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Understanding the formation processes of nitrous acid (HONO) is crucial due to its role as a primary source of hydroxyl radicals (OH) in the urban atmosphere and its involvement in haze events. In this study, we propose a new pathway for HONO formation via the UVA-light-promoted photosensitized conversion of nitrogen dioxide (NO2) in the presence of ammonia (NH3) and polycyclic aromatic hydrocarbons (PAHs, common compounds in urban grime). This new mechanism differs from the traditional mechanism, as it does not require the formation of the NO2 dimer. Instead, the enhanced electronic interaction between the UVA-light excited triplet state of PAHs and NO2-H2O/NO2-NH3-H2O significantly reduces the energy barrier and facilitates the exothermic formation of HONO from monomeric NO2. Furthermore, the performed experiments confirmed our theoretical findings and revealed that the synergistic effect from light-excited PAHs and NH3 boosts the HONO formation with determined HONO fluxes of 3.6 × 1010 molecules cm-2 s-1 at 60% relative humidity (RH) higher than any previously reported HONO fluxes. Intriguingly, light-induced NO2 to HONO conversion yield on authentic urban grime in presence of NH3 is unprecedented 130% at 60% RH due to the role of NH3 acting as a hydrogen carrier, facilitating the transfer of hydrogen from H2O to NO2. These results show that NH3-assisted UVA-light-induced NO2 to HONO conversion on urban surfaces can be a dominant source of HONO in the metropolitan area.
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Comorbid anxiety and depressive symptoms in chronic pain are a common health problem, but the underlying mechanisms remain unclear. Previously, we have demonstrated that sensitization of the CeA neurons via decreased GABAergic inhibition contributes to anxiety-like behaviors in neuropathic pain rats. In this study, by using male Sprague Dawley rats, we reported that the CeA plays a key role in processing both sensory and negative emotional-affective components of neuropathic pain. Bilateral electrolytic lesions of CeA, but not lateral/basolateral nucleus of the amygdala (LA/BLA), abrogated both pain hypersensitivity and aversive and depressive symptoms of neuropathic rats induced by spinal nerve ligation (SNL). Moreover, SNL rats showed structural and functional neuroplasticity manifested as reduced dendritic spines on the CeA neurons and enhanced LTD at the LA/BLA-CeA synapse. Disruption of GluA2-containing AMPAR trafficking and endocytosis from synapses using synthetic peptides, either pep2-EVKI or Tat-GluA2(3Y), restored the enhanced LTD at the LA/BLA-CeA synapse, and alleviated the mechanical allodynia and comorbid aversive and depressive symptoms in neuropathic rats, indicating that the endocytosis of GluA2-containing AMPARs from synapses is probably involved in the LTD at the LA/BLA-CeA synapse and the comorbid aversive and depressive symptoms in neuropathic pain in SNL-operated rats. These data provide a novel mechanism for elucidating comorbid aversive and depressive symptoms in neuropathic pain and highlight that structural and functional neuroplasticity in the amygdala may be important as a promising therapeutic target for comorbid negative emotional-affective disorders in chronic pain.SIGNIFICANCE STATEMENT Several studies have demonstrated the high comorbidity of negative affective disorders in patients with chronic pain. Understanding the affective aspects related to chronic pain may facilitate the development of novel therapies for more effective management. Here, we unravel that the CeA plays a key role in processing both sensory and negative emotional-affective components of neuropathic pain, and LTD at the amygdaloid LA/BLA-CeA synapse mediated by GluA2-containing AMPAR endocytosis underlies the comorbid aversive and depressive symptoms in neuropathic pain. This study provides a novel mechanism for elucidating comorbid aversive and depressive symptoms in neuropathic pain and highlights that structural and functional neuroplasticity in the amygdala may be important as a promising therapeutic target for comorbid negative emotional-affective disorders in chronic pain.
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Ansiedad/fisiopatología , Reacción de Prevención/fisiología , Complejo Nuclear Basolateral/fisiopatología , Núcleo Amigdalino Central/fisiopatología , Depresión/fisiopatología , Hiperalgesia/fisiopatología , Depresión Sináptica a Largo Plazo/fisiología , Neuralgia/fisiopatología , Receptores AMPA/fisiología , Animales , Ansiedad/etiología , Comorbilidad , Condicionamiento Clásico , Depresión/etiología , Emociones , Endocitosis , Potenciales Postsinápticos Excitadores/efectos de los fármacos , Potenciales Postsinápticos Excitadores/fisiología , Conducta Exploratoria , Preferencias Alimentarias , Vectores Genéticos/administración & dosificación , Vectores Genéticos/farmacología , Lentivirus/genética , Ligadura , Depresión Sináptica a Largo Plazo/efectos de los fármacos , Masculino , Neuralgia/psicología , Técnicas de Placa-Clamp , Péptidos/farmacología , Ratas , Ratas Sprague-Dawley , Receptores AMPA/genética , Prueba de Desempeño de Rotación con Aceleración Constante , Método Simple Ciego , Nervios Espinales/lesiones , NataciónRESUMEN
The competitive adsorption behavior, the synergistic catalytic reaction, and deactivation mechanisms under double components of sulfur-containing volatile organic compounds (VOCs) are a bridge to solve their actual pollution problems. However, they are still unknown. Herein, simultaneous catalytic decomposition of methyl mercaptan (CH3SH) and ethyl mercaptan (C2H5SH) is investigated over lanthanum (La)-modified ZSM-5, and kinetic and thermodynamic results confirm a great difference in the adsorption property and catalytic transformation behavior. Meanwhile, the new synergistic reaction and deactivation mechanisms are revealed at the molecular level by combining with in situ diffuse reflectance infrared spectroscopy (in situ DRIFTS) and density functional theory (DFT) calculations. The CH3CH2* and SH* groups are presented in decomposing C2H5SH, while the new species of CH2*, active H* and S*, instead of CH3* and SH*, are proved as the key elementary groups in decomposing CH3SH. The competitive recombining of SH* in C2H5SH with highly active H* in dimethyl sulfide (CH3SCH3), an intermediate in decomposing CH3SH, would aggravate the deposition of carbon and sulfur. La/ZSM-5 exhibits potential environmental application due to the excellent stability of 200 h and water resistance. This work gives an understanding of the adsorption, catalysis, reaction, and deactivation mechanisms for decomposing double components of sulfur-containing VOCs.
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Methoxyphenols represent important pollutants that can participate in the formation of secondary organic aerosols (SOAs) through chemical reactions with atmospheric oxidants. In this study, we determine the influence of ionic strength, pH, and temperature on the heterogeneous reaction of NO2 with an aqueous film consisting of acetosyringone (ACS), as a proxy for methoxyphenols. The uptake coefficient of NO2 (50 ppb) on ACS (1 × 10-5 mol L-1) is γ = (9.3 ± 0.09) × 10-8 at pH 5, and increases by one order of magnitude to γ = (8.6 ± 0.5) × 10-7 at pH 11. The lifetime of ACS due to its reaction with NO2 is largely affected by the presence of nitrate ions and sulfate ions encountered in aqueous aerosols. The analysis performed by membrane inlet single-photon ionization-time-of-flight mass spectrometry (MI-SPI-TOFMS) reveals an increase in the number of product compounds and a change of their chemical composition upon addition of nitrate ions and sulfate ions to the aqueous thin layer consisting of ACS. These outcomes indicate that inorganic ions can play an important role during the heterogeneous oxidation processes in aqueous aerosol particles.
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Photodynamic therapy (PDT) is a treatment procedure that relies on cytotoxic reactive oxygen species (ROS) generated by the light activation of a photosensitizer. The photophysical and biological properties of photosensitizers are vital for the therapeutic outcome of PDT. In this work a 2D rhomboidal metallacycle and a 3D octahedral metallacage were designed and synthesized via the coordination-driven self-assembly of a Ru(II)-based photosensitizer and complementary Pt(II)-based building blocks. The metallacage showed deep-red luminescence, a large 2-photon absorption cross-section, and highly efficient ROS generation. The metallacage was encapsulated into an amphiphilic block copolymer to form nanoparticles to encourage cell uptake and localization. Upon internalization into cells, the nanoparticles selectively accumulate in the lysosomes, a favorable location for PDT. The nanoparticles are almost nontoxic in the dark, and can efficiently destroy tumor cells via the generation of ROS in the lysosomes under 2-photon near-infrared light irradiation. The superb PDT efficacy of the metallacage-containing nanoparticles was further validated by studies on 3D multicellular spheroids (MCS) and in vivo studies on A549 tumor-bearing mice.
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Nanopartículas del Metal , Fotoquimioterapia/métodos , Fármacos Fotosensibilizantes/farmacología , Compuestos de Platino , Compuestos de Rutenio , Células A549 , Animales , Desarrollo de Medicamentos , Humanos , Lisosomas , Ratones , Neoplasias Experimentales/tratamiento farmacológico , Fármacos Fotosensibilizantes/químicaRESUMEN
Photodynamic therapy (PDT), a therapeutic mode involving light triggering, has been recognized as an attractive oncotherapy treatment. However, nonnegligible challenges remain for its further clinical use, including finite tumor suppression, poor tumor targeting, and limited therapeutic depth. The photosensitizer (PS), being the most important element of PDT, plays a decisive role in PDT treatment. This review summarizes recent progress made in the development of PSs for overcoming the above challenges. This progress has included PSs developed to display enhanced tolerance of the tumor microenvironment, improved tumor-specific selectivity, and feasibility of use in deep tissue. Based on their molecular photophysical properties and design directions, the PSs are classified by parent structures, which are discussed in detail from the molecular design to application. Finally, a brief summary of current strategies for designing PSs and future perspectives are also presented. We expect the information provided in this review to spur the further design of PSs and the clinical development of PDT-mediated cancer treatments.
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Neoplasias/tratamiento farmacológico , Fármacos Fotosensibilizantes/química , Animales , Complejos de Coordinación/química , Complejos de Coordinación/uso terapéutico , Colorantes Fluorescentes/química , Humanos , Neoplasias/patología , Fotoquimioterapia , Fármacos Fotosensibilizantes/uso terapéutico , Porfirinas/química , Elementos de Transición/químicaRESUMEN
Cancer-associated pain is debilitating. However, the mechanism underlying cancer-induced spontaneous pain and evoked pain remains unclear. Here, using behavioral tests with immunofluorescent staining, overexpression, and knockdown of TRESK methods, we found an extensive distribution of TRESK potassium channel on both CGRP+ and IB4+ nerve fibers in the hindpaw skin, on CGRP+ nerve fibers in the tibial periosteum which lacks IB4+ fibers innervation, and on CGRP+ and IB4+ dorsal root ganglion (DRG) neurons in rats. Moreover, we found a decreased expression of TRESK in the corresponding nerve fibers within the hindpaw skin, the tibial periosteum and the DRG neurons in bone cancer rats. Overexpression of TRESK in DRG neurons attenuated both cancer-induced spontaneous pain (partly reflect skeletal pain) and evoked pain (reflect cutaneous pain) in tumor-bearing rats, in which the relief of evoked pain is time delayed than spontaneous pain. In contrast, knockdown of TRESK in DRG neurons produced both spontaneous pain and evoked pain in naïve rats. These results suggested that the differential distribution and decreased expression of TRESK in the periosteum and skin, which is attributed to the lack of IB4+ fibers innervation within the periosteum of the tibia, probably contribute to the behavioral divergence of cancer-induced spontaneous pain and evoked pain in bone cancer rats. Thus, the assessment of spontaneous pain and evoked pain should be accomplished simultaneously when evaluating the effect of some novel analgesics in animal models. Also, this study provides solid evidence for the role of peripheral TRESK in both cancer-induced spontaneous pain and evoked cutaneous pain.
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Neoplasias Óseas , Canales de Potasio , Animales , Neoplasias Óseas/complicaciones , Ganglios Espinales , Dolor/complicaciones , Ratas , Ratas Sprague-DawleyRESUMEN
Fatty acids are ubiquitous constituents of grime on urban and indoor surfaces and they represent important surfactants on organic aerosol particles in the atmosphere. Here, we assess the heterogeneous processing of NO2 on films consisting of pure oleic acid (OA) or a mixture of OA and representative salts for urban grime and aerosol particles, namely Na2SO4 and NaNO3. The uptake coefficients of NO2 on OA under light irradiation (300 nm < λ < 400 nm) decreased with increasing relative humidity (RH), from (1.4 ± 0.1) × 10-6 at 0% RH to (7.1 ± 1.6) × 10-7 at 90% RH. The uptake process of NO2 on OA gives HONO as a reaction product, and the highest HONO production was observed upon the heterogeneous reaction of NO2 with OA in the presence of nitrate (NO3-) ions. The formation of gaseous nitroaromatic compounds was also enhanced in the presence of NO3- ions upon light-induced heterogeneous processing of NO2 with OA, as revealed by membrane inlet single-photon ionization time-of-flight mass spectrometry (MI-SPI-TOFMS). These results suggest that inorganic salts can affect the heterogeneous conversion of gaseous NO2 on fatty acids and enhance the formation of HONO and other N-containing organic compounds in the atmosphere.
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Dióxido de Nitrógeno , Ácido Nitroso , Atmósfera , Ácido Oléico , Sales (Química)RESUMEN
As an effective and noninvasive treatment of various diseases, photodynamic therapy (PTD) relies on the combination of light, a photosensitizer, and oxygen to generate cytotoxic reactive oxygen species that can damage malignant tissue. Much attention has been paid to covalent modifications of the photosensitizers to improve their photophysical properties and to optimize the pathway of the photosensitizers interacting with cells within the target tissue. Herein we report the design and synthesis of a supramolecular heterometallic Ru-Pt metallacycle via coordination-driven self-assembly. While inheriting the excellent photostability and two-photon absorption characteristics of the Ru(II) polypyridyl precursor, the metallacycle also exhibits red-shifted luminescence to the near-infrared region, a larger two-photon absorption cross-section, and higher singlet oxygen generation efficiency, making it an excellent candidate as a photosensitizer for PTD. Cellular studies reveal that the metallacycle selectively accumulates in mitochondria and nuclei upon internalization. As a result, singlet oxygen generated by photoexcitation of the metallacycle can efficiently trigger cell death via the simultaneous damage to mitochondrial function and intranuclear DNA. In vivo studies on tumor-bearing mice show that the metallacycle can efficiently inhibit tumor growth under a low light dose with minimal side effects. The supramolecular approach presented in this work provides a paradigm for the development of PDT agents with high efficacy.
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Complejos de Coordinación , Fotoquimioterapia/métodos , Fármacos Fotosensibilizantes , Platino (Metal) , Rutenio , Células A549 , Animales , Supervivencia Celular/efectos de los fármacos , Complejos de Coordinación/química , Complejos de Coordinación/farmacología , Células HeLa , Humanos , Ratones , Mitocondrias/efectos de los fármacos , Mitocondrias/metabolismo , Fotones , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Platino (Metal)/química , Platino (Metal)/farmacología , Rutenio/química , Rutenio/farmacología , Oxígeno Singlete/metabolismo , Oxígeno Singlete/farmacología , Ensayos Antitumor por Modelo de XenoinjertoRESUMEN
Live cell imaging of lysosome positioning and motility is critical to studying lysosome status and function for pharmacological interventions. To create a super stable lysosomal probe for long-term live cell imaging, we have designed and synthesized an aromatic-peptide-conjugated cyclometalated iridium(III) complex that emits light via π-π stacking oriented self-assembly in water at extremely low concentration. Through endocytic trafficking, self-assemblies are transformed from nanoparticles into sturdily packed networks that are stabilized in lysosomal acidic environment. Upon short time/low dose treatment of the iridium complex at passage 0, live cell lysosomal tracking is applicable beyond the 14th passage of cells with high labelling rate and a mild decline in luminescence intensity. The illuminated lysosomes are trackable using super-resolution imaging to study their response to cellular processes.
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Complejos de Coordinación/química , Colorantes Fluorescentes/química , Iridio/química , Lisosomas/metabolismo , Rastreo Celular , Dimerización , Células HeLa , Humanos , Concentración de Iones de Hidrógeno , Conformación Molecular , Nanopartículas/química , Imagen Óptica , Péptidos/química , Espectrometría de FluorescenciaRESUMEN
Nitrous acid (HONO) is an important gaseous pollutant contributing to indoor air pollution because it causes adverse health effects and is the main source of hydroxyl radicals (OH). Here, we present direct measurements of HONO produced through light-induced heterogeneous reactions of NO2 with grime adsorbed on glass window. The uptake coefficients of NO2 [γ(NO2)] on the glass plates from the kitchen increased markedly from (2.3 ± 0.1) × 10-6 at 0% RH to (4.1 ± 0.5) × 10-6 at 90% RH. We report a significant quantity of daytime HONO produced in the kitchen, compared to the living room and bedroom. Kinetic modeling suggests that phase state and bulk diffusivity play important roles in the NO2 uptake; the best fit to the measured uptake coefficients is obtained with fixed diffusion coefficients. Photon scattering may be occurring at the surface of the films, leading to enhanced photon-excitation rates of polycyclic aromatic hydrocarbons. By taking these effects into account, the results from this study indicate that the HONO yields obtained in this study can explain the missing HONO in the photochemical models describing the indoor air chemistry.
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Contaminación del Aire Interior , Dióxido de Nitrógeno , Contaminación del Aire Interior/análisis , Gases , Radical Hidroxilo , Dióxido de Nitrógeno/análisis , Ácido Nitroso/análisisRESUMEN
Polycyclic aromatic hydrocarbons (PAHs) as constituents of urban grime and indoor surfaces can impact the photochemical conversion of nitrogen dioxide (NO2) to nitrous acid (HONO) thereby impacting the oxidation capacity of the atmosphere. In this study we investigate the effect of relative humidity (RH%), light intensity, and NO2 concentrations on uptake coefficients (γ) of NO2 on solid film consisting of fluorene (FL) and a mixture of FL and Na2SO4 as a proxy for urban and indoor grime at ambient pressure and temperature. γ(NO2) on solid FL increased markedly from (5.7 ± 1.7) × 10-7 at 0% RH to (4.6 ± 1.0) × 10-6 at 90% RH. The NO2 to HONO conversion yield, (ΔHONO/ΔNO2)%, increases with RH from 40% at 0% RH up to 80% at 60-90% RH, indicating that the water molecules favor the formation of HONO up to 60% RH. These results suggest that the heterogeneous photochemical reaction of NO2 on FL and FL/Na2SO4 can be an important source of HONO in the urban environment and indoor atmosphere and should be considered in photochemical models.
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Dióxido de Nitrógeno , Ácido Nitroso , Atmósfera , Fluorenos , TemperaturaRESUMEN
Compared to 2PE (two-photon excitation) microscopy, 3PE microscopy has superior spatial resolution, deeper tissue penetration, and less defocused interference. The design of suitable agents with a large Stokes shift, good three-photon absorption (3PA), subcellular targeting, and fluorescence lifetime imaging (FLIM) properties, is challenging. Now, two IrIII complexes (3PAIr1 and 3PAIr2) were developed as efficient three-photon phosphorescence (3PP) agents. Calculations reveal that the introduction of a new group to the molecular scaffold confers a quadruple promotion in three-photon transition probability. Confocal and lifetime imaging of mitochondria using IrIII complexes as 3PP agents is shown. The complexes exhibit low working concentration (50â nm), fast uptake (5â min), and low threshold for three-photon excitation power (0.5â mW at 980â nm). The impressive tissue penetration depth (ca. 450â µm) allowed the 3D imaging and reconstruction of brain vasculature from a living specimen.
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Complejos de Coordinación/química , Iridio/química , Imagen Óptica/métodos , Animales , Células HeLa , Humanos , Ratones , Fotones , Pez CebraRESUMEN
In the present study, four mitochondria-specific and two-photon phosphorescence iridium(III) complexes, Ir1-Ir4, were developed for mitochondria imaging in hypoxic tumor cells. The iridium(III) complex has two anthraquinone groups that are hypoxia-sensitive moieties. The phosphorescence of the iridium(III) complex was quenched by the functions of the intramolecular quinone unit, and it was restored through two-electron bioreduction under hypoxia. When the probes were reduced by reductase to hydroquinone derivative products under hypoxia, a significant enhancement in phosphorescence intensity was observed under one- (λ=405â nm) and two-photon (λ=720â nm) excitation, with a two-photon absorption cross section of 76-153â GM at λ=720â nm. More importantly, these probes possessed excellent specificity for mitochondria, which allowed imaging and tracking of the mitochondrial morphological changes in a hypoxic environment over a long period of time. Moreover, the probes can visualize hypoxic mitochondria in 3D multicellular spheroids and living zebrafish through two-photon phosphorescence imaging.
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Antraquinonas/química , Hipoxia de la Célula , Complejos de Coordinación/química , Iridio/química , Mitocondrias/patología , Células A549 , Animales , Encéfalo/metabolismo , Encéfalo/patología , Línea Celular Tumoral , Supervivencia Celular/efectos de los fármacos , Complejos de Coordinación/metabolismo , Complejos de Coordinación/toxicidad , Humanos , Concentración de Iones de Hidrógeno , Imagenología Tridimensional , Espectrometría de Masas , Microscopía Confocal , Microscopía de Fluorescencia por Excitación Multifotónica , Microsomas Hepáticos/metabolismo , Mitocondrias/metabolismo , Ratas , Espectrometría de Fluorescencia , Esferoides Celulares/citología , Esferoides Celulares/metabolismo , Pez Cebra/metabolismoRESUMEN
Five cyclometalated iridium(III) complexes with 2-phenylimidazo[4,5-f][1,10]phenanthroline derivatives (IrL1-IrL5) were synthesized and developed to image and track mitochondria in living cells under two-photon (750â nm) excitation, with two-photon absorption cross-sections of 48.8-65.5â GM at 750â nm. Confocal microscopy and inductive coupled plasma-mass spectrometry (ICP-MS) demonstrated that these complexes selectively accumulate in mitochondria within 5â min, without needing additional reagents for membrane permeabilization, or replacement of the culture medium. In addition, photobleaching experiments and luminescence measurements confirmed the photostability of these complexes under continuous laser irradiation and physiological pH resistance. Moreover, results using 3D multicellular spheroids demonstrate the proficiency of these two-photon luminescent complexes in deep penetration imaging. Two-photon excitation using such novel complexes of iridium(III) for exclusive visualization of mitochondria in living cells may substantially enhance practical applications of bioimaging and tracking.
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Iridio/química , Sustancias Luminiscentes/química , Dinámicas Mitocondriales/efectos de los fármacos , Compuestos Organometálicos/química , Células HeLa , Humanos , Mediciones Luminiscentes/métodos , Espectrometría de Masas , FotonesRESUMEN
The fast-moving field of photodynamic therapy (PDT) has provided fresh opportunities to expand the potential of metallodrugs to combat cancers in a light-controlled manner. As such, in the present study, a series of cyclometalated Ir(III) complexes modified with a tetrazine functional group (namely, Ir-ppy-Tz, Ir-pbt-Tz, and Ir-dfppy-Tz) are developed as potential two-photon photodynamic anticancer agents. These complexes target mitochondria but exhibit low toxicity towards HLF primary lung fibroblast normal cells in the dark. When receiving a low-dose one- or two-photon PDT, they become highly potent towards A549 lung cancer cells (with IC50 values ranging from 24.0 nM to 96.0 nM) through the generation of reactive oxygen species (ROS) to induce mitochondrial damage and subsequent apoptosis. Our results indicated that the incorporation of tetrazine with cyclometalated Ir(III) matrices would increase the singlet oxygen (1O2) quantum yield (ΦΔ) and, meanwhile, enable a type I PDT mechanism. Ir-pbt-Tz, with the largest two-photon absorption (TPA) cross-section (σ2 = 102 GM), shows great promise in serving as a two-photon PDT agent for phototherapy.
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Antineoplásicos , Complejos de Coordinación , Iridio , Mitocondrias , Fotoquimioterapia , Fármacos Fotosensibilizantes , Iridio/química , Iridio/farmacología , Humanos , Mitocondrias/efectos de los fármacos , Mitocondrias/metabolismo , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/síntesis química , Complejos de Coordinación/química , Complejos de Coordinación/farmacología , Complejos de Coordinación/síntesis química , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Fotones , Especies Reactivas de Oxígeno/metabolismo , Apoptosis/efectos de los fármacos , Células A549 , Supervivencia Celular/efectos de los fármacos , Ensayos de Selección de Medicamentos Antitumorales , Estructura MolecularRESUMEN
As a representative sulfur-containing volatile organic compounds (S-VOCs), CH3SH has attracted widespread attention due to its adverse environmental and health risks. The performance of Mn-based catalysts and the effect of their crystal structure on the CH3SH catalytic reaction have yet to be systematically investigated. In this paper, two different crystalline phases of tunneled MnO2 (α-MnO2 and ß-MnO2) with the similar nanorod morphology were used to remove CH3SH, and their physicochemical properties were comprehensively studied using high-resolution transmission electron microscope (HRTEM) and electron paramagnetic resonance (EPR), H2-TPR, O2-TPD, Raman, and X-ray photoelectron spectroscopy (XPS) analysis. For the first time, we report that the specific reaction rate for α-MnO2 (0.029 mol g-1 h-1) was approximately 4.1 times higher than that of ß-MnO2 (0.007 mol g-1 h-1). The as-synthesized α-MnO2 exhibited higher CH3SH catalytic activity towards CH3SH than that of ß-MnO2, which can be ascribed to the additional oxygen vacancies, stronger surface oxygen migration ability, and better redox properties from α-MnO2. The oxygen vacancies on the catalyst surface provided the main active sites for the chemisorption of CH3SH, and the subsequent electron transfer led to the decomposition of CH3SH. The lattice oxygen on catalysts could be released during the reaction and thus participated in the further oxidation of sulfur-containing species. CH3SSCH3, S0, SO32-, and SO42- were identified as the main products of CH3SH conversion. This work offers a new understanding of the interface interaction mechanism between Mn-based catalysts and S-VOCs.
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Hypoxia represents a remarkably exploitable target for cancer therapy, is encountered only in solid human tumors, and is highly associated with cancer resistance and recurrence. Here, a hypoxia-activated mitochondria-accumulated Ru(II) polypyridyl prodrug functionalized with conjugated azo (Az) and nitrogen mustard (NM) functionalities, RuAzNM, is reported. This prodrug has multimodal theranostic properties toward hypoxic cancer cells. Reduction of the azo group in hypoxic cell microenvironments gives rise to the generation of two primary amine products, a free aniline mustard, and the polypyridyl RuNH2 complex. Thus, the aniline mustard triggers generation of reactive oxygen species (ROS) and mtDNA crosslinking. Meanwhile, the resultant biologically benign phosphorescent RuNH2 gives rise to a diagnostic signal and signals activation of the phototherapy. This multimodal therapeutic effect eventually elevates ROS levels, depletes reduced nicotinamide adenine dinucleotide (NADH) and adenosine triphosphate (ATP), and induces mitochondrial membrane damage, mtDNA damage, and ultimately cell apoptosis. This unique strategy allows controlled multimodal theranostics to be realized in hypoxic cells and multicellular spheroids, making RuAzNM a highly selective and effective cancer-cell-selective theranostic agent (IC50 = 2.3 µm for hypoxic HepG2 cancer cells vs 58.2 µm for normoxic THL-3 normal cells). This is the first report of a metal-based compound developed as a multimodal theranostic agent for hypoxia.
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Mostaza de Anilina , Antineoplásicos , Neoplasias , Profármacos , Humanos , Especies Reactivas de Oxígeno/metabolismo , Profármacos/farmacología , Profármacos/uso terapéutico , Hipoxia/metabolismo , ADN Mitocondrial , Oxidación-Reducción , Antineoplásicos/farmacología , Antineoplásicos/uso terapéutico , Neoplasias/tratamiento farmacológicoRESUMEN
Heterogeneous reaction of gas phase NO2 with atmospheric humic-like substances (HULIS) is potentially an important source of volatile organic compounds (VOCs) including nitrogen (N)-containing compounds, a class of brown carbon of emerging importance. However, the role of ubiquitous water-soluble aerosol components in this multiphase chemistry, namely nitrate and iron ions, remains largely unexplored. Here, we used secondary electrospray ionization ultrahigh-resolution mass spectrometry for real-time measurements of VOCs formed during the heterogeneous reaction of gas phase NO2 with a solution containing gallic acid (GA) as a proxy of HULIS at pH 5 relevant for moderately acidic aerosol particles. Results showed that the number of detected N-containing organic compounds largely increased from 4 during the NO2 reaction with GA in the absence of nitrate and iron ions to 55 in the presence of nitrate and iron ions. The N-containing compounds have reduced nitrogen functional groups, namely amines, imines and imides. These results suggest that the number of N-containing compounds is significantly higher in deliquescent aerosol particles due to the influence of relatively higher ionic strength from nitrate ions and complexation/redox reactivity of iron cations compared to that in the dilute aqueous phase representative of cloud, fog, and rain water.
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In order to realize the real-time and accurate prediction of dissolved oxygen concentration in the sewage treatment process, a prediction model of dissolved oxygen concentration in the sewage treatment process based on a data identification algorithm was proposed. Combined with the data characteristics of the sewage treatment process, a new sample similarity measure is defined to extract more representative modeling data. In the improved algorithm, in order to improve the quality of the initial members of the basic fireworks algorithm, the chaos algorithm is integrated. The search mechanism of the basic fireworks algorithm is improved, and the optimization process is divided into two stages based on the set criteria, and two groups are used simultaneously. The results show that compared with the basic FWA algorithm, the CFWA algorithm makes better use of the chaotic search mechanism. On the one hand, it avoids the excessive random or blind selection of the initial weight threshold of the neural network in the initial stage; on the other hand, in the optimization process of the weight threshold, two types of search mechanisms, FWA and COA, are used to give full play to their respective strengths and to continuously conduct information exchange and mutual cooperation between groups and individuals. The number of times is better than the basic FWA algorithm, and the training error and generalization error of the CFWA model in the simulation results of the soft sensor model are also better than those of the FWA model, which fully verifies the effectiveness of the CFWA algorithm. It is proved that the data recognition algorithm can effectively predict sewage treatment. It is proved that the data recognition algorithm can effectively predict the dissolved oxygen concentration in wastewater treatment process. It provides a new measurement method for some key process variables that cannot be measured or are difficult to measure in complex chemical processes.