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Journal of Hazardous Materials Aug 2024Photochemical transformation is an important attenuation process for the non-steroidal anti-inflammatory drug naproxen (NPX) in both engineered and natural waters....
Photochemical transformation is an important attenuation process for the non-steroidal anti-inflammatory drug naproxen (NPX) in both engineered and natural waters. Herein, we investigated the photolysis of NPX in aqueous solution exposed to both ultraviolet (UV, 254 nm) and natural sunlight irradiation. Results show that N purging significantly promoted NPX photolysis under UV irradiation, suggesting the formation of excited triplet state (NPX*) as a critical transient. This inference was supported by benzophenone photosensitization and transient absorption spectra. Sunlight quantum yield of NPX was only one fourteenth of that under UV irradiation, suggesting the wavelength-dependence of NPX photochemistry. NPX* formed upon irradiation of NPX underwent photodecarboxylation leading to the formation of 2-(1-hydroxyethyl)-6-methoxynaphthalene (2HE6MN), 2-(1-hydroperoxyethyl)-6-methoxynaphthalene (2HPE6MN), and 2-acetyl-6-methoxynaphthalene (2A6MN). Notably, the conjugation and spin-orbit coupling effects of carbonyl make 2A6MN a potent triplet sensitizer, therefore promoting the photodegradation of the parent NPX. In hospital wastewater, the photolysis of NPX was influenced because the photoproduct 2A6MN and wastewater components could competitively absorb photons. Bioluminescence inhibition assay demonstrated that photoproducts of NPX exhibited higher toxicity than the parent compound. Results of this study provide new insights into the photochemical behaviors of NPX during UV treatment and in sunlit surface waters.
Topics: Naproxen; Photolysis; Ultraviolet Rays; Sunlight; Water Pollutants, Chemical; Anti-Inflammatory Agents, Non-Steroidal; Benzophenones; Photosensitizing Agents
PubMed: 38852251
DOI: 10.1016/j.jhazmat.2024.134841 -
Advanced Science (Weinheim,... Jun 2024The wavelength-by-wavelength resolved photoreactivity of two photo-caged carboxylic acids, i. e. 7-(diethylamino)-coumarin- and 3-perylene-modified substrates, is...
The wavelength-by-wavelength resolved photoreactivity of two photo-caged carboxylic acids, i. e. 7-(diethylamino)-coumarin- and 3-perylene-modified substrates, is investigated via photochemical action plots. The observed wavelength-dependent reactivity of the chromophores is contrasted with their absorption profile. The photochemical action plots reveal a remarkable mismatch between the maximum reactivity and the absorbance. Through the action plot data, the study is able to uncover photochemical reactivity maxima at longer and shorter wavelengths, where the molar absorptivity of the chromophores is strongly reduced. Finally, the laser experiments are translated to light emitting diode (LED) irradiation and show efficient visible-light-induced release in a near fully wavelength-orthogonal, sequence-independent fashion (λ = 405 nm, λ = 505 nm) with both chromophores in the same reaction solution. The herein pioneered wavelength orthogonal release systems open an avenue for releasing two different molecular cargos with visible light in a fully orthogonal fashion.
PubMed: 38852174
DOI: 10.1002/advs.202402011 -
Ecotoxicology and Environmental Safety Jul 2024Isoprenoid metabolism and its derivatives took part in photosynthesis, growth regulation, signal transduction, and plant defense to biotic and abiotic stresses. However,...
Isoprenoid metabolism and its derivatives took part in photosynthesis, growth regulation, signal transduction, and plant defense to biotic and abiotic stresses. However, how aluminum (Al) stress affects the isoprenoid metabolism and whether isoprenoid metabolism plays a vital role in the Citrus plants in coping with Al stress remain unclear. In this study, we reported that Al-treatment-induced alternation in the volatilization rate of monoterpenes (α-pinene, β-pinene, limonene, α-terpinene, γ-terpinene and 3-carene) and isoprene were different between Citrus sinensis (Al-tolerant) and C. grandis (Al-sensitive) leaves. The Al-induced decrease of CO assimilation, maximum quantum yield of primary PSII photochemistry (F/F), the lower contents of glucose and starch, and the lowered activities of enzymes involved in the mevalonic acid (MVA) pathway and 2-C-methyl-D-erythritol 4-phosphate (MEP) pathway might account for the different volatilization rate of isoprenoids. Furthermore, the altered transcript levels of genes related to isoprenoid precursors and/or derivatives metabolism, such as geranyl diphosphate (GPP) synthase (GPPS) in GPP biosynthesis, geranylgeranyl diphosphate synthase (GGPPS), chlorophyll synthase (CHS) and GGPP reductase (GGPPR) in chlorophyll biosynthesis, limonene synthase (LS) and α-pinene synthase (APS) in limonene and α-pinene synthesis, respectively, might be responsible for the different contents of corresponding products in C. grandis and C. sinensis. Our data suggested that isoprenoid metabolism was involved in Al tolerance response in Citrus, and the alternation of some branches of isoprenoid metabolism could confer different Al-tolerance to Citrus species.
Topics: Aluminum; Terpenes; Citrus; Limonene; Photosynthesis; Bicyclic Monoterpenes; Plant Leaves; Stress, Physiological; Monoterpenes; Hemiterpenes; Cyclohexenes; Sugar Phosphates; Butadienes; Erythritol; Mevalonic Acid; Cyclohexane Monoterpenes; Citrus sinensis; Chlorophyll; Alkyl and Aryl Transferases; Volatilization
PubMed: 38850709
DOI: 10.1016/j.ecoenv.2024.116545 -
ChemSusChem Jun 2024A convenient and sustainable method for synthesizing sulfonyl-containing compounds through a catalyst-free aqueous-phase hydrosulfonylation of alkenes and alkynes with...
A convenient and sustainable method for synthesizing sulfonyl-containing compounds through a catalyst-free aqueous-phase hydrosulfonylation of alkenes and alkynes with sulfonyl chlorides under visible light irradiation is presented. Unactivated alkenes, electron-deficient alkenes, alkyl and aryl alkynes can be hydrosulfonylated with various sulfonyl chlorides at room temperature with excellent yields and geometric selectivities by using tris(trimethylsilyl)silane as a hydrogen atom donor and silyl radical precursor to activate sulfonyl chlorides. Mechanistic studies revealed that the photolysis of tris(trimethylsilyl)silane in aqueous solution to produce silyl radical is crucial for the success of this reaction.
PubMed: 38850152
DOI: 10.1002/cssc.202400650 -
Environmental Geochemistry and Health Jun 2024In our previous study, the decontamination efficiency of cesium-137 (Cs) by Napier grass (Pennisetum purpureum Schum.) in the field was shown to be variable and often...
In our previous study, the decontamination efficiency of cesium-137 (Cs) by Napier grass (Pennisetum purpureum Schum.) in the field was shown to be variable and often influenced by natural environmental factors. To elucidate the factors influencing this variable Cs-decontamination efficiency, we investigated the influences of soil type and drought stress on Cs accumulation using cesium-133 (Cs) in Napier grass grown in plastic containers. The experiment was performed using two soil types (Soil A and B) and three different soil moisture conditions: well-watered control (CL), slight drought stress (SD), and moderate drought stress (MD). Overall, our results indicate that soil type and drought have a significant impact on plant growth and Cs accumulation in Napier grass. Plant height (PH), tiller number (TN), leaf width (W), and dry matter weight of aboveground parts (DW) and root parts (DW) in Soil B were greater than those in Soil A. Drought stress negatively affected chlorophyll fluorescence parameters (maximal quantum efficiency of photosystem (PS) II photochemistry and potential activity of PS II), PH, TN, W, DW, DW, and total Cs content (TCs), but it had a positive effect on Cs concentration. The Cs concentration in the aboveground parts (Cs) was increased by MD approximately 1.62-fold in Soil A and 1.11-fold in Soil B compared to each CL counterpart. The TCs in the aboveground parts (TCs) decreased due to drought by approximately 19.9%-39.0% in Soil A and 49.9%-62.7% in Soil B; however, there was no significant effect on TCs due to soil type. The results of this study indicate that soil moisture is a key factor in maintaining Napier grass Cs-decontamination efficiency.
Topics: Cesium Radioisotopes; Droughts; Soil Pollutants, Radioactive; Pennisetum; Soil
PubMed: 38849625
DOI: 10.1007/s10653-024-02023-1 -
Unraveling the role of Mn(V)/Mn(III) in the enhanced permanganate oxidation under Vis-LED radiation.The Science of the Total Environment Sep 2024A novel approach of visible light-emitting diode (Vis-LED) radiation was employed to activate permanganate (Mn(VII)) for efficient organic micropollutant (OMP) removal....
A novel approach of visible light-emitting diode (Vis-LED) radiation was employed to activate permanganate (Mn(VII)) for efficient organic micropollutant (OMP) removal. The degradation rates of OMPs by Vis-LED/Mn(VII) were 2-5.29 times higher than those by Mn(VII) except for benzoic acid and atrazine. Increasing wavelengths (445-525 nm) suppressed the degradation of diclofenac (DCF) and 4-chlorophenol (4-CP) owing to the decreased quantum yields of Mn(VII). Comparatively, light intensity and Mn(VII) dosage had a positive effect on the degradation of DCF and 4-CP. Experimental data revealed that Mn(V) dominated the DCF degradation whereas Mn(III) was the active oxidant in the 4-CP degradation. Mn(V) and Mn(III) formed from the photo-decomposition of Mn(VII), meanwhile, Mn(III) also formed from the Mn(V) photo-decomposition. The increase in solution pH inhibited DCF degradation but had a positive impact on 4-CP degradation, mainly due to the changing speciation of DCF and 4-CP. Inorganic anions (Cl and HCO) had little impact on DCF and 4-CP degradation, while humic acid (HA) showed a positive impact because of the π-π interaction between HA and DCF/4-CP. The transformation products of DCF and 4-CP were identified and transformation pathways were proposed. Finally, the Vis-LED/Mn(VII) exhibited great degradation performance in various authentic waters. Overall, this study boosts the development of Mn(VII)-based oxidation processes.
PubMed: 38848904
DOI: 10.1016/j.scitotenv.2024.173655 -
Journal of Chemical Theory and... Jun 2024State-specific complete active space self-consistent field (SS-CASSCF) theory has emerged as a promising route to accurately predict electronically excited energy...
State-specific complete active space self-consistent field (SS-CASSCF) theory has emerged as a promising route to accurately predict electronically excited energy surfaces away from molecular equilibria. However, its accuracy and practicality for chemical systems of photochemical interest have yet to be fully determined. We investigate the performance of the SS-CASSCF theory for the low-lying ground and excited states in the double bond rotation of ethylene. We show that state-specific approximations with a minimal (2e,2o) active space provide comparable accuracy to state-averaged calculations with much larger active spaces, while optimizing the orbitals for each excited state significantly improves the spatial diffusivity of the wave function. However, the incorrect ordering of state-specific solutions causes excited state solutions to coalesce and disappear, creating unphysical discontinuities in the potential energy surface. Our findings highlight the theoretical challenges that must be overcome to realize practical applications of state-specific electronic structure theory for computational photochemistry.
PubMed: 38847452
DOI: 10.1021/acs.jctc.4c00212 -
Scientific Reports Jun 2024New sulfonamide-triazole-glycoside hybrids derivatives were designed, synthesised, and investigated for anticancer efficacy. The target glycosides' cytotoxic activity...
New sulfonamide-triazole-glycoside hybrids derivatives were designed, synthesised, and investigated for anticancer efficacy. The target glycosides' cytotoxic activity was studied with a panel of human cancer cell lines. Sulfonamide-based derivatives, 4, 7 and 9 exhibited promising activity against HepG-2 and MCF-7 (IC = 8.39-16.90 μM against HepG-2 and 19.57-21.15 μM against MCF-7) comparing with doxorubicin (IC = 13.76 ± 0.45, 17.44 ± 0.46 μM against HepG-2 and MCF-7, rescpectively). To detect the probable action mechanism, the inhibitory activity of these targets was studied against VEGFR-2, carbonic anhydrase isoforms hCA IX and hCA XII. Compoumds 7 and 9 gave favorable potency (IC = 1.33, 0.38 μM against VEGFR-2, 66, 40 nM against hCA IX and 7.6, 3.2 nM against hCA XII, respectively), comparing with sorafenib and SLC-0111 (IC = 0.43 μM, 53 and 4.8 nM, respectively). Moreover, the docking simulation was assessed to supply better rationalization and gain insight into the binding affinity between the promising derivatives and their targeted enzymes that was used for further modification in the anticancer field.
Topics: Humans; Carbonic Anhydrase Inhibitors; Sulfonamides; Glycosides; Triazoles; Vascular Endothelial Growth Factor Receptor-2; Antineoplastic Agents; Molecular Docking Simulation; Carbonic Anhydrase IX; Carbonic Anhydrases; MCF-7 Cells; Hep G2 Cells; Cell Line, Tumor; Antigens, Neoplasm; Structure-Activity Relationship
PubMed: 38844493
DOI: 10.1038/s41598-024-62864-9 -
Naunyn-Schmiedeberg's Archives of... Jun 2024Cancer is a major global health challenge, being the second leading cause of morbidity and mortality after cardiovascular disease. The growing economic burden and... (Review)
Review
Cancer is a major global health challenge, being the second leading cause of morbidity and mortality after cardiovascular disease. The growing economic burden and profound psychosocial impact on patients and their families make it urgent to find innovative and effective anticancer solutions. For this reason, interest in using natural compounds to develop new cancer treatments has grown. In this respect, antofine, an alkaloid class found in Apocynaceae, Lauraceae, and Moraceae family plants, exhibits promising biological properties, including anti-inflammatory, anticancer, antiviral, and antifungal activities. Several molecular mechanisms have been identified underlying antofine anti-cancerous effects, including the inhibition of nuclear factor κB (NF-κB) and AKT/mTOR signaling pathways, epigenetic inhibition of protein synthesis, ribosomal targeting, induction of apoptosis, inhibition of DNA synthesis, and cell cycle arrest. This study discusses the molecular structure, sources, photochemistry, and anticancer properties of antofine in relation to its structure-activity relationship and molecular targets. Then, examine in vitro and in vivo studies and analyze the mechanisms of action underpinning antofine efficacy against cancer cells. This review also discusses multidrug resistance in human cancer and the potential of antofine in this context. Safety and toxicity concerns are also addressed as well as current challenges in antofine research, including the need for clinical trials and bioavailability optimization. This review aims to provide comprehensive information for more effective natural compound-based cancer treatments.
PubMed: 38842561
DOI: 10.1007/s00210-024-03180-x -
The Analyst Jun 2024Chiral recognition of enantiomers with identical mirror-symmetric molecular structures is important for the analysis of biomolecules, and it conventionally relies on...
Chiral recognition of enantiomers with identical mirror-symmetric molecular structures is important for the analysis of biomolecules, and it conventionally relies on stereoselective interactions in chiral chemical environments. Here, we develop a magneto-electrochemical method for the enhanced detection of chiral amino acids (AAs), that combines the advantages of the high sensitivity of electrochemiluminescent (ECL) biosensors and chirality-induced effects under a magnetic field. The ECL difference between L- and D-enantiomers can be amplified over 35-fold under a field of 3.5 kG, and the chiral discrimination can be achieved in dilute AA solutions down to the nM level. The field-dependent ECL and chronocoulometry measurements suggest that chiral AAs can lock the spins on their radicals and thus enlarge the ECL change under applied magnetic fields (magneto-ECL, MECL), which explains the field-enhanced chiral discrimination of AA enantiomers. Finally, a detailed protocol is demonstrated for the identification of unknown AA solutions, in which the species, chirality and concentration of AAs can be determined simultaneously from the 2D plots of the ECL and MECL results. This work benefits the development of field-assisted detection methods and represents a promising and universal strategy for the comprehensive analysis of chiral biomolecules.
PubMed: 38842499
DOI: 10.1039/d4an00547c