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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 125013, 2025 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-39186875

RESUMO

As a reactive sulfur species, sulfur dioxide (SO2) and its derivatives play crucial role in various physiological processes, which can maintain redox homeostasis at normal levels and lead to the occurrence of many diseases at abnormal levels. So, the development of a suitable fluorescent probe is a crucial step in advancing our understanding of the role of SO2 derivatives in living organisms. Herein, we developed a near-infrared fluorescent probe (SP) based on the ICT mechanism to monitor SO2 derivatives in living organisms in a ratiometric manner. The probe SP exhibited excellent selectivity, good sensitivity, fast response rate (within 50 s), and low detection limit (1.79 µM). In addition, the cell experiment results suggested that the SP has been successfully employed for the real-time monitoring of endogenous and exogenous SO2 derivatives with negligible cytotoxicity. Moreover, SP was effective in detecting SO2 derivatives in mice.


Assuntos
Corantes Fluorescentes , Dióxido de Enxofre , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Dióxido de Enxofre/análise , Animais , Camundongos , Humanos , Limite de Detecção , Espectrometria de Fluorescência , Imagem Óptica , Células HeLa
2.
J Environ Sci (China) ; 148: 57-68, 2025 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-39095190

RESUMO

The expandable graphite (EG) modified TiO2 nanocomposites were prepared by the high shear method using the TiO2 nanoparticles (NPs) and EG as precursors, in which the amount of EG doped in TiO2 was 10 wt.%. Followed by the impregnation method, adjusting the pH of the solution to 10, and using the electrostatic adsorption to achieve spatial confinement, the Pt elements were mainly distributed on the exposed TiO2, thus generating the Pt/10EG-TiO2-10 catalyst. The best CO oxidation activity with the excellent resistance to H2O and SO2 was obtained over the Pt/10EG-TiO2-10 catalyst: CO conversion after 36 hr of the reaction was ca. 85% under the harsh condition of 10 vol.% H2O and 100 ppm SO2 at a high gaseous hourly space velocity (GHSV) of 400,000 hr-1. Physicochemical properties of the catalysts were characterized by various techniques. The results showed that the electrostatic adsorption, which riveted the Pt elements mainly on the exposed TiO2 of the support surface, reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs, hence significantly improving CO oxidation activity over the Pt/10EG-TiO2-10 catalyst. The 10 wt.% EG doped in TiO2 caused the TiO2 support to form a more hydrophobic surface, which reduced the adsorption of H2O and SO2 on the catalyst, greatly inhibited deposition of the TiOSO4 and formation of the PtSO4 species as well as suppressed the oxidation of SO2, thus resulting in an improvement in the resistance to H2O and SO2 of the Pt/10EG-TiO2-10 catalyst.


Assuntos
Grafite , Oxirredução , Platina , Dióxido de Enxofre , Titânio , Titânio/química , Grafite/química , Dióxido de Enxofre/química , Platina/química , Catálise , Monóxido de Carbono/química , Água/química , Poluentes Atmosféricos/química , Modelos Químicos
3.
J Comput Chem ; 2024 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-39240057

RESUMO

Sulfonyl fluorides hold significant importance as highly valued intermediates in chemical biology due to their optimal balance of biocompatibility with both aqueous stability and protein reactivity. The Cornella group introduced a one-pot strategy for synthesizing aryl sulfonyl fluorides via Bi(III) redox-neutral catalysis, which facilitates the transmetallation and direct insertion of SO2 into the BiC(sp2) bond giving the aryl sulfonyl fluorides. We report herein a comprehensive computational investigation of the redox-neutral Bi(III) catalytic mechanism, disclose the critical role of the Bi(III) catalyst and base (i.e., K3PO4), and uncover the origin of SO2 insertion into the Bi(III)C(sp2) bond. The entire catalysis can be characterized via three stages: (i) transmetallation generating the Bi(III)-phenyl intermediate IM3 facilitated by K3PO4. (ii) SO2 insertion into IM3 leading to the formation of Bi(III)-OSOAr intermediate IM5. (iii) IM5 undergoes S(IV)-oxidation yielding the aryl sulfonyl fluoride product 4 and liberating the Bi(III) catalyst for the next catalytic cycle. Each stage is kinetically and thermodynamically feasible. Moreover, we explored other some small molecules (NO2, CO2, H2O, N2O, etc.) insertion reactions mediated by the Bi(III)-complex, and found that NO2 insertions could be easily achieved due to the low insertion barriers (i.e., 17.5 kcal/mol). Based on the detailed mechanistic study, we further rationally designed additional Bi(III) and Sb(III) catalysts, and found that some of which exhibit promising potential for experimental realization due to their low barriers (<16.4 kcal/mol). In this regard, our study contributes significantly to enhancing current Bi(III)-catalytic systems and paving the way for novel Bi(III)-catalyzed aryl sulfonyl fluoride formation reactions.

4.
Molecules ; 29(18)2024 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-39339501

RESUMO

Selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR) has been implemented in response to the regulation of NOx emissions from stationary and mobile sources above 300 °C. However, the development of NH3-SCR catalysts active at low temperatures below 200 °C is still needed to improve the energy efficiency and to cope with various fuels. In this review article, recent reports on low-temperature NH3-SCR catalysts are systematically summarized. The redox property as well as the surface acidity are two main factors that affect the catalytic activity. The strong redox property is beneficial for the low-temperature NH3-SCR activity but is responsible for N2O formation. The multiple electron transfer system is more plausible for controlling redox properties. H2O and SOx, which are often found with NOx in flue gas, have a detrimental effect on NH3-SCR activity, especially at low temperatures. The competitive adsorption of H2O can be minimized by enhancing the hydrophobic property of the catalyst. Various strategies to improve the resistance to SOx poisoning are also discussed.

5.
Angew Chem Int Ed Engl ; : e202415088, 2024 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-39297429

RESUMO

We report the inaugural experimental investigation of covalent organic frameworks (COFs) to address the formidable challenge of SO2 detection. Specifically, an imine-functionalized COF (SonoCOF-9) demonstrated a modest and reversible SO2 sorption of 3.5 mmol g-1 at 1 bar and 298 K. At 0.1 bar (and 298 K), the total SO2 uptake reached 0.91 mmol g-1 with excellent reversibility for at least 50 adsorption-desorption cycles. An isosteric enthalpy of adsorption (ΔHads) for SO2 equaled -42.3 kJ mol-1, indicating a relatively strong interaction of SO2 molecules with the COF material. Also, molecular dynamics simulations and Møller-Plesset perturbation theory calculations showed the interaction of SO2 with π density of the rings and lone pairs of the N atoms of SonoCOF-9. The combination of experimental data and theoretical calculations corroborated the potential use of this COF for the selective detection and sensing of SO2 at the sub-ppm level (0.0064 ppm of SO2).

6.
Environ Epidemiol ; 8(5): e341, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-39323988

RESUMO

Background: The relationship between sulfur dioxide (SO2) and cardiovascular disease (CVD) remains inconclusive. We aimed to clarify the association between short-term exposure to SO2 and emergency ambulance dispatches (EADs) due to CVD. Methods: We collected daily data on the number of EADs due to CVD, air pollutants, and meteorological factors between October 2013 and June 2018 in Guangzhou, China. We used the quasi-Poisson generalized additive model combined with a distributed lag nonlinear model to estimate the short-term effect of SO2 on EADs due to CVD in multivariable models. Subgroup and sensitivity analyses were also performed. Results: A total of 37,889 EADs due to CVD were documented during the study period. The average daily SO2 concentration was 12.5 µg/m3. A significant relationship between SO2 and EADs due to CVD was found, with a relative risk of 1.04 (95% confidence interval: 1.02, 1.06) with each 10 µg/m3 increment of SO2 at lag 0-1. The relationship was stronger in males, for participants aged ≥65 years, and in the cold season; however, no significant modification by subgroup was found in the association between SO2 and EADs due to CVD. Similar results from sensitivity analyses to the main findings were observed. Conclusions: Short-term exposure to SO2 was significantly associated with increased EADs due to CVD.

7.
Environ Sci Technol ; 2024 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-39324328

RESUMO

The effects of sulfur dioxide (SO2) in the catalytic purification of short-chain hydrocarbons are still controversial, and the exact role of SO2 on adsorption and reaction pathways during the catalytic oxidation of different volatile organic compounds (VOCs) remains unclear. Herein, a three-dimensional ordered macroporous Ce0.8Zr0.2O2 supported Pt nanoparticle monolithic catalyst (Pt/OM CZO) was synthesized to investigate these effects. Our findings uncover the diverse effects of SO2: Upon SO2 treatment, the coupling between the S 3p and Pt 5d orbitals promotes the Pt-O-SO3 structure in situ formed on the catalyst surface. The propene (C3H6) molecule readily binds with the oxygen atom in Pt-O-SO3, resulting in the accumulation of acetone and carbon deposition, thereby hindering C3H6 oxidation. Conversely, a cleaved oxygen atom within the Pt-O-SO3 structure enhances propane (C3H8) adsorption and activates the C-H bond, facilitating C3H8 oxidation. These insights are pivotal for advancing the frontier of sulfur-tolerant catalysts, addressing both economic and environmental challenges.

8.
Molecules ; 29(17)2024 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-39274985

RESUMO

As "chemical chameleons," organosulfones have been widely applied in various desulfonylative functionalization reactions. However, the desulfonylative functionalization of (hetero)arylsulfones through the cleavage of inert C(sp2)-SO2 bonds remains a challenging and underexplored task. Over the past twenty years, the use of (hetero)arylsulfones as arylation reagents has gradually gained attention in diverse cross-coupling reactions under specific catalytic conditions, especially in transition metal-catalysis and photocatalysis chemistry. In this review, we discuss the representative accomplishments and mechanistic insights achieved in desulfonylative reactions of inactive C(sp2)-SO2 bonds in (hetero)arylsulfones, including: (i) transition-metal-catalyzed desulfonylative cross-coupling reactions and (ii) photo-/electrocatalytic radical desulfonylative coupling reactions. We anticipate that this review will provide an overall perspective in this area to a general audience of researchers and stimulate further innovative strategies for desulfonylative functionalization of inert arylsulfones.

9.
Eur J Med Chem ; 277: 116778, 2024 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-39151274

RESUMO

Myocardial infarction (MI), one of the leading causes of death worldwide, urgently needs further understanding of the pathological process and effective therapies. SO2 in endoplasmic reticulum in several cardiovascular diseases has been reported to be particularly important. However, the role of endogenous SO2 in endoplasmic reticulum in treating myocardial infarction is still ambiguous and needs to be elucidated. Herein, we developed TPA-HI-SO2 as the first endoplasmic reticulum-targeting fluorescent agent for specific imaging and detection of sulfur dioxide derivatives both in vitro and in vivo. TPA-HI-SO2 shows a highly sensitive and selective response to SO2 derivatives over other anions in aqueous solution with a satisfactory response time and detection limit. Furthermore, TPA-HI-SO2 decreased the SO2 concentration in H9C2 cells treated with H2O2 and in an MI mouse model. Most importantly, TPA-HI-SO2 protects H9C2 cells from H2O2-induced apoptosis and obviously protects against myocardial infarction in vivo through neutralization of endogenous SO2. Taken together, we developed the first ER-targeting ratiometric fluorescent probe for endogenous SO2 with excellent biocompatibility, high selectivity and sensitivity in this paper. More importantly, we demonstrated an obvious increase of the endogenous SO2 concentration in a myocardial infarction mouse model for the first time, which suggests that neutralization of endogenous SO2 in endoplasmic reticulum could be a promising therapeutic strategy for myocardial infarction.


Assuntos
Retículo Endoplasmático , Corantes Fluorescentes , Infarto do Miocárdio , Dióxido de Enxofre , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Corantes Fluorescentes/farmacologia , Animais , Infarto do Miocárdio/tratamento farmacológico , Infarto do Miocárdio/diagnóstico por imagem , Infarto do Miocárdio/metabolismo , Dióxido de Enxofre/farmacologia , Dióxido de Enxofre/metabolismo , Retículo Endoplasmático/metabolismo , Retículo Endoplasmático/efeitos dos fármacos , Camundongos , Estrutura Molecular , Apoptose/efeitos dos fármacos , Imagem Óptica , Masculino , Humanos , Nanomedicina Teranóstica , Linhagem Celular , Ratos , Relação Dose-Resposta a Droga , Relação Estrutura-Atividade
10.
J Hazard Mater ; 478: 135613, 2024 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-39180994

RESUMO

This investigation explored the potential of utilizing alkali-treated corn cob (CC) as a solid carbon source to improve NOX and SO2 removal from flue gas. Leaching experiments unveiled a hierarchy of chemical oxygen demand release capacity: 0.03 mol/L alkali-treated CC > 0.02 mol/L > 0.01 mol/L > 0.005 mol/L > control. In NOX and SO2 removal experiments, as the inlet NOX concentration rose from 300 to 1000 mg/m3, the average NOX removal efficiency increased from 58.56 % to 80.00 %. Conversely, SO2 removal efficiency decreased from 99.96 % to 91.05 %, but swiftly rebounded to 98.56 % by day 18. The accumulation of N intermediates (NH4+, NO3-, NO2-) increased with escalating inlet NOX concentration, while the accumulation of S intermediates (SO42-, SO32-, S0) varied based on shifts in the population of functional bacteria. The elevation in inlet NOX concentration stimulated the growth of denitrifying bacteria, enhancing NOX removal efficiency. Concurrently, the population of nitrate-reducing sulfur-oxidizing bacteria and sulfate-reducing bacteria expanded, aiding in the accumulation of S0 and the removal of SO2. The comparison experiments on carbon sources confirmed the comparable NOX and SO2 removal efficiencies of alkali-treated CC and glucose, yet underscored differences in intermediates accumulation due to distinct genus structures.


Assuntos
Poluentes Atmosféricos , Álcalis , Carbono , Dióxido de Enxofre , Zea mays , Zea mays/química , Dióxido de Enxofre/química , Carbono/química , Poluentes Atmosféricos/química , Álcalis/química , Óxidos de Nitrogênio/química , Análise da Demanda Biológica de Oxigênio
11.
Talanta ; 279: 126654, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39106645

RESUMO

Mitochondrial sulfur dioxide (SO2) plays important roles in physiological and pathological activities. Unfortunately, it is lack of a reliable tool to precisely visualize the mitochondrial SO2 and elaborate its complicated functions in various cytoactivities. Here we report a mitochondrial-immobilized fluorescent probe PM-Cl consisting of coumarin and benzyl chloride modified benzothiazole, which enables selective visualization of mitochondrial SO2via chemical immobilization. The spectral results demonstrated that probe PM-Cl could respond to SO2 with high selectivity and sensitivity. Co-localization and the fluorescence of cytolysis extraction verified the excellent mitochondrial targeting and anchoring abilities. Due to the chemical immobilization, probe PM-Cl could firmly retain into mitochondria after stimulation of carbonyl cyanide m-chlorophenyl hydrazone (CCCP) and H2O2. Significantly, a series of fluorescence images are indicative of capability for detecting the fluctuations of SO2 in mitochondria during ferroptosis. Furthermore, PM-Cl also could visualize SO2 in myocardium and muscle tissues after the stimulation of CCCP. Taken together, probe PM-Cl is a very potential molecular tool for precisely detecting mitochondrial SO2 to explore its complex functions in physiological and pathological activities.


Assuntos
Ferroptose , Corantes Fluorescentes , Mitocôndrias , Dióxido de Enxofre , Corantes Fluorescentes/química , Dióxido de Enxofre/análise , Dióxido de Enxofre/química , Dióxido de Enxofre/metabolismo , Mitocôndrias/metabolismo , Mitocôndrias/química , Humanos , Animais , Camundongos , Cumarínicos/química , Imagem Óptica , Células HeLa , Carbonil Cianeto m-Clorofenil Hidrazona/farmacologia , Benzotiazóis/química
12.
Sci Total Environ ; 951: 175701, 2024 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-39179037

RESUMO

Wetlands are widely recognized as hot spots for the emission or deposition of biogenic sulfur gases, including hydrogen sulfur (H2S) and sulfur dioxide (SO2), which significantly affect air quality and climate change. With the expansion of urban wetlands, it is critical to know the roles that urban wetlands played in atmospheric H2S and SO2 budget. In this study, the surface-air exchange fluxes of H2S and SO2 were measured by the Dynamic Flux Chamber (DFC) method in a typical urban wetland in eastern China from Sep 2022 to July 2023. It was found that the urban wetland did not have the expected high H2S emission, might be caused by the relatively high pH value and low sulfate concentration in the soil. Although H2S showed emission in the daytime of spring and summer, an overall H2S flux of -0.04 kg S ha-1 yr-1 was observed throughout the year. Meanwhile, the urban wetland presented a net sink of SO2, with a deposition flux of 0.14 kg S ha-1 yr-1. The negative peaks of SO2 flux corresponded to the suddenly elevated SO2 concentration in the ambient air especially in spring and winter. Through linear fitting of SO2 flux and concentration, the concept of SO2 "compensation point" was proposed. The compensation point is the concentration level at which the observed SO2 flux equals zero. The "compensation point" changed with the season and was related to temperature and humidity. The "compensation point" in summer and autumn were larger, being 2.37 ppb and 1.40 ppb, respectively, while they were 1.07 ppb and 0.86 ppb in spring and winter respectively. Our results suggest that the urban wetland expansion may have little risk of increasing air H2S but could act as a significant sink of SO2 with high SO2 concentration in the urban region.

13.
Environ Geochem Health ; 46(10): 406, 2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-39212763

RESUMO

The Qinghai-Tibet Plateau is particularly vulnerable to the effects of climate change and disturbances caused by human activity. To better understand the interactions between soil nitrogen and sulfur cycles and human activities on the plateau, the distribution characteristics of soil nitrogen and sulfur density and their influencing factors for three soil layers in Machin County at depths of 0-20 cm, 0-100 cm, and 0-180 cm are discussed in this paper. The results indicated that at depths of 0-180 cm, soil nitrogen density in Machin County varied between 1.36 and 16.85 kg/m2, while sulfur density ranged from 0.37 to 4.61 kg/m2. The effects of three factors-geological background, land use status, and soil type-on soil nitrogen and sulfur density were all highly significant (p < 0.01). Specifically, natural factors such as soil type and geological background, along with anthropogenic factors including land use practices and grazing intensity, were identified as decisive in causing spatial variations in soil nitrogen and sulfur density. Machin County on the Tibetan Plateau exhibits natural nitrogen and sulfur sinks; However, it is crucial to monitor the emissions of N2O and SO2 into the atmosphere from areas with high external nitrogen and sulfur inputs and low fertility retention capacities, such as bare land. On this basis, changes in the spatial and temporal scales of the nitrogen and sulfur cycles in soils and their source-sink relationships remain the focus of future research.


Assuntos
Gases de Efeito Estufa , Nitrogênio , Solo , Enxofre , Solo/química , Nitrogênio/análise , Gases de Efeito Estufa/análise , Enxofre/análise , Tibet , Monitoramento Ambiental , Mudança Climática
14.
ACS Appl Mater Interfaces ; 16(32): 42717-42725, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39086140

RESUMO

The emissions of sulfur dioxide (SO2) from combustion exhaust gases pose significant risks to public health and the environment due to their harmful effects. Therefore, the development of highly efficient adsorbent polymers capable of capturing SO2 with high capacity and selectivity has emerged as a critical challenge in recent years. However, existing polymers often exhibit poor SO2/CO2 and SO2/N2 selectivity. Herein, we report two triazine-functionalized triphenylamine-based nanoporous organic polymers (ANOP-6 and ANOP-7) that demonstrate both good SO2 uptake and high SO2/CO2 and SO2/N2 selectivity. These polymers were synthesized through cost-effective Friedel-Crafts reactions using cyanuric chloride, 3,6-diphenylaminecarbazole, and 2,2',7,7'-tetrakis(diphenylamino)-9,9'-spirobifluorene. The resultant ANOPs are composed of triazine and triphenylamine units and feature an ultramicroporous structure. Remarkably, ANOPs exhibit impressive adsorption capacities for SO2, with uptakes of approximately 3.31-3.72 mmol·g-1 at 0.1 bar, increasing to 9.52-9.94 mmol·g-1 at 1 bar. The static adsorption isotherms effectively illustrate the ability of ANOPs to separate SO2 from SO2/CO2 and SO2/N2 mixtures. At 298 K and 1 bar, ANOP-6 shows outstanding selectivity toward SO2/CO2 (248) and SO2/N2 (13146), surpassing all previously reported triazine-based nanoporous organic polymers. Additionally, dynamic breakthrough tests demonstrate the superior separation properties of ANOPs for SO2 from an SO2/CO2/N2 mixture. ANOPs exhibit a breakthrough time of 73.1 min·g-1 and a saturated SO2 capacity of 0.53 mmol·g-1. These results highlight the exceptional adsorption properties of ANOPs for SO2, indicating their promising potential for the highly efficient capture of SO2 from flue gas.

15.
Small ; : e2404548, 2024 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-39092680

RESUMO

Herein, a variety of 2,6-diaminopyridine (DAP) derived nitrogen-doped hierarchically porous carbon (DAP-NHPC-T) prepared from carbonization-induced structure transformation of DAP-Zn-SiO2-P123 nanocomposites are reported, which are facilely prepared from solvent-free co-assembly of block copolymer templates P123 with pyridine-rich monomer of DAP, Zn(NO3)2 and tetramethoxysilane. In the pyrolysis process, P123 and SiO2 templates promote the formation of mesoporous and supermicroporous structures in the DAP-NHPC-T, while high-temperature volatilization of Zn contributed to generation of micropores. The DAP-NHPC-T possess large BET surface areas (≈956-1126 m2 g-1), hierarchical porosity with micro-supermicro-mesoporous feature and high nitrogen contents (≈10.44-5.99 at%) with tunable density of pyridine-based nitrogen sites (≈5.99-3.32 at%), exhibiting good accessibility and reinforced interaction with SO2. Consequently, the DAP-NHPC-T show high SO2 capacity (14.7 mmol g-1, 25 °C and 1.0 bar) and SO2/CO2/N2 IAST selectivities, extraordinary dynamic breakthrough separation efficiency and cycling stability, far beyond any other reported nitrogen-doped metal-free carbon. As verified by in situ spectroscopy and theoretical calculations, the pyridine-based nitrogen sites of the DAP-NHPC-T boost SO2 adsorption via the unique charge transfer, the adsorption mechanism and reaction model have been finally clarified.

16.
Environ Sci Technol ; 2024 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-39138907

RESUMO

Hitherto, sulfur poisoning and hydrothermal aging have still been the challenges faced in practical applications of the Cu-SSZ-13 catalyst for the selective catalytic reduction (SCR) of NOx from diesel engine exhaust. Here, we elaborately design and conduct an in-depth investigation of the synthetic effects of hydrothermal aging and SO2 poisoning on pristine Cu-SSZ-13 and Cu-SSZ-13@Ce0.75Zr0.25O2 core@shell structure catalysts (Cu@CZ). It has been discovered that Cu@CZ susceptible to 750 °C with 5 vol % H2O followed by 200 ppm SO2 with 5 vol % H2O (Cu@CZ-A-S) could still maintain nearly 100% NOx conversion across the significantly wider temperature region of 200-425 °C, which is remarkably broader than that of the Cu-SSZ-13-A-S (300-400 °C) counterpart. The experimental results show that the hydrothermal aging process results in the migration of highly active Cu species within the cage of Cu-SSZ-13 to the CZ surface, forming CuO/CZ with abundant interfaces, which significantly enhances the adsorption and subsequent activation of NO, leading to the generation of reactive N2O3 and HONO intermediates. Moreover, density functional theory (DFT) calculations reveal that the H of the HONO* species can function as Brønsted acid sites, effectively adsorbing NH3 to generate the active NH4NO2* intermediate, which readily decomposes into N2 and H2O. Furthermore, this pathway is the rate-determining step with an energy barrier of 0.93 eV, notably lower than that of the "standard SCR" pathway (1.42 eV). Therefore, the formation of the new CuO/CZ interface profoundly boosts the low-temperature NH3-SCR activity and improves the coresistance of the Cu@CZ catalyst to sulfur poisoning and hydrothermal aging.

17.
Eur J Cancer ; 209: 114259, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39111206

RESUMO

BACKGROUND: HER2 is a key biomarker for breast cancer treatment and prognosis. Traditional assessment methods like immunohistochemistry (IHC) and fluorescence in situ hybridization (FISH) are effective but costly and time-consuming. Our model incorporates these methods alongside photoacoustic imaging to enhance diagnostic accuracy and provide more comprehensive clinical insights. MATERIALS AND METHODS: A total of 301 breast tumors were included in this study, divided into HER2-positive (3+ or 2+ with gene amplification) and HER2-negative (below 3+ and 2+ without gene amplification) groups. Samples were split into training and validation sets in a 7:3 ratio. Statistical analyses involved t-tests, chi-square tests, and rank-sum tests. Predictive factors were identified using univariate and multivariate logistic regression, leading to the creation of three models: ModA (clinical factors only), ModB (clinical plus ultrasound factors), and ModC (clinical, ultrasound, and photoacoustic imaging-derived oxygen saturation (SO2)). RESULTS: The area under the curve (AUC) for ModA was 0.756 (95 % CI: 0.69-0.82), ModB increased to 0.866 (95 % CI: 0.82-0.91), and ModC showed the highest performance with an AUC of 0.877 (95 % CI: 0.83-0.92). These results indicate that the comprehensive model combining clinical, ultrasound, and photoacoustic imaging data (ModC) performed best in predicting HER2 expression. CONCLUSION: The findings suggest that integrating clinical, ultrasound, and photoacoustic imaging data significantly enhances the accuracy of predicting HER2 expression. For personalised breast cancer treatment, the integrated model could provide a comprehensive and reproducible decision support tool.


Assuntos
Neoplasias da Mama , Nomogramas , Técnicas Fotoacústicas , Receptor ErbB-2 , Humanos , Feminino , Neoplasias da Mama/diagnóstico por imagem , Neoplasias da Mama/metabolismo , Neoplasias da Mama/patologia , Técnicas Fotoacústicas/métodos , Receptor ErbB-2/metabolismo , Receptor ErbB-2/análise , Pessoa de Meia-Idade , Adulto , Idoso , Biomarcadores Tumorais/metabolismo , Biomarcadores Tumorais/análise , Ultrassonografia Mamária/métodos , Valor Preditivo dos Testes
18.
Chem Asian J ; : e202400716, 2024 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-39041455

RESUMO

Excessive sulfur dioxide (SO2) disturbs physiology of lysosomes causing diseases and threatening human health. A fluorescent probe has been regarded as one of the most attractive approaches, which is compatible with living cells and possesses high sensitivity. However, most of fluorescent probes' reaction sites are activated before they reach the destination. In this work, an acid-activatable fluorescent probe PT1 was synthesized, characterized, and used for SO2 detection. The introduction of oxazolines in PT1 enables the intelligent response of probe to release the activation stie for SO2 derivatives through Michael addition upon exposure to acid. In vitro studies showed a remarkable selectivity of PT1 to SO2 derivatives than other biothiols with a limit of detection as low as 62 nM. Precise spatiotemporal identification of lysosomal SO2 fluctuations has been successfully performed by PT1. Furthermore, PT1 can be applied for monitoring SO2 derivatives in traditional Chinese medicines.

19.
Sci Rep ; 14(1): 15503, 2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-38969703

RESUMO

In this study, we have examined the air quality within a revitalized, post-industrial urban area in Lódz, Poland. The use of Dron technology with mobile measurement equipment allowed for accurate assessment of air quality (particulate matter and gaseous pollutants) and factors influencing air quality (wind speed and direction) on a local scale in an area of 0.18 km2 and altitudes from 2 to 50 m. The results show that the revitalization carried out in the Lodz special economic zone area contributed to eliminate internal air pollution emitters through the use of ecological and effective heat sources. The exceedances permissible concentration values were local, and concerned mainly the higher measurement zones of the troposphere (more than 30 m above ground level). In the case of gaseous pollutants, higher wind speeds were associated with a decrease in the concentration of SO2 and an increase in H2S concentration. In both cases, the wind contributed to the occurrence of local areas of accumulation of these gaseous pollutants in the spaces between buildings or wooded areas.

20.
ACS Appl Mater Interfaces ; 16(28): 37298-37307, 2024 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-38970147

RESUMO

Interfacial electric field holds significant importance in determining both the polar molecular configuration and surface coverage during electrocatalysis. This study introduces a methodology leveraging the varying electric dipole moment of SO2 under distinct interfacial electric field strengths to enhance the selectivity of the SO2 electroreduction process. This approach presented the first attempt to utilize pulsed voltage application to the Au/PTFE membrane electrode for the control of the molecular configuration and coverage of SO2 on the electrode surface. Remarkably, the modulation of pulse duration resulted in a substantial inhibition of the hydrogen evolution reaction (HER) (FEH2 < 3%) under millisecond pulse conditions (ta = 10 ms, tc = 300 ms, Ea = -0.8 V (vs Hg/Hg2SO4), Ec = -1.8 V (vs Hg/Hg2SO4)), concomitant with a noteworthy enhancement in H2S selectivity (FEH2S > 97%). A comprehensive analysis, incorporating in situ Raman spectroscopy, electrochemical quartz crystal microbalance, COMSOL simulations, and DFT calculations, corroborated the increased selectivity of H2S products was primarily associated with the inherently large dipole moment of the SO2 molecule. The enhancement of the interfacial electric field induced by millisecond pulses was instrumental in amplifying SO2 coverage, activating SO2, facilitating the formation of the pivotal intermediate product *SOH, and effectively reducing the reaction energy barrier in the SO2 reduction process. These findings provide novel insights into the influences of ion and molecular transport dynamics, as well as the temporal intricacies of competitive pathways during the SO2 electroreduction process. Moreover, it underscores the intrinsic correlation between the electric dipole moment and surface-molecule interaction of the catalyst.

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