dicarboxylic acids (HO2C-(CH2)n-CO2H (n = 4-30), while PS released cis/trans-chalcone, trans-dypnone, 3-phenylpropiophenone, and dibenzoylmethane. PVC released dicarboxylic acids and aromatic compounds. Upon irradiation, PE was stable while PS released the same compounds as under chemical oxidation but at lower yields. Under the above condition, PVC generated HO2C-[CH2-CHCl]n-CH2-CO2H and HO2C-[CH2-CHCl]n-CO2H (n = 2-19) dicarboxylic acids. The same products were detected on sand but at a lower concentration than on silica due to better retention within the pores. Detection of markers of PE and PS on natural sand allowed us to screen microplastics by following a targeted analysis. Markers of PVC were not detected before or after thermal/photo-oxidation due to the low release of compounds and limitations associated with surface exposure/penetration of radiation.

Additional HONO and OH Generation from Photoexcited Phenyl Organic Nitrates in the Photoreaction of Aromatics and NOx.

HONO acts as a major OH source, playing a vital role in secondary pollutant formation to deteriorate regional air quality. Strong unknown sources of daytime HONO have been widely reported, which significantly limit our understanding of radical cycling and atmospheric oxidation capacity. Here, we identify a potential daytime HONO and OH source originating from photoexcited phenyl organic nitrates formed during the photoreaction of aromatics and NOx. Significant HONO (1.56-4.52 ppb) and OH production is observed during the photoreaction of different kinds of aromatics with NOx (18.1-242.3 ppb). We propose an additional mechanism involving photoexcited phenyl organic nitrates (RONO2) reacting with water vapor to account for the higher levels of measured HONO and OH than the model prediction. The proposed HONO formation mechanism was evidenced directly by photolysis experiments using typical RONO2 under UV irradiation conditions, during which HONO formation was enhanced by relative humidity. The 0-D box model incorporated in this mechanism accurately reproduced the evolution of HONO and aromatic. The proposed mechanism contributes 5.9-36.6% of HONO formation as the NOx concentration increased in the photoreaction of aromatics and NOx. Our study implies that photoexcited phenyl organic nitrates are an important source of atmospheric HONO and OH that contributes significantly to atmospheric oxidation capacity.

Forecasting Photo-Dissolution for Future Oil Spills at Sea: Effects of Oil Properties and Composition.

Photo-dissolution, the photochemical production of water-soluble species from oil, can transfer oil-derived dissolved organic carbon (DOC) from floating surface slicks to the underlying seawater. Photo-dissolution was likely a quantitatively relevant fate process for the Macondo crude oil spilled during the 2010 Deepwater Horizon spill, but the importance of photo-dissolution for other oils is poorly constrained. This study evaluated the photo-dissolution reactivities (apparent quantum yields) and modeled rates for oils with diverse physical properties and chemical compositions, including an ultra low sulfur fuel oil (ULSFO). Photo-dissolution from UV (310 nm) light was strongly positively correlated with the fraction of small, gas-oil range compounds (

Degradation of Argan oils used in edible and cosmetic applications after exposure to UV light.

This study investigates for the first time the effects of UV light exposure on the chemical composition of artisanal and cold-pressed culinary and cosmetic argan oils, as well as their quality and biological activities. We ascertained the oxidative stability of both types of oil through measurements of the peroxide value, acidity, UV-spectrophotometric indexes (E232 and E270), and iodine value. Over the course of eight hours at room temperature, the impact of UV light on the breakdown of tocopherols, polyphenols, chlorophylls, and carotenoid pigments was examined. The findings showed that during photo-oxidation, acidity, peroxide value, and particular extinction coefficients (E232 and E270) gradually increased. On the other hand, a decline in the content of polyphenols, tocopherols, carotenoid, and chlorophyll was noted. Interestingly, iodine levels failed to improve. Although after an eight-hour degradation, the physicochemical profile of argan oils remained exceptional. DPPH• (1,1-Diphenyl-2-picrylhydrazyl) antioxidant activity tests showed a gradual decrease in radical inhibition over time, which was attributed to lower levels of tocopherol and polyphenol. However, roasted oils showed antifungal action against Botrytis cinerea fungus, while Argan vegetable oils showed no activity against Escherichia coli, Microbacterium resistens, Staphylococcus saprophyticus, and Raoultella ornithinolytica, according to antimicrobial assays.

Catalytic Protein Inhibitors.

Many of the highest priority targets in a wide range of disease states are difficult-to-drug proteins. The development of reversible small molecule inhibitors for the active sites of these proteins with sufficient affinity and residence time on-target is an enormous challenge. This has engendered interest in strategies to increase the potency of a given protein inhibitor by routes other than further improvement in gross affinity. Amongst these, the development of catalytic protein inhibitors has garnered the most attention and investment, particularly with respect to protein degraders, which catalyze the destruction of the target protein. This article discusses the genesis of the burgeoning field of catalytic inhibitors, the current state of the art, and exciting future directions.

Towards Copper(I) Clusters for Photo-Induced Oxidation of Biological Thiols in Living Cells.

The cell redox balance can be disrupted by the oxidation of biological peptides, eventually leading to cell death, which provides opportunities to develop cytotoxic drugs. With the aim of developing compounds capable of specifically inducing fatal redox reactions upon light irradiation, we have developed a library of copper compounds. This metal is abundant and considered essential for human health, making it particularly attractive for the development of new anticancer drugs. Copper(I) clusters with thiol ligands (including 5 novel ones) have been synthesized and characterized. Structures were elucidated by X-ray diffraction and showed that the compounds are oligomeric clusters. The clusters display high photooxidation capacity towards cysteine - an essential amino acid - upon light irradiation in the visible range (450 nm), while remaining completely inactive in the dark. This photoredox activity against a biological thiol is very encouraging for the development of anticancer photoredox drugs.The in vitro assay on murine colorectal cancer cells (CT26) did not show any toxicity - whether in the dark or when exposed to 450 nm light, likely because of the poor solubility of the complexes in biological medium.

Self-Immolative Polythiophene for Sunlight Inactivation of Harmful Cyanobacteria.

Harmful cyanobacterial blooms and the released microcystins (MCs) caused serious environmental and public health concerns to drinking water safety. Photo-oxidation is an appealing treatment option and alternative to conventional flocculation and microbial antagonists, but the performances of current photosensitizers (either inorganic or organic) are unsatisfactory. Here, a polythiophene photosensitizer (PT10) with both high yield of reactive oxygen species (ROS) production (mainly 1O2, ΦΔ = 0.51, > 8 h continuous generation) and moderate photostability was used as a powerful algaecide to inhibit Microcystis aeruginosa. Due to the positive charge of PT10, the algal cells were quickly flocculated, followed by efficient inactivation in 4 h under white light irradiation (96.7%, 10 mW/cm2). Meanwhile, PT10 was self-immolated in about 6 h. Upon biosafety evaluation with adult zebrafish, the low toxicity of PT10 and the degradation products of PT10 and algae (early logarithmic growth stage) were confirmed. In addition, microcystin-LR (MC-LR), a toxic microcystin that will be released during the destruction of the algal cells, was also degraded. Therefore, PT10-based photoinactivation of M. aeruginosa featured both high performance and low secondary pollution. In real-world aquatic systems, PT10 was confirmed to be capable of sunlight-assisted inactivation of M. aeruginosa and prevent algal blooms, thus making it appealing for environmental remediation.

Hot and Cold: Photochemical Weathering Mediates Oil Properties and Fate Differently Depending on Seawater Temperature.

Photochemical weathering transforms petroleum oil and changes its bulk physical properties, as well as its partitioning into seawater. This transformation process is likely to occur in a cold water marine oil spill, but little is known about the behavior of photochemically weathered oil in cold water. We quantified the effect of photochemical weathering on oil properties and partitioning across temperatures. Compared to weathering in the dark, photochemical weathering increases oil viscosity and water-soluble content, decreases oil-seawater interfacial tension, and slightly increases density. Many of these photochemical changes are much larger than changes caused by evaporative weathering. Further, the viscosity and water-soluble content of photochemically weathered oil are more temperature-sensitive compared to evaporatively weathered oil, which changes the importance of key fate processes in warm versus cold environments. Compared to at 30 °C, photochemically weathered oil at 5 °C would have a 16× higher viscosity and a 7× lower water-soluble content, resulting in lower entrainment and dissolution. Collectively, the physical properties and thus fate of photochemically weathered oil in a cold water spill may be substantially different from those in a warm water spill. These differences could affect the choice of oil spill response options in cold, high-light environments.

A Temporal Graph Model to Predict Chemical Transformations in Complex Dissolved Organic Matter.

Dissolved organic matter (DOM) is a complex mixture of thousands of natural molecules that undergo constant transformation in the environment, such as sunlight induced photochemical reactions. Despite molecular level resolution from ultrahigh resolution mass spectrometry (UHRMS), trends of mass peak intensities are currently the only way to follow photochemically induced molecular changes in DOM. Many real-world relationships and temporal processes can be intuitively modeled using graph data structures (networks). Graphs enhance the potential and value of AI applications by adding context and interconnections allowing the uncovering of hidden or unknown relationships in data sets. We use a temporal graph model and link prediction to identify transformations of DOM molecules in a photo-oxidation experiment. Our link prediction algorithm simultaneously considers educt removal and product formation for molecules linked by predefined transformation units (oxidation, decarboxylation, etc.). The transformations are further weighted by the extent of intensity change and clustered on the graph structure to identify groups of similar reactivity. The temporal graph is capable of identifying relevant molecules subject to similar reactions and enabling to study their time course. Our approach overcomes previous data evaluation limitations for mechanistic studies of DOM and leverages the potential of temporal graphs to study DOM reactivity by UHRMS.

Macular Pigment Carotenoids and Bisretinoid A2E.

Lutein (L), zeaxanthin (Z), and meso-zeaxanthin (MZ) are the three macular pigments (MP) carotenoids that uniquely accumulate in the macula lutea region of the human retina. L and Z are obtained by humans through dietary intake. The third MP, MZ, is rarely present in diet, and its abundance in the human fovea is due to the metabolic conversion of dietary L by the retinal pigment epithelium's RPE65 enzyme. The major functions of MP in ocular health are to filter high-intensity, phototoxic blue light and to act as effective antioxidants for scavenging free radicals. The pyridinium bisretinoid, N-retinylidene-N-retinylethanolamine (A2E), contributes to drusen formation in dry age-related macular degeneration (AMD) and to the autofluorescent flecks in autosomal recessive Stargardt disease (STGD1). Retinal carotenoids attenuate A2E formation and can directly and indirectly alleviate A2E-mediated oxidative damage. In this chapter, we review these more recently recognized interconnections between MP carotenoids and A2E bisretinoids.

External Catalyst- and Additive-Free Photo-Oxidation of Aromatic Alcohols to Carboxylic Acids or Ketones Using Air/O2.

We present an environment-friendly and highly efficient method for the oxidation of aromatic alcohols to carboxylic acids or ketones in air via light irradiation under external catalyst-, additive-, and base-free conditions. The photoreaction system exhibits a wide substrate scope and the potential for large-scale applications. Most of the desired products are easily obtained via recrystallization and separation from low-boiling reaction medium acetone in good yields, and the products can be subsequent directly transformed without further purification.

Photo-Driven Iron-Induced Non-Oxidative Coupling of Methane to Ethane.

Photo-driven CH4 conversion to multi-carbon products and H2 is attractive but challenging, and the development of efficient catalytic systems is critical. Herein, we construct a solar-energy-driven redox cycle for combining CH4 conversion and H2 production using iron ions. A photo-driven iron-induced reaction system was developed, which is efficient at selective coupling of CH4 as well as conversion of benzene and cyclohexane under mild conditions. For CH4 conversion, 94 % C2 selectivity and a C2 H6 formation rate of 8.4 µmol h-1 is achieved. Mechanistic studies reveal that CH4 coupling is induced by hydroxyl radical, which is generated by photo-driven intermolecular charge migration of an Fe3+ complex. The delicate coordination structure of the [Fe(H2 O)5 OH]2+ complex ensures selective C-H bond activation and C-C coupling of CH4 . The produced Fe2+ can be used to reduce the potential for electrolytic H2 production, and then turns back into Fe3+ , forming an energy-saving and sustainable recyclable system.

Mitochondria-targeted cyclometalated iridium (III) complex for H2S-responsive intracellular redox regulation as potent photo-oxidation anticancer agent.

Owing to the safety and low toxicity, photodynamic therapy (PDT) for cancer treatment has received extensive attention. However, the excess H2S in cancer cells reduces the PDT efficiency, because H2S indirectly depletes the reactive oxygen species (ROS). To improve anticancer efficiency, a mitochondria-targeted iridium(III) complex Ir-MMB has been developed as H2S consumer and photo-oxidation anticancer agent. On the one hand, complex Ir-MMB can consume H2S with sensitive phosphorescence turn-on, which has been successfully applied to exogenous and endogenous H2S response imaging in living cells. On the other hand, Ir-MMB can enhance its anticancer activity and cause photo-oxidation damage via catalyzing the oxidation of reduced form of nicotinamide-adenine dinucleotide (NADH) to NAD+ and producing H2O2 under light, and ultimately results in cell apoptosis through mitochondrial depolarization and ROS production.

Photo-Oxidizing Ruthenium(II) Complexes with Enhanced Visible-Light Absorption and G-quadruplex DNA Binding Abilities.

Photosensitizers that gather high photo-oxidizing power and strong visible-light absorption are of great interest in the development of new photo-chemotherapeutics. Indeed, such compounds constitute attractive candidates for the design of type I photosensitizers that are not dependent on the presence of oxygen. In this paper, we report on the synthesis and studies of new ruthenium(II) complexes that display strong visible-light absorption and can oxidize guanine residues under visible-light irradiation, as evidenced by nanosecond transient absorption spectroscopy. The reported compounds also tightly bind to G-quadruplex DNA structures from the human telomeric sequence (TTAGGG repeat). The kinetic and thermodynamic parameters of the interaction of these Ru(II) complexes with G-quadruplex and duplex DNA were studied thanks to luminescence titrations and bio-layer interferometry measurements, which revealed higher affinities towards the non-canonical G-quadruplex architecture. Docking experiments and non-covalent ionic analysis allowed us to gain information on the mode and the strength of the interaction of the compounds towards G-quadruplex and duplex DNA. The different studies emphasize the substantial influence of the position and the number of non-chelating nitrogen atoms on the interaction with both types of DNA secondary structures.

Photochemical Csp2-H bond thiocyanation and selenocyanation of activated arenes, batch and continuous-flow approaches.

Herein, we report an eco-friendly photochemical oxidative Csp2-H thiocyanation and selenocyanation of activated arenes. The reaction proceeds under Violet LED irradiation in the presence of K2S2O8, which quickly oxidizes KSCN and KSeCN, finally producing arylthio/selenocyanates. Using this benign, atom-economic protocol, the desired chalcogenide products were obtained regioselectively, with isolated yields that range from very good to excellent. Although, mechanistic study indicates that it is difficult to distinguish between a radical to a SEAr reaction mechanism between the photo-induced formed •SCN, for the former, or NCSSCN, for the latter, to the aromatic heterocycles. The inhibition experiment together with the observed reactivity and regioselectivity, would be in agreement with the latter. The synthetic methodology designed could be successfully adapted to continuous-flow systems in a segmented-flow regime, employing the organic phase as the product reservoir. Using this setup, the advantage of the latter can be demonstrated by reducing the reaction time and improving the product yields. Similarly, the scaling up of the reaction to gram scale resulted in favorable outcomes by the flow setup, which installs the photo-flow chemistry as a powerful tool to be included into routine reaction procedures, which have great relevance for the pharmaceutical industry.

Photoaging of Baby Bottle-Derived Polyethersulfone and Polyphenylsulfone Microplastics and the Resulting Bisphenol S Release.

This study evaluated the release of bisphenol S (BPS) from polyethersulfone (PES) and polyphenylsulfone microplastics (MPs) derived from baby bottles under UV irradiation. Released BPS fluctuates over time because it undergoes photolysis under UV254 irradiation. Under UV365 irradiation, the highest released concentration at 50 °C was 1.7 and 3.2 times that at 35 and 25 °C, respectively, as the activation energy of the photochemical reactions responsible for MP decay was reduced at high temperatures. Low concentrations of humic acid (HA, ≤10 mg·L-1) promote BPS release because HA acts as a photosensitizer. A high concentration of HA (10∼50 mg·L-1) decreases the BPS release because HA shields MPs from light and scavenges reactive radicals that are produced via photochemical reactions. For example, under UV irradiation, hydroxyl radicals (•OH) attack results in the breakage of ether bonds and the formation of phenyl radicals (Ph•) and phenoxy radicals (Ph-O•).The•OH addition and hydrogen extractions further produce BPS from the decayed MPs. A leaching kinetics model was developed and calibrated by the experimental data. The calibrated model predicts the equilibrium level of BPS release from MPs that varies with the surface coverage density of BPS and leaching rate constants. This study provides groundwork that deepens our understanding of environmental aging and the chemical release of MPs.

Comparative photo-oxidative degradation of etodolac, febuxostat and imatinib mesylate by UV-C/H2O2 and UV-C/S2O82- processes: Modeling, treatment optimization and biodegradability enhancement.

The pharmaceutical contamination in aquatic environment has arisen increasing concern due to its potentially chronic toxicity. In recent years, HO° and SO4°- based advanced oxidation processes (AOPs) have been widely applied in water and wastewater treatments due to their highly efficiency on contaminant removal. Here, the response surface modeling (RSM) was used to investigate the degradation of three typical pharmaceuticals (i.e., etodolac (ETD), febuxostat (FBU) and imatinib mesylate (IMT)) by UV/H2O2 and UV/S2O82- processes. Based on the multiple regression analysis on full factorial design matrix and calculated reaction rate constants, the RSM was built. The experimental rate constants under optimal conditions were quite close to those obtained from the model, implying the good fit of the RSM. In addition, the RSM results indicated that UV/S2O82- process was less sensitive to pH in comparison to the UV/H2O2 process on target contaminant removal. Finally, it showed that UV/S2O82- process was superior to the UV/H2O2 process to on the enhancement of target contaminant biodegradability.

Novel Antioxidant Peptides from Crassostrea Hongkongensis Improve Photo-Oxidation in UV-Induced HaCaT Cells.

Enzymatic hydrolysates from Oysters (OAH) display multiple biological activities. Previously, a 3~5 KDa oyster ultrafiltration component (OUP) showed a high property of preventing skin oxidation. Subsequently, we identified specific peptides with such activity. OUP was fractionated stepwise by Sephadex-G25 and RP-HPLC, and active fractions were screened using UV-irradiated HaCaT cells. The most active fractions (OP5-3) were analyzed by LC-MS/MS and a total of 17 peptides were identified. Results from mass spectrometry showed that OP5-3 consisted of peptides with a molecular weight range of 841.51-1786.92 Da. Six of these peptides were synthesized for validating the activity of resisting skin oxidation in the same cell model. All six peptides showed varying degrees of antioxidant activity, while pretreatment of HaCaT cells with AIVAEVNEAAK alleviated UV cytotoxicity, inhibited metalloproteinase 1 (MMP-1) expression, and showed the highest activity to resist UV-induced skin photo-oxidation among these peptides. In addition, results from molecular docking analysis of MMP-1 with AIVAEVNEAAK showed that AIVAEVNEAAK suppresses its enzymatic activity by directly interacting with MMP-1 and thus exhibit anti-photoaging activity.