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Plants grown under low magnesium (Mg) soils are highly susceptible to encountering light intensities that exceed the capacity of photosynthesis (A), leading to a depression of photosynthetic efficiency and eventually to photooxidation (i.e., leaf chlorosis). Yet, it remains unclear which processes play a key role in limiting the photosynthetic energy utilization of Mg-deficient leaves, and whether the plasticity of A in acclimation to irradiance could have cross-talk with Mg, hence accelerating or mitigating the photodamage. We investigated the light acclimation responses of rapeseed (Brassica napus) grown under low- and adequate-Mg conditions. Magnesium deficiency considerably decreased rapeseed growth and leaf A, to a greater extent under high than under low light, which is associated with higher level of superoxide anion radical and more severe leaf chlorosis. This difference was mainly attributable to a greater depression in dark reaction under high light, with a higher Rubisco fallover and a more limited mesophyll conductance to CO2 (gm ). Plants grown under high irradiance enhanced the content and activity of Rubisco and gm to optimally utilize more light energy absorbed. However, Mg deficiency could not fulfill the need to activate the higher level of Rubisco and Rubisco activase in leaves of high-light-grown plants, leading to lower Rubisco activation and carboxylation rate. Additionally, Mg-deficient leaves under high light invested more carbon per leaf area to construct a compact leaf structure with smaller intercellular airspaces, lower surface area of chloroplast exposed to intercellular airspaces, and CO2 diffusion conductance through cytosol. These caused a more severe decrease in within-leaf CO2 diffusion rate and substrate availability. Taken together, plant plasticity helps to improve photosynthetic energy utilization under high light but aggravates the photooxidative damage once the Mg nutrition becomes insufficient.
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Anemia Hipocrômica , Brassica napus , Brassica napus/metabolismo , Ribulose-Bifosfato Carboxilase/metabolismo , Magnésio , Dióxido de Carbono , Fotossíntese/fisiologia , Folhas de Planta/metabolismoRESUMO
Oxygen-mediated triplet-triplet annihilation upconversion (TTA-UC) quenching limits the application of such organic upconversion materials. Here, we report that the photooxidation of organic amines is an effective and versatile strategy to suppress oxygen-mediated upconversion quenching in both organic solvents and aqueous solutions. The strategy is based on the dual role of organic amines in photooxidation, i.e., as singlet oxygen scavengers and electron donors. Under photoexcitation, the photosensitizer sensitizes oxygen to produce singlet oxygen for the oxidation of alkylamine, reducing the oxygen concentration. However, photoinduced electron transfer among photosensitizers, organic amines, and oxygen leads to the production of superoxide anions that suppress TTA-UC. To observe oxygen-tolerating TTA-UC, we find that alkyl secondary amines can balance the production of singlet oxygen and superoxide anions. We then utilize polyethyleneimine (PEI) to synthesize amphiphilic polymers to encapsulate TTA-UC pairs for the formation of water-dispersible, ultrasmall, and multicolor-emitting TTA-UC nanoparticles.
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Noninvasive control over the reversible generation of singlet oxygen (1O2) has found the enormous practical implications in the field of biomedical science. However, metal-free pure organic emitters, connected with a photoswitch, capable of generating "on-demand" 1O2 via triplet harvesting remain exceedingly rare; therefore, the utilization of these organic materials for the reversible control of singlet oxygen production remains at its infancy. Herein, an ambient triplet mediated emission in quinoline-dithienylethene (DTE)-core-substituted naphthalene diimide (cNDI) derivative is unveiled via delayed fluorescence. The quinoline-DTE-cNDI triad displayed enhanced photoswitching efficiency via double FRET mechanism. It was found to have direct utilization in controlled photosensitized organic transformations via efficient generation of singlet oxygen (yield ΦΔ ~ 0.73). The designed molecule exhibits a long-lived emission (τ â¼ 1.1 µs) and very small singlet-triplet splitting (ΔSET) of 0.13 eV empowering it to display delayed fluorescence. Comprehensive steady state and time-resolved emission spectroscopy (TRES) analyses along with DFT calculations offer detailed understandings into the excited-state manifolds of organic compound and energy transfer (ET) pathways involved in 1O2 generation.
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Photobiomodulation (PBM) therapy uses light of different wavelengths to treat various retinal degeneration diseases, but the potential damage to the retina caused by long-term light irradiation is still unclear. This study were designed to detect the difference between long- and short-wavelength light (650-nm red light and 450-nm blue light, 2.55 mW/cm2, reference intensity in PBM)-induced injury. In addition, a comparative study was conducted to investigate the differences in retinal light damage induced by different irradiation protocols (short periods of repeated irradiation and a long period of constant irradiation). Furthermore, the protective role of PARP-1 inhibition on the molecular mechanism of blue light-induced injury was confirmed by a gene knockdown technique or a specific inhibitor through in vitro and in vivo experiments. The results showed that the susceptibility to retinal damage caused by irradiation with long- and short-wavelength light is different. Shorter wavelength lights, such as blue light, induce more severe retinal damage, while the retina exhibits better resistance to longer wavelength lights, such as red light. In addition, repeated irradiation for short periods induces less retinal damage than constant exposure over a long period. PARP-1 plays a critical role in the molecular mechanism of blue light-induced damage in photoreceptors and retina, and inhibiting PARP-1 can significantly protect the retina against blue light damage. This study lays an experimental foundation for assessing the safety of phototherapy products and for developing target drugs to protect the retina from light damage.
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Luz , Poli(ADP-Ribose) Polimerase-1 , Retina , Degeneração Retiniana , Animais , Poli(ADP-Ribose) Polimerase-1/metabolismo , Camundongos , Luz/efeitos adversos , Retina/efeitos da radiação , Retina/patologia , Degeneração Retiniana/etiologia , Degeneração Retiniana/metabolismo , Degeneração Retiniana/patologia , Degeneração Retiniana/prevenção & controle , Camundongos Endogâmicos C57BL , Lesões Experimentais por Radiação/patologia , Lesões Experimentais por Radiação/metabolismo , Modelos Animais de Doenças , Western Blotting , Masculino , Terapia com Luz de Baixa Intensidade , Luz AzulRESUMO
Polycyclic aromatic hydrocarbons (PAHs) are the primary organic carbons in soot. In addition to PAHs with even carbon numbers (PAHeven), substantial odd-carbon PAHs (PAHodd) have been widely observed in soot and ambient particles. Analyzing and understanding the photoaging of these compounds are essential for assessing their environmental effects. Here, using laser desorption ionization mass spectrometry (LDI-MS), we reveal the substantially different photoreactivity of PAHodd from PAHeven in the aging process and their MS detection through their distinct behaviors in the presence and absence of elemental carbon (EC) in soot. During direct photooxidation of organic carbon (OC) alone, the PAHeven are oxidized more rapidly than the PAHodd. However, the degradation of PAHodd becomes preponderant over PAHeven in the presence of EC during photoaging of the whole soot. All of these observations are proposed to originate from the more rapid hydrogen abstraction reaction from PAHodd in the EC-photosensitized reaction, owing to its unique structure of a single sp3-hybridized carbon site. Our findings reveal the photoreactivity and reaction mechanism of PAHodd for the first time, providing a comprehensive understanding of the oxidation of PAHs at a molecular level during soot aging and highlight the enhanced effect of EC on PAHodd ionization in LDI-MS analysis.
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Carbono , Hidrocarbonetos Policíclicos Aromáticos , Fuligem , Hidrocarbonetos Policíclicos Aromáticos/química , Carbono/química , Fuligem/química , Processos Fotoquímicos , Oxirredução , FotoquímicaRESUMO
The environmental impact of sunscreen is a growing concern, yet the combined effects of its components on marine animals are poorly understood. In this study, we investigated the combined effects of sunscreen-extracted zinc oxide nanoparticles (nZnO) and microplastics (MPs) on the development of barnacle larvae, focusing on the different roles played by primary microplastics (PMPs) and secondary microplastics (SMPs) generated through the phototransformation of PMPs. Our findings revealed that a lower concentration of nZnO (50 µg/L) enhanced molting and eye development in barnacle larvae, while a higher concentration (500 µg/L) inhibited larval growth. Co-exposure to PMPs had no significant effect on larval development, whereas SMPs mitigated the impact of nZnO by restricting the in vivo transformation to ionic Zn. Accumulated SMPs reduced gut dissolution of nZnO by up to 40%, lowering gut acidity by 85% and buffering the in vivo dissolution of nZnO. We further identified a rough-surfaced Si-5 fragment in SMPs that damaged larval guts, resulting in decreased acidity. Another Si-32 resisted phototransformation and had no discernible effects. Our study presented compelling evidence of the impacts of SMPs on the bioeffect of nZnO, highlighting the complex interactions between sunscreen components and their combined effects on marine organisms.
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Nanopartículas , Thoracica , Poluentes Químicos da Água , Óxido de Zinco , Animais , Microplásticos , Plásticos , Larva , Protetores SolaresRESUMO
There is a growing concern that nanoplastic pollution may pose planetary threats to human and ecosystem health. However, a quantitative and mechanistic understanding of nanoplastic release via nanoscale mechanical degradation of bulk plastics and its interplay with photoweathering remains elusive. We developed a lateral force microscope (LFM)-based nanoscratch method to investigate mechanisms of nanoscale abrasive wear of low-density polyethylene (LDPE) surfaces by a single sand particle (simulated by a 300 nm tip) under environmentally relevant load, sliding motion, and sand size. For virgin LDPE, we found plowing as the dominant wear mechanism (i.e., deformed material pushed around the perimeter of scratch). After UVA-weathering, the wear mechanism of LDPE distinctively shifted to cutting wear (i.e., deformed material detached and pushed to the end of scratch). The shift in the mechanism was quantitatively described by a new parameter, which can be incorporated into calculating the NP release rate. We determined a 10-fold higher wear rate due to UV weathering. We also observed an unexpected resistance to initiate wear for UV-aged LDPE, likely due to nanohardness increase induced by UV. For the first time, we report 0.4-4 × 10-3 µm3/µm sliding distance/µN applied load as an initial approximate nanoplastic release rate for LDPE. Our novel findings reveal nanoplastic release mechanisms in the environment, enabling physics-based prediction of the global environmental inventory of nanoplastics.
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Polietileno , Polietileno/química , Raios Ultravioleta , Propriedades de SuperfícieRESUMO
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.
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Microplásticos , Plásticos , Polietileno/química , Monitoramento Ambiental , Biomarcadores AmbientaisRESUMO
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.
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Poluentes Ambientais , Microbiota , Poluentes Químicos da Água , Microplásticos , Adsorção , Oxirredução , PlásticosRESUMO
Formation of highly oxygenated molecules (HOMs) such as organic peroxides (ROOR, ROOH, and H2O2) is known to degrade food and organic matter. Gas-phase unimolecular autoxidation and bimolecular RO2 + HO2/RO2 reactions are prominently renowned mechanisms associated with the formation of peroxides. However, the reaction pathways and conditions favoring the generation of peroxides in the aqueous phase need to be evaluated. Here, we identified bulk aqueous-phase ROOHs in varying organic precursors, including a laboratory model compound and monoterpene oxidation products. Our results show that formation of ROOHs is suppressed at enhanced oxidant concentrations but exhibits complex trends at elevated precursor concentrations. Furthermore, we observed an exponential increase in the yield of ROOHs when UV light with longer wavelengths was used in the experiment, comparing UVA, UVB, and UVC. Water-soluble organic compounds represent a significant fraction of ambient cloud-water components (up to 500 µM). Thus, the reaction pathways facilitating the formation of HOMs (i.e., ROOHs) during the aqueous-phase oxidation of water-soluble species add to the climate and health burden of atmospheric particulate matter.
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Peróxido de Hidrogênio , Peróxidos , Material Particulado/análise , Oxidantes , Água , AerossóisRESUMO
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.
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Poluentes Ambientais , Ácido Nitroso , Ácido Nitroso/análise , Radical Hidroxila , Oxirredução , Raios Ultravioleta , NitratosRESUMO
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 (
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Numerous application of pyrethroid insecticides has led to their accumulation in the environment, threatening ecological environment and human health. Its fate in the presence of iron-bearing minerals and natural organic matter under light irradiation is still unknown. We found that goethite (Gt) and humic acid (HA) could improve the photodegradation of bifenthrin (BF) in proper concentration under light irradiation. The interaction between Gt and HA may further enhance BF degradation. On one hand, the adsorption of HA on Gt may decrease the photocatalytic activity of HA through decreasing HA content in solution and sequestering the functional groups related with the production of reactive species. On the other hand, HA could improve the photocatalytic activity of Gt through extending light absorption, lowing of bandgap energy, hindering the recombination of photo-generated charges, and promoting the oxidation and reduction reaction on Gt surface. The increased oxygen vacancies on Gt surface along with the reduction of trivalent iron and the nucleophilic attack of hole to surface hydroxyl group contributed to the increasing photocatalytic activity of Gt. Electron paramagnetic resonance and quenching studies demonstrated that both oxidation species, such as hydroxyl radical (â¢OH) and singlet oxygen (1O2), and reducing species, such as hydrogen atoms (Hâ¢) and superoxide anion radical (O2â¢-), contributed to BF degradation in UV-Gt-HA system. Mass spectrometry, ion chromatography, and toxicity assessment indicated that less toxic C23H22ClF3O3 (OH-BF), C9H10ClF3O (TFP), C14H14O2 (OH-MBP), C14H12O2 (MBP acid), C14H12O3 (OH-MBP acid), and chloride ions were the main degradation products. The production of OH-BF, MPB, and TFP acid through oxidation and the production of MPB and TFP via reduction were the two primary pathways of BF degradation.
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Substâncias Húmicas , Compostos de Ferro , Minerais , Oxirredução , Piretrinas , Substâncias Húmicas/análise , Minerais/química , Compostos de Ferro/química , Piretrinas/química , Fotólise , Inseticidas/químicaRESUMO
The literature rarely compiles studies devoted to the removal of pollutants in aqueous media comparing adsorption and photocatalytic degradation, and does not pay enough attention to the analysis of combined adsorption-photocatalytic oxidation processes. In the present manuscript, the removal of malachite green (MG) from aqueous solutions has been investigated in three different sustainable scenarios: i) adsorption on activated carbon (AC) derived from a residue, luffa cylindrica, ii) photocatalytic oxidation under simulated solar light using titanium dioxide (TP) and iii) combined adsorption-photocatalytic oxidation using TP-AC (70/30 wt./wt.) under simulated solar light. The study has revealed that in the three scenarios and studied conditions, the total removal of this endocrine-disrupting dye from the solution takes place in the assayed time, 2 h, in some cases just in a few minutes. MG adsorption in the AC is a very fast and efficient removal method. MG photocatalytic oxidation with TP also occurs efficiently, although the oxidized MG is not totally mineralized. MG removal using the TP-AC composite under simulated solar light occurs only slightly faster to the MG adsorption in the AC, being adsorption the dominating MG removal mechanism for TP-AC. Thus, more than 90% of the removed MG with TP-AC under simulated solar light is adsorbed in this carbon-containing composite. The obtained results highlight the interest in adsorption, being the selection of the most suitable removal method dependent on several factors (i.e., the cost of the AC regeneration, for adsorption, or the toxicity of the intermediate oxidation species, for photooxidation). Paying attention to MG photooxidation with TiO2, comparison of two working photodegradation schemes shows that the direct photodegradation of MG from solution, avoiding any initial dark equilibrium period, is more efficient from a time perspective. The use of scavengers has proved that MG photodegradation occurs via an oxidation mechanism dominated by superoxide anion radicals.
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Oxirredução , Corantes de Rosanilina , Titânio , Poluentes Químicos da Água , Corantes de Rosanilina/química , Titânio/química , Adsorção , Poluentes Químicos da Água/química , Catálise , Carvão Vegetal/química , Purificação da Água/métodos , Fotólise , Processos FotoquímicosRESUMO
The oxidation of benzylic alcohols is an important transformation in modern organic synthesis. A plethora of photoredox protocols have been developed to achieve the aerobic oxidation of alcohols into carbonyls. Recently, several groups described that ultraviolet (UV) or purple light can initiate the aerobic oxidation of benzylic alcohols in the absence of an external catalyst, and depicted different mechanisms involving the photoinduction of â¢O2- as a critical reactive oxygen species (ROS). However, based on comprehensive mechanistic investigations, including control experiments, radical quenching experiments, EPR studies, UV-vis spectroscopy, kinetics studies, and density functional theory calculations (DFT), we elucidate here that HOOâ¢, which is released via the H2O2 elimination of α-hydroxyl peroxyl radicals [ArCR(OH)OOâ¢], serves as the real chain carrier for the autocatalytic photooxidation of benzylic alcohols. The mechanistic ambiguities depicted in the precedent literature are clarified, in terms of the crucial ROS and its evolution, the rate-limiting step, and the primary radical cascade. This work highlights the necessity of stricter mechanistic analyses on UV-driven oxidative reactions that involve aldehydes' (or ketones) generation.
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Photochemical reactions in cell DNA are induced in various organisms by solar UV radiation and may lead to a series of biological responses to DNA damage, including apoptosis, mutagenesis, and carcinogenesis. The chemical nature and the amount of DNA lesions depend on the wavelength of UV radiation. UV type B (UVB, 290-320 nm) causes two main lesions, cyclobutane pyrimidine dimers (CPDs) and, with a lower yield, pyrimidine (6-4) pyrimidone photoproducts (6-4PPs). Their formation is a result of direct UVB photon absorption by DNA bases. UV type A (UVA, 320-400 nm) induces only cyclobutane dimers, which most likely arise via triplet-triplet energy transfer (TTET) from cell chromophores to DNA thymine bases. UVA is much more effective than UVB in inducing sensitized oxidative DNA lesions, such as single-strand breaks and oxidized bases. Of the latter, 8-oxo-dihydroguanine (8-oxodG) is the most frequent, being produced in several oxidation processes. Many recent studies reported novel, more detailed information about the molecular mechanisms of the photochemical reactions that underlie the formation of various DNA lesions. The information is mostly summarized and analyzed in the review. Special attention is paid to the oxidation reactions that are initiated by reactive oxygen species (ROS) and radicals generated by potential endogenous photosensitizers, such as pterins, riboflavin, protoporphyrin IX, NADH, and melanin. The review discusses the role that specific DNA photoproducts play in genotoxic processes induced in living systems by UV radiation of various wavelengths, including human skin carcinogenesis.
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Dano ao DNA , Dímeros de Pirimidina , Raios Ultravioleta , Raios Ultravioleta/efeitos adversos , Humanos , Dano ao DNA/efeitos da radiação , Dímeros de Pirimidina/metabolismo , Dímeros de Pirimidina/genética , Dímeros de Pirimidina/efeitos da radiação , Espécies Reativas de Oxigênio/metabolismo , DNA/efeitos da radiação , DNA/metabolismo , DNA/genética , Animais , Apoptose/efeitos da radiação , Oxirredução/efeitos da radiação , 8-Hidroxi-2'-Desoxiguanosina/metabolismoRESUMO
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.
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Proteínas , Catálise , Domínio Catalítico , ProteóliseRESUMO
The tetratopic linker, 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4 TBAPy) along with rare-earth (RE) ions is used for the synthesis of 9 isostructures of a metal-organic framework (MOF) with shp topology, named RE-CU-10 (RE = Y(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III)). The synthesis of each RE-CU-10 analogue requires different reaction conditions to achieve phase pure products. Single crystal X-ray diffraction indicates the presence of a RE9 -cluster in Y- to Tm-CU-10, while a RE11 -cluster is observed for Yb- and Lu-CU-10. The photooxidation performance of RE-CU-10 analogues is evaluated, observing competition between linker-to-metal energy transfer versus the generation of singlet oxygen. The singlet oxygen produced is used to detoxify a mustard gas simulant 2-chloroethylethyl sulfide, with half-lives ranging from 4.0 to 5.8 min, some of the fastest reported to date using UV-irradiation and < 1 mol% catalyst, in methanol under O2 saturation.
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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 (includingâ 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 (450â 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 inâ vitro assay on murine colorectal cancer cells (CT26) did not show any toxicity - whether in the dark or when exposed to 450â nm light, likely because of the poor solubility of the complexes in biological medium.
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Antineoplásicos , Compostos de Sulfidrila , Humanos , Animais , Camundongos , Compostos de Sulfidrila/química , Cobre/química , Oxirredução , Cisteína/química , Antineoplásicos/farmacologia , Antineoplásicos/químicaRESUMO
Dual-emissive photoconvertible fluorophores (DPCFs) are powerful tools to unambiguously track labeled cells in bioimaging. We recently introduced a new rational mechanism called directed photooxidation-induced conversion (DPIC) enabling efficient DPCFs to be obtained by conjugating a coumarin to aromatic singlet-oxygen reactive moieties (ASORMs). Pyrrole was found to be a suitable ASORM as it provided a high hypsochromic shift along with a fast and efficient conversion. By synthesizing various pyrrole-based styryl coumarin dyes, we showed that the photoconversion properties, including the quantum yield of photoconversion and the chemical yield of conversion can be tuned by chemical modification of the pyrrole. These modifications led to an improved dual emissive converter, SCP-Boc, which displayed a high brightness and an enhanced photoconversion yield of 63 %. SCP-Boc was successfully used to sequentially photoconvert cells by laser scanning confocal microscopy.