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1.
Artículo en Inglés | LILACS-Express | LILACS | ID: biblio-1565199

RESUMEN

ABSTRACT Objective: To identify and characterize the population of Pediatric patients referred to our hyperbaric oxygen therapy center. Methods: Retrospective and observational study, including pediatric patients treated with hyperbaric oxygen therapy, from 2006 to 2021, at the hyperbaric medicine reference center in the north of Portugal. Variables of interest were extracted from electronic medical records. Results: Our study included 134 patients. The most frequent reasons for referral were carbon monoxide poisoning (n=59) and sudden sensorineural hearing loss (n=41). In 75 cases (56%), treatment was initiated in an urgent context. Symptom presentation at Emergency Department varied among patients, the most frequent being headache and nausea/vomiting. Concerning carbon monoxide poisoning, the most common sources were water heater, fireplace/brazier, and boiler. Regarding adverse effects, it was identified one case of intoxication by oxygen and four cases of middle ear barotrauma. Conclusions: The most frequent cause for referral was carbon monoxide poisoning. All patients evolved favorably, with few side effects being reported, emphasizing the safety of this therapy. While most pediatricians may not be aware of the potential benefits arising with hyperbaric oxygen therapy, it is of upmost importance to promote them, so that this technique is increasingly implemented.


RESUMO Objetivo: Identificar e caracterizar a população de casos pediátricos encaminhados para o nosso centro de oxigenoterapia hiperbárica. Métodos: Estudo retrospetivo e observacional, que incluiu doentes pediátricos tratados com oxigenoterapia hiperbárica, de 2006 a 2021, no centro de referência de medicina hiperbárica do norte de Portugal. As variáveis de interesse foram extraídas dos processos clínicos eletrônicos. Resultados: O nosso estudo incluiu 134 casos. Os motivos de encaminhamento mais frequentes foram intoxicação por monóxido de carbono (n=59) e surdez súbita neurossensorial (n=41). Em 75 casos (56%) o tratamento foi iniciado em contexto de urgência. Os sintomas de apresentação à admissão variaram entre os diferentes casos, sendo os mais frequentes cefaleias e náuseas/vômitos. No que diz respeito à intoxicação por monóxido de carbono, as fontes mais comuns foram o aquecedor, lareira/braseiro e caldeira. Com relação aos efeitos adversos, foram identificados um caso de intoxicação por oxigênio e quatro casos de barotrauma do ouvido médio. Conclusões: A causa mais frequente de encaminhamento foi a intoxicação por monóxido de carbono. Todos os pacientes evoluíram favoravelmente e foram registrados poucos efeitos adversos, o que enfatiza a segurança desta terapia. Uma vez que a maioria dos pediatras pode não estar informada sobre os potenciais benefícios da oxigenoterapia hiperbárica, é de extrema importância promovê-los para que esta técnica seja cada vez mais implementada.

2.
J Environ Sci (China) ; 149: 164-176, 2025 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-39181631

RESUMEN

Cerium and cobalt loaded Co-Ce/TiO2 catalyst prepared by impregnation method was investigated for photothermal catalytic toluene oxidation. Based on catalyst characterizations (XPS, EPR and H2-TPR), redox cycle between Co and TiO2 (Co2+ + Ti4+ ↔ Co3+ + Ti3+) results in the formation of Co3+, Ti3+ and oxygen vacancies, which play important roles in toluene catalytic oxidation reaction. The introduction of Ce brings in the dual redox cycles (Co2+ + Ti4+ ↔ Co3+ + Ti3+, Co2+ + Ce4+ ↔ Co3+ + Ce3+), further promoting the elevation of reaction sites amount. Under full spectrum irradiation with light intensity of 580 mW/cm2, Co-Ce/TiO2 catalyst achieved 96% of toluene conversion and 73% of CO2 yield, obviously higher than Co/P25 and Co/TiO2. Co-Ce/TiO2 efficiently maintains 10-hour stability test under water vapor conditions and exhibits better photothermal catalytic performance than counterparts under different wavelengths illumination. Photothermal catalytic reaction displays improved activities compared with thermal catalysis, which is attributed to the promotional effect of light including photocatalysis and light activation of reactive oxygen species.


Asunto(s)
Cerio , Cobalto , Oxidación-Reducción , Titanio , Tolueno , Titanio/química , Cobalto/química , Catálisis , Tolueno/química , Cerio/química , Modelos Químicos , Procesos Fotoquímicos
3.
J Environ Sci (China) ; 149: 476-487, 2025 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-39181660

RESUMEN

Herein, three supported catalysts, CuO/Al2O3, CeO2/Al2O3, and CuO-CeO2/Al2O3, were synthesized by the convenient impregnation method to reveal the effect of CeO2 addition on catalytic performance and reaction mechanism for toluene oxidation. Compared with CuO/Al2O3, the T50 and T90 (the temperatures at 50% and 90% toluene conversion, respectively) of CuO-CeO2/Al2O3 were reduced by 33 and 39 °C, respectively. N2 adsorption-desorption experiment, XRD, SEM, EDS mapping, Raman, EPR, H2-TPR, O2-TPD, XPS, NH3-TPD, Toluene-TPD, and in-situ DRIFTS were conducted to characterize these catalysts. The excellent catalytic performance of CuO-CeO2/Al2O3 could be attributed to its strong copper-cerium interaction and high oxygen vacancies concentration. Moreover, in-situ DRIFTS proved that CuO-CeO2/Al2O3 promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene. This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.


Asunto(s)
Cerio , Cobre , Oxidación-Reducción , Tolueno , Tolueno/química , Catálisis , Cobre/química , Cerio/química , Modelos Químicos , Contaminantes Atmosféricos/química
4.
J Environ Sci (China) ; 149: 512-523, 2025 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-39181663

RESUMEN

Oxygen activation leading to the generation of reactive oxygen species (ROS) is essential for photocatalytic environmental remediation. The limited efficiency of O2 adsorption and reductive activation significantly limits the production of ROS when employing C3N4 for the degradation of emerging pollutants. Doping with metal single atoms may lead to unsatisfactory efficiency, due to the recombination of photogenerated electron-hole pairs. Here, Mn and S single atoms were introduced into C3N4, resulting in the excellent photocatalytic performances. Mn/S-C3N4 achieved 100% removal of bisphenol A, with a rate constant 11 times that of pristine C3N4. According to the experimental results and theoretical simulations, S-atoms restrict holes, facilitating the photo-generated carriers' separation. Single-atom Mn acts as the O2 adsorption site, enhancing the adsorption and activation of O2, resulting the generation of ROS. This study presents a novel approach for developing highly effective photocatalysts that follows a new mechanism to eliminate organic pollutants from water.


Asunto(s)
Oxígeno , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/química , Oxígeno/química , Catálisis , Manganeso/química , Compuestos de Bencidrilo/química , Nitrilos/química , Adsorción , Especies Reactivas de Oxígeno , Restauración y Remediación Ambiental/métodos , Fenoles/química
5.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 124953, 2025 Jan 05.
Artículo en Inglés | MEDLINE | ID: mdl-39128385

RESUMEN

Improving the ease of operation and portability of hydrogen peroxide (H2O2) detection in daily production and life holds significant application value. However, it remains a challenge to achieve rapid colorimetric detection of H2O2 and color change quantification. In this study, we achieved rapid and visual detection of H2O2 by MoOx (2 ≤ x ≤ 3) nanoparticles with rich oxygen vacancies using machine vision. As the concentration of H2O2 increases, the detection system exhibited a visible multi-color change from blue to green and then yellow and the absorption peak near 680 nm measured by the UV-visible spectrophotometer gradually decreased. With excellent sensitivity, a wide linear range of 0.1-600 µmol/L, concentrations as low as 0.1 µmol/L can be detected with good selectivity towards H2O2. The sensing mechanism of detecting H2O2 by the change of oxygen vacancies in MoOx was revealed through characterization methods such as XPS, EPR, and DFT. In addition, the Hue, Saturation, Value (HSV) visual analysis system based on MoOx was constructed to assist in the rapid, portable, and sensitive monitoring of H2O2 in practical application scenarios. This work offers an easy-to operate, low cost, and convenience for achieving rapid colorimetric determination of H2O2 and has broad application prospects in daily life and industrial production.

6.
Biomaterials ; 313: 122792, 2025 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-39226652

RESUMEN

The accumulation of photosensitizers (PSs) in lesion sites but not in other organs is an important challenge for efficient image guiding in photodynamic therapy. Cancer cells are known to express a significant number of albumin-binding proteins that take up albumin as a nutrient source. Here, we converted albumin to a novel BODIPY-like PS by generating a tetrahedral boron environment via a flick reaction. The formed albumin PS has almost the same 3-dimensional structural feature as free albumin because binding occurs at Sudlow Site 1, which is located in the interior space of albumin. An i.v. injection experiment in tumor-bearing mice demonstrated that the human serum albumin PS effectively accumulated in cancer tissue and, more surprisingly, albumin PS accumulated much more in the cancer tissue than in the liver and kidneys. The albumin PS was effective at killing tumor cells through the generation of reactive oxygen species under light irradiation. The crystal structure of the albumin PS was fully elucidated by X-ray crystallography; thus, further tuning of the structure will lead to novel physicochemical properties of the albumin PS, suggesting its potential in biological and clinical applications.


Asunto(s)
Compuestos de Boro , Fotoquimioterapia , Fármacos Fotosensibilizantes , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/uso terapéutico , Fotoquimioterapia/métodos , Animales , Compuestos de Boro/química , Humanos , Ratones , Línea Celular Tumoral , Ratones Endogámicos BALB C , Especies Reactivas de Oxígeno/metabolismo , Ratones Desnudos , Albúminas/química , Albúminas/metabolismo , Neoplasias/tratamiento farmacológico , Neoplasias/patología , Neoplasias/metabolismo
7.
Biomaterials ; 313: 122765, 2025 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-39244824

RESUMEN

Accurate and early detection of atherosclerosis (AS) is imperative for their effective treatment. However, fluorescence probes for efficient diagnosis of AS often encounter insufficient deep tissue penetration, which hinders the reliable assessment of plaque vulnerability. In this work, a reactive oxygen species (ROS) activated near-infrared (NIR) fluorescence and photoacoustic (FL/PA) dual model probe TPA-QO-B is developed by conjugating two chromophores (TPA-QI and O-OH) and ROS-specific group phenylboronic acid ester. The incorporation of ROS-specific group not only induces blue shift in absorbance, but also inhibits the ICT process of TPA-QO-OH, resulting an ignorable initial FL/PA signal. ROS triggers the convertion of TPA-QO-B to TPA-QO-OH, resulting in the concurrent amplification of FL/PA signal. The exceptional selectivity of TPA-QO-B towards ROS makes it effectively distinguish AS mice from the healthy. The NIR emission can achieve a tissue penetration imaging depth of 0.3 cm. Moreover, its PA775 signal possesses the capability to penetrate tissues up to a thickness of 0.8 cm, ensuring deep in vivo imaging of AS model mice in early stage. The ROS-triggered FL/PA dual signal amplification strategy improves the accuracy and addresses the deep tissue penetration problem simultaneously, providing a promising tool for in vivo tracking biomarkers in life science and preclinical applications.


Asunto(s)
Colorantes Fluorescentes , Técnicas Fotoacústicas , Placa Aterosclerótica , Especies Reactivas de Oxígeno , Animales , Especies Reactivas de Oxígeno/metabolismo , Técnicas Fotoacústicas/métodos , Placa Aterosclerótica/diagnóstico por imagen , Placa Aterosclerótica/metabolismo , Colorantes Fluorescentes/química , Ratones , Imagen Óptica/métodos , Ratones Endogámicos C57BL , Humanos , Masculino
8.
Biomaterials ; 313: 122762, 2025 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-39178559

RESUMEN

Osteomyelitis is an osseous infectious disease that primarily affects children and the elderly with high morbidity and recurrence. The conventional treatments of osteomyelitis contain long-term and high-dose systemic antibiotics with debridements, which are not effective and lead to antibiotic resistance with serious side/adverse effects in many cases. Hence, developing novel antibiotic-free interventions against osteomyelitis (especially antibiotic-resistant bacterial infection) is urgent and anticipated. Here, a bone mesenchymal stem cell membrane-constructed nanocell (CFE@CM) was fabricated against osteomyelitis with the characteristics of acid-responsiveness, hydrogen peroxide self-supplying, enhanced chemodynamic therapeutic efficacy, bone marrow targeting and cuproptosis induction. Notably, mRNA sequencing was applied to unveil the underlying biological mechanisms and found that the biological processes related to copper ion binding, oxidative phosphorylation, peptide biosynthesis and metabolism, etc., were disturbed by CFE@CM in bacteria. This work provided an innovative antibiotic-free strategy against osteomyelitis through copper-enhanced Fenton reaction and distinct cuproptosis, promising to complement the current insufficient therapeutic regimen in clinic.


Asunto(s)
Cobre , Osteomielitis , Osteomielitis/tratamiento farmacológico , Animales , Cobre/química , Cobre/farmacología , Concentración de Iones de Hidrógeno , Células Madre Mesenquimatosas/efectos de los fármacos , Células Madre Mesenquimatosas/citología , Ratones , Peróxido de Hidrógeno/metabolismo , Antibacterianos/farmacología , Antibacterianos/uso terapéutico , Antibacterianos/química , Humanos , Staphylococcus aureus/efectos de los fármacos
9.
J Environ Sci (China) ; 147: 11-21, 2025 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-39003033

RESUMEN

Microbial oxidation and the mechanism of Sb(III) are key governing elements in biogeochemical cycling. A novel Sb oxidizing bacterium, Klebsiella aerogenes HC10, was attracted early and revealed that extracellular metabolites were the main fractions driving Sb oxidation. However, linkages between the extracellular metabolite driven Sb oxidation process and mechanism remain elusive. Here, model phenolic and quinone compounds, i.e., anthraquinone-2,6-disulfonate (AQDS) and hydroquinone (HYD), representing extracellular oxidants secreted by K. aerogenes HC10, were chosen to further study the Sb(III) oxidation mechanism. N2 purging and free radical quenching showed that oxygen-induced oxidation accounted for 36.78% of Sb(III) in the metabolite reaction system, while hydroxyl free radicals (·OH) accounted for 15.52%. ·OH and H2O2 are the main driving factors for Sb oxidation. Radical quenching, methanol purification and electron paramagnetic resonance (EPR) analysis revealed that ·OH, superoxide radical (O2•-) and semiquinone (SQ-•) were reactive intermediates of the phenolic induced oxidation process. Phenolic-induced ROS are one of the main oxidants in metabolites. Cyclic voltammetry (CV) showed that electron transfer of quinone also mediated Sb(III) oxidation. Part of Sb(V) was scavenged by the formation of the secondary Sb(V)-bearing mineral mopungite [NaSb(OH)6] in the incubation system. Our study demonstrates the microbial role of oxidation detoxification and mineralization of Sb and provides scientific references for the biochemical remediation of Sb-contaminated soil.


Asunto(s)
Antimonio , Oxidación-Reducción , Especies Reactivas de Oxígeno , Transporte de Electrón , Antimonio/metabolismo , Especies Reactivas de Oxígeno/metabolismo
10.
J Environ Sci (China) ; 147: 652-664, 2025 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-39003080

RESUMEN

Ball milling is an environmentally friendly technology for the remediation of petroleum-contaminated soil (PCS), but the cleanup of organic pollutants requires a long time, and the post-remediation soil needs an economically viable disposal/reuse strategy due to its vast volume. The present paper develops a ball milling process under oxygen atmosphere to enhance PCS remediation and reuse the obtained carbonized soil (BCS-O) as wastewater treatment materials. The total petroleum hydrocarbon removal rates by ball milling under vacuum, air, and oxygen atmospheres are 39.83%, 55.21%, and 93.84%, respectively. The Langmuir and pseudo second-order models satisfactorily describe the adsorption capacity and behavior of BCS-O for transition metals. The Cu2+, Ni2+, and Mn2+ adsorbed onto BCS-O were mainly bound to metal carbonates and metal oxides. Furthermore, BCS-O can effectively activate persulfate (PDS) oxidation to degrade aniline, while BCS-O loaded with transition metal (BCS-O-Me) shows better activation efficiency and reusability. BCS-O and BCS-O-Me activated PDS oxidation systems are dominated by 1O2 oxidation and electron transfer. The main active sites are oxygen-containing functional groups, vacancy defects, and graphitized carbon. The oxygen-containing functional groups and vacancy defects primarily activate PDS to generate 1O2 and attack aniline. Graphitized carbon promotes aniline degradation by accelerating electron transfer. The paper develops an innovative strategy to simultaneously realize efficient remediation of PCS and sequential reuse of the post-remediation soil.


Asunto(s)
Restauración y Remediación Ambiental , Oxígeno , Petróleo , Contaminantes del Suelo , Eliminación de Residuos Líquidos , Aguas Residuales , Contaminantes del Suelo/química , Contaminantes del Suelo/análisis , Adsorción , Aguas Residuales/química , Oxígeno/química , Oxígeno/análisis , Eliminación de Residuos Líquidos/métodos , Restauración y Remediación Ambiental/métodos , Suelo/química , Catálisis
11.
J Environ Sci (China) ; 147: 83-92, 2025 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-39003086

RESUMEN

The environmental threat posed by stibnite is an important geoenvironmental issue of current concern. To better understand stibnite oxidation pathways, aerobic abiotic batch experiments were conducted in aqueous solution with varying δ18OH2O value at initial neutral pH for different lengths of time (15-300 days). The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined. The sulfur isotope fractionation factor (Δ34SSO4-stibnite) values decreased from 0.8‰ to -2.1‰ during the first 90 days, and increased to 2.6‰ at the 180 days, indicating the dominated intermediate sulfur species such as S2O32-, S0, and H2S (g) involved in Sb2S3 oxidation processes. The incorporation of O into sulfate derived from O2 (∼100%) indicated that the dissociated O2 was only directly adsorbed on the stibnite-S sites in the initial stage (0-90 days). The proportion of O incorporation into sulfate from water (27%-52%) increased in the late stage (90-300 days), which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O2 on stibnite-Sb sites. The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42-. The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.


Asunto(s)
Oxidación-Reducción , Isótopos de Oxígeno , Sulfatos , Isótopos de Azufre , Isótopos de Azufre/análisis , Sulfatos/química , Isótopos de Oxígeno/análisis , Antimonio/química , Modelos Químicos , Aerobiosis , Oxígeno/química , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química , Óxidos
12.
Artículo en Español | LILACS, BNUY, UY-BNMED | ID: biblio-1568770

RESUMEN

La evaluación de la marcha en cinta caminadora puede resultar relevante para la toma de decisiones clínicas. No obstante, factores demográficos como la edad y el IMC pueden alterar la interpretación de los resultados. Nuestro objetivo fue obtener variables espacio- temporales, energéticas y costo de transporte durante la velocidad autoseleccionada en cinta caminadora para una muestra representativa de adultos uruguayos (n=28) y evaluar si diferentes rangos de edades e IMC pueden ser factores a tener en cuenta en pruebas clínicas donde se consideren dichas variables. Participaron 17 hombres y 11 mujeres (39,3 ± 14,8 años, 75,9 ± 12,5 kg, 1,74 ± 0,09 m, IMC 25,2 ± 4,06). Se realizó una reconstrucción 3D del movimiento en forma sincronizada con el consumo energético. Se obtuvieron valores de referencia y luego de agrupar los participantes según su IMC y rango de edad se compararon los datos mediante test de t (p≤0.05). Los resultados revelaron discrepancias significativas en las medidas espacio-temporales y energéticas de los adultos uruguayos al caminar en cinta con respecto a la literatura. La marcha difiere entre adultos jóvenes y de mediana edad en su velocidad autoseleccionada (p=0,03), longitud de zancada (p=0,01), trabajo mecánico externo (<0,001) y recuperación de energía mecánica (0,009), destacando la importancia de considerar la edad en evaluaciones clínicas. El IMC no influyó significativamente en estas variables. Estos hallazgos subrayan la necesidad de ajustar las interpretaciones de las pruebas clínicas de la marcha sobre cinta caminadora en adultos uruguayos de mediana edad (45 a 65 años).


Treadmill gait assessment can be relevant for clinical decision-making. However, demographic factors such as age and BMI may alter result interpretation. Our aim was to obtain spatiotemporal, energetic, and cost of transport variables during self-selected treadmill walking speed for a representative sample of Uruguayan adults (n=28) and to assess if different age ranges and BMI could be factors to consider in clinical tests involving these variables. Seventeen men and eleven women participated (39.3 ± 14.8 years, 75.9 ± 12.5 kg, 1.74 ± 0.09 m, BMI 25.2 ± 4.06). A synchronized 3D motion reconstruction was performed with energy consumption. Reference values were obtained and data were compared using t-tests (p≤0.05), after grouping participants by BMI and age range. Results revealed significant discrepancies in spatiotemporal and energetic measures of Uruguayan adults walking on the treadmill, compared to the literature. Gait differed between young and middle-aged adults in their self-selected speed (p=0.03), stride length (p=0.01), external mechanical work (p<0.001), and mechanical energy recovery (0.009), emphasizing the importance of considering age in clinical evaluations. BMI did not significantly influence these variables. These findings underscore the need to adjust interpretations of treadmill gait clinical tests in middle-aged Uruguayan adults (45 to 65 years).


A avaliação da marcha na esteira pode ser relevante para a tomada de decisões clínicas. No entanto, fatores demográficos como idade e IMC podem alterar a interpretação dos resultados. Nosso objetivo foi obter variáveis espaço-temporais, energéticas e custo de transporte durante a velocidade de caminhada autoselecionada na esteira para uma amostra representativa de adultos uruguaios (n = 28) e avaliar se diferentes faixas etárias e IMC podem ser fatores a serem considerados em testes clínicos que envolvam essas variáveis. Dezessete homens e onze mulheres participaram (39,3 ± 14,8 anos, 75,9 ± 12,5 kg, 1,74 ± 0,09 m, IMC 25,2 ± 4,06). Foi realizada uma reconstrução tridimensional do movimento sincronizada com o consumo de energia. Foram obtidos valores de referência e os dados foram comparados usando testes t (p≤0,05), após agrupar os participantes por IMC e faixa etária. Os resultados revelaram discrepâncias significativas nas medidas espaço-temporais e energéticas dos adultos uruguaios ao caminhar na esteira, em comparação com a literatura. A marcha diferiu entre adultos jovens e de meia-idade em sua velocidade autoselecionada (p=0,03), comprimento da passada (p=0,01), trabalho mecânico externo (<0,001) e recuperação de energia mecânica (0,009), destacando a importância de considerar a idade em avaliações clínicas. O IMC não influenciou significativamente essas variáveis. Esses achados destacam a necessidade de ajustar as interpretações dos testes clínicos de marcha na esteira em adultos uruguaios de meia- idade (45 a 65 anos).


Asunto(s)
Humanos , Masculino , Femenino , Adolescente , Adulto , Persona de Mediana Edad , Adulto Joven , Composición Corporal/fisiología , Caminata/fisiología , Prueba de Esfuerzo/estadística & datos numéricos , Índice de Masa Corporal , Distribución por Edad
13.
Proc Natl Acad Sci U S A ; 121(38): e2401175121, 2024 Sep 17.
Artículo en Inglés | MEDLINE | ID: mdl-39250664

RESUMEN

Singlet oxygen (1O2) is important in the environmental remediation field, however, its efficient production has been severely hindered by the ultrafast self-quenching of the as-generated radical precursors in the Fenton-like reactions. Herein, we elaborately designed lamellar anthraquinone-based covalent organic frameworks (DAQ-COF) with sequential localization of the active sites (C═O) at molecular levels for visible-light-assisted peroxymonosulfate (PMS) activation. Theoretical and experimental results revealed that the radical precursors (SO5·-) were formed in the nearby layers with the migration distance less than 0.34 nm, via PMS donating electrons to the photogenerated holes. This interlayer synergistic effect eventually led to ultraefficient 1O2 production (14.8 µM s-1), which is 12 times that of the highest reported catalyst. As an outcome, DAQ-COF enabled the complete degradation of bisphenol A in 5 min with PMS under natural sunlight irradiation. This interlayer synergistic concept represents an innovative and effective strategy to increase the utilization efficiency of ultrashort-lived radical precursors, providing inspirations for subtle structural construction of Fenton-like catalysts.

14.
Environ Sci Technol ; 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39250812

RESUMEN

Water is ubiquitous in various heterogeneous catalytic reactions, where it can be easily adsorbed, chemically dissociated, and diffused on catalyst surfaces, inevitably influencing the catalytic process. However, the specific role of water in these reactions remains unclear. In this study, we innovatively propose that H2O-driven surface lattice oxygen activation in γ-MnO2 significantly enhances low-temperature NH3-SCR. The proton from water dissociation activates the surface lattice oxygen in γ-MnO2, giving rise to a doubling of catalytic activity (achieving 90% NO conversion at 100 °C) and remarkable stability. Comprehensive in situ characterizations and calculations reveal that spontaneous proton diffusion to the surface lattice oxygen reduces the orbital overlap between the protonated oxygen atom and its neighboring Mn atom. Consequently, the Mn-O bond is weakened and the surface lattice oxygen is effectively activated to provide excess oxygen vacancies available for converting O2 into O2-. Therefore, the redox property of Mn-H is improved, leading to enhanced NH3 oxidation-dehydrogenation and NO oxidation processes, which are crucial for low-temperature NH3-SCR. This work provides a deeper understanding and fresh perspectives on the water promotion mechanism in low-temperature NOx elimination.

15.
Artículo en Inglés | MEDLINE | ID: mdl-39250820

RESUMEN

Intervertebral disc degeneration (IVDD) may lead to an increase in extracellular matrix (ECM) stiffness, contributing to the progression of the disease. Melatonin reportedly mitigates IVDD; while its potential to attenuate elevated matrix stiffness-induced IVDD remains unexplored. Therefore, we aimed to investigate whether melatonin can alleviate the progression of IVDD triggered by increased matrix stiffness and elucidate its mechanisms. Nucleus pulposus (NP) tissues were collected from patients, and ECM stiffness, reactive oxygen species (ROS) levels, apoptosis rates, and p65 expression in these tissues with varying Pfirrmann scores were determined. In vitro experiments were conducted to investigate the effects of melatonin on the NP cells cultured on soft substrate with differing stiffness levels. Our findings revealed a positive correlation between ECM stiffness in human NP tissue and degree of IVDD. Additionally, phosphorylation of P65 exhibited a strong association with matrix stiffness. Enhanced levels of ROS and cellular apoptosis were observed within degenerated intervertebral discs. In vitro experiments demonstrated that melatonin significantly inhibited catabolism and apoptosis induced by stiff matrices, along with elevated ROS levels. Furthermore, we observed that melatonin inhibited NP cell catabolism and apoptosis by reducing the melatonin receptors mediated activation of the PI3K/AKT and NF-κB pathways. Also, we found that the reduction of ROS by melatonin can assist in inhibiting the activation of the NF-κB pathway. The outcomes of the in vivo experiments corroborated the results of the in vitro experiments. Collectively, melatonin can potentially alleviate high matrix stiffness-induced IVDD by reducing intracellular ROS levels and inhibiting the PI3K/AKT/NF-κB pathway.

16.
ACS Nano ; 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39250826

RESUMEN

Photodynamic therapy (PDT) and sonodynamic therapy (SDT), using nonionizing light and ultrasound to generate reactive oxygen species, offer promising localized treatments for cancers. However, the effectiveness of PDT is hampered by inadequate tissue penetration, and SDT largely relies on pyrolysis and sonoluminescence, which may cause tissue injury and imprecise targeting. To address these issues, we have proposed a mechanochemical dynamic therapy (MDT) that uses free radicals generated from mechanophore-embedded polymers under mechanical stress to produce reactive oxygen species for cancer treatment. Yet, their application in vivo is constrained by the bulk form of the polymer and the need for high ultrasound intensities for activation. In this study, we developed injectable, nanoscale mechanophore particles with enhanced ultrasound sensitivity by leveraging a core-shell structure comprising silica nanoparticles (NPs) whose interfaces are linked to polymer brushes by an azo mechanophore moiety. Upon focused ultrasound (FUS) treatment, this injectable NP generates reactive oxygen species (ROS), demonstrating promising results in both an in vitro 4T1 cell model and an in vivo mouse model of orthotopic breast cancers. This research offers an alternative therapy technique, integrating force-responsive azo mechanophores and FUS under biocompatible conditions.

17.
J Colloid Interface Sci ; 678(Pt B): 343-352, 2024 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-39250837

RESUMEN

Magnesium hydride (MgH2) as an ideal hydrogen storage carrier whose hydrogen storage performance can be effectively improved by transition metal-based catalysts. To construct highly active catalysts, much attention has been paid to the regulation of transition metal components while less attention has been paid to non-transition metal components especially oxygen, leading certain limitations. Herein, further improved hydrogen storage performance of MgH2 can be obtained by adjusting oxygen vacancy content in molybdenum trioxide (MoO3) catalyst. Specifically, compared with pure MgH2 (1.1 wt%) and MgH2-10 wt% MoO3 (4.5 wt%), more hydrogen (5.9 wt%) can be released by MgH2-10 wt% MoO3-x (MoO3 with abundant oxygen vacancies) at 300.0 °C within 499.0 s. Besides, superb capacity retention (6.1 wt%, 99.0 %) after 50 isothermal hydrogen ab/desorption cycles can be obtained for MgH2-10 wt% MoO3-x. Through rigorous comparative experiments and theoretical calculations, the excellent catalytic activity of MoO3-x is demonstrated to come from the abundant oxygen vacancies and the active substances (polyvalent Mo and nano-sized MgO) it assists to form during ball milling process. This work verifies the feasibility for further improving the catalytic activity of transition metal-based catalysts by tuning non-transition metal elements and thus provides a new strategy in catalyzed MgH2 system.

18.
Spectrochim Acta A Mol Biomol Spectrosc ; 325: 125078, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-39250849

RESUMEN

Luminous marine bacteria are traditionally used as a bioassay due to the convenience and high rate of registering the intensity of their physiological function - luminescence. This study aimed to develop the application of Photobacterium phosphoreum in traditional and novel fields - toxicity monitoring and biotechnology. We demonstrated (1) effects of selenite ions on bioluminescence, and (2) biotransformation of selenite to selenium(0) in the form of nanoparticles. The effects of selenite (SeO32-) on the intensity of bacterial bioluminescence were studied, and its dependencies on exposure time and concentration of Na2SeO3 were analyzed. Bioluminescence activation and inhibition were revealed; dose-effect dependencies corresponded to the hormesis model. The toxicity of SeO32- was characterized by an effective concentration of 10-3 M. Effects of SeO32- on reactive oxygen species (ROS) in bacterial suspensions were studied. High positive correlations were found between the bioluminescence intensity and ROS content, which indicates the decisive role of ROS and associated redox processes in the bioeffects of selenite ions. Scanning and transmission electron microscopy revealed the presence of nano-structures in the bacteria exposed to selenite. The energy dispersion spectrum detected a high content of selenium in the nanoparticles. The particle size distribution depended on Na2SeO3 concentration; maxima of the distribution varied within 45-55 nm.

19.
J Hazard Mater ; 479: 135775, 2024 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-39250861

RESUMEN

Glomalin-related soil protein (GRSP) has demonstrated significant potential for water purification and remediation of heavy metals in soils; however, its redox reactivity for As(III) sequestration and the corresponding redox-active component are still poorly understood. This study investigated the photochemical properties of GRSP and its mechanism of oxidation/adsorption of As(III). The results showed that UV irradiation triggered electron transfer and the production of reactive oxygen species (ROS) in GRSP, thereby facilitating As(III) oxidation with promotion rates ranging from 43.34 % to 111.1 %. The oxidation of As(III) occurred both on the GRSP photoforming holes and in the ROS reaction from the oxygen reduction products of the photoforming electrons. OH• and H2O2 played an important role in the oxidation of As(III) by GRSP, especially under alkaline conditions. Moreover, the presence of Fe(III) in GRSP facilitated the formation of OH• and its the oxidation capacity towards As(III). The binding of As(III) to the -COOH, -OH, and -FeO groups on the GRSP surface occurred through surface complexation. Overall, these findings provided new insights into the roles of the redox-active moieties and Fe(III) on GRSP in the promoted oxidation of As(III), which would help to deepen our understanding of the migration and transformation of As(III) in soils.

20.
Environ Monit Assess ; 196(10): 908, 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39249565

RESUMEN

Chemical and isotopic indicators were used to recognize the origin of hydrothermal groundwater, to assess the mineralization processes and groundwater quality, to identify the source of solutes and the likely mixing with cold, and elucidate the fluid geothermometry in the Jérid field of Southern Tunisia. The results show that the geothermal groundwater is neutral to slightly alkaline. They are characterized by SO4-Cl-Na-Ca water type. The dissolution of evaporates and pyrite-bearing rocks is the dominant mineralization process. The groundwater quality index indicates that the majority of samples are very hard and belong to poor to unsuitable for drinking classes. Applications and calculations of hydrogeochemical parameters, including SAR, %Na, PI, Kr, and MAR, showed that the majority of samples are unsuitable for agricultural practices. The human health risk was assessed based on hazard quotient and total hazard index through ingestion and dermal contact with iron-rich groundwater. The consumption of CI groundwaters does not present non-carcinogenic risk to adults and children. The δ18 O and δ2H signatures indicate that the geothermal groundwater was recharged by ocean precipitation during cold and wet paleoclimatic periods. The slight enrichment of oxygen-18 and deuterium contents suggests a limited mixing effect between geothermal water and cold groundwater within the same aquifer. This mixing effect is confirmed by the Na-K-Mg and the chloride-enthalpy diagrams. The K-Mg and SiO2 geothermometers provided fairly reliable reservoir temperature values, ranging between 69.6 and 99 °C. Calculated geothermal potential values, varying between 469 and 16987 kWth, which allow several applications such as domestic and agricultural heating.


Asunto(s)
Monitoreo del Ambiente , Agua Subterránea , Contaminantes Químicos del Agua , Túnez , Agua Subterránea/química , Monitoreo del Ambiente/métodos , Contaminantes Químicos del Agua/análisis , Isótopos de Oxígeno/análisis
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