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1.
Environ Geochem Health ; 46(8): 269, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38954139

RESUMO

In the confined space of the underground coal mine, which is dominated by transportation lanes, explosion-proof diesel-powered trackless rubber-wheeled vehicles are becoming the main transportation equipment, and the exhaust gas produced by them is hazardous to the health of workers and pollutes the underground environment. In this experiment, a similar test platform is built to study the effects of wind speed, vehicle speed, and different wind directions on the diffusion characteristics of exhaust gas. In this paper, CO and SO2 are mainly studied. The results show that the diffusion of CO and SO2 gas is similar and the maximum SO2 concentration only accounts for 11.4% of the CO concentration. Exhaust gas is better diluted by increasing the wind speed and vehicle speed, respectively. Downwind is affected by the reverse wind flow and diffuses to the driver's position, which is easy to cause occupational diseases. When the wind is a headwind, the exhaust gases spread upwards and make a circumvention movement, gathering at the top. When the wind speed and vehicle speed are both 0.6 m/s, the CO concentration corresponds to the change trend of the Lorentz function when the wind is downwind and the CO concentration corresponds to the change trend of the BiDoseResp function when the wind is headwind. The study of exhaust gas diffusion characteristics is of great significance for the subsequent purification of the air in the restricted mine space and the protection of the workers' occupational health.


Assuntos
Minas de Carvão , Espaços Confinados , Emissões de Veículos , Vento , Emissões de Veículos/análise , Dióxido de Enxofre/análise , Monóxido de Carbono/análise , Difusão , Monitoramento Ambiental/métodos , Poluentes Atmosféricos/análise , Poluentes Ocupacionais do Ar/análise , Exposição Ocupacional/análise
2.
Zhong Nan Da Xue Xue Bao Yi Xue Ban ; 49(3): 476-481, 2024 Mar 28.
Artigo em Inglês, Chinês | MEDLINE | ID: mdl-38970522

RESUMO

There are 2 techniques for detecting red blood cell survival (RBCS) detection techniques: red blood cell labeling test and carbon monoxide (CO) breath test. The former has disadvantages such as long measurement times and complicated procedures, while the latter is simple, convenient, moderately priced, and capable of dynamically monitoring changes in RBCS before and after treatment. Currently, the CO breath test is gradually being implemented in clinical practice. RBCS is not only applied to hematologic diseases such as multiple myeloma, myelodysplastic syndromes, lymphoma, and thalassemia, but also to non-hematologic diseases like type 2 diabetes and chronic kidney disease. It can assist in diagnosis, guide treatment, evaluate drug treatment efficacy, and predict disease progression.


Assuntos
Eritrócitos , Humanos , Eritrócitos/citologia , Monóxido de Carbono/sangue , Testes Respiratórios/métodos , Sobrevivência Celular , Diabetes Mellitus Tipo 2/sangue , Doenças Hematológicas/sangue , Doenças Hematológicas/diagnóstico
3.
Sci Rep ; 14(1): 16220, 2024 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-39003417

RESUMO

Long-term mortality effects of particulate air pollution have been investigated in a causal analytic frame, while causal evidence for associations with gaseous air pollutants remains extensively lacking, especially for carbon monoxide (CO) and sulfur dioxide (SO2). In this study, we estimated the causal relationship of long-term exposure to nitrogen dioxide (NO2), CO, SO2, and ozone (O3) with mortality. Utilizing the data from National Morbidity, Mortality, and Air Pollution Study, we applied a variant of difference-in-differences (DID) method with conditional Poisson regression and generalized weighted quantile sum regression (gWQS) to investigate the independent and joint effects. Independent exposures to NO2, CO, and SO2 were causally associated with increased risks of total, nonaccidental, and cardiovascular mortality, while no evident associations with O3 were identified in the entire population. In gWQS analyses, an interquartile range-equivalent increase in mixture exposure was associated with a relative risk of 1.067 (95% confidence interval: 1.010-1.126) for total mortality, 1.067 (1.009-1.128) for nonaccidental mortality, and 1.125 (1.060-1.193) for cardiovascular mortality, where NO2 was identified as the most significant contributor to the overall effect. This nationwide DID analysis provided causal evidence for independent and combined effects of NO2, CO, SO2, and O3 on increased mortality risks among the US general population.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Exposição Ambiental , Dióxido de Nitrogênio , Ozônio , Dióxido de Enxofre , Humanos , Estados Unidos/epidemiologia , Poluição do Ar/efeitos adversos , Poluição do Ar/análise , Poluentes Atmosféricos/efeitos adversos , Poluentes Atmosféricos/análise , Exposição Ambiental/efeitos adversos , Dióxido de Enxofre/análise , Dióxido de Enxofre/efeitos adversos , Ozônio/análise , Ozônio/efeitos adversos , Ozônio/toxicidade , Dióxido de Nitrogênio/análise , Dióxido de Nitrogênio/efeitos adversos , Dióxido de Nitrogênio/toxicidade , Masculino , Feminino , Pessoa de Meia-Idade , Idoso , Adulto , Mortalidade , Monóxido de Carbono/análise , Monóxido de Carbono/efeitos adversos , Doenças Cardiovasculares/mortalidade , Material Particulado/efeitos adversos , Material Particulado/análise , Adolescente , Adulto Jovem
4.
Environ Geochem Health ; 46(9): 313, 2024 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-39001902

RESUMO

The presence of pollutants in the earth's atmosphere has a direct impact on human health and the environment. So that pollutants such as carbon monoxide (CO) and particulate matter (PM) cause respiratory diseases, cough headache, etc. Since the amount of pollutants in the air is related to environmental and urban factors, the aim of the current research is to investigate the relationship between the concentration of CO, PM2.5 and PM10 with urban-environmental factors including land use, wind speed and wind direction, topography, traffic, road network, and population through a Land use regression (LUR) model. The concentrations of CO, PM2.5 and PM10 were measured during four seasons from 26th of March 2022 to 16th of March 2023 at 25 monitoring stations and then the information about pollutant measurement points and Land use data were entered into the ArcGIS software. The annual average concentrations of CO, PM2.5 and PM10 were 0.7 ppm, 18.94 and 60.76 µg/m3, respectively, in which the values of annual average concentration of CO and PMs were outside the air quality guideline standard. The results of the health risk assessment showed that the hazard quotient values for all three investigated pollutants were lower than 1 and therefore, they were not in adverse conditions in terms of health effects. Among the urban-environmental factors affecting air pollution, the traffic variable is the most important factor affecting the annual LUR model of CO, PM2.5 and PM10, and then the topography variable is the second most effective factor on the annual LUR model of the aforementioned pollutants.


Assuntos
Poluentes Atmosféricos , Monóxido de Carbono , Monitoramento Ambiental , Material Particulado , Poluentes Atmosféricos/análise , Medição de Risco , Material Particulado/análise , Humanos , Monóxido de Carbono/análise , Monitoramento Ambiental/métodos , Análise de Regressão , Poluição do Ar/análise , Cidades , Exposição Ambiental , Modelos Teóricos
5.
Environ Sci Technol ; 58(28): 12731-12741, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38958431

RESUMO

Effective synthesis and application of single-atom catalysts on supports lacking enough defects remain a significant challenge in environmental catalysis. Herein, we present a universal defect-enrichment strategy to increase the surface defects of CeO2-based supports through H2 reduction pretreatment. The Pt catalysts supported by defective CeO2-based supports, including CeO2, CeZrOx, and CeO2/Al2O3 (CA), exhibit much higher Pt dispersion and CO oxidation activity upon reduction activation compared to their counterpart catalysts without defect enrichment. Specifically, Pt is present as embedded single atoms on the CA support with enriched surface defects (CA-HD) based on which the highly active catalyst showing embedded Pt clusters (PtC) with the bottom layer of Pt atoms substituting the Ce cations in the CeO2 surface lattice can be obtained through reduction activation. Embedded PtC can better facilitate CO adsorption and promote O2 activation at PtC-CeO2 interfaces, thereby contributing to the superior low-temperature CO oxidation activity of the Pt/CA-HD catalyst after activation.


Assuntos
Monóxido de Carbono , Oxirredução , Platina , Monóxido de Carbono/química , Platina/química , Catálise , Cério/química , Adsorção , Propriedades de Superfície
6.
Anal Chem ; 96(28): 11588-11594, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38967368

RESUMO

Fluorescence sensing and imaging techniques are being widely studied for detecting carbon monoxide (CO) in living organisms due to their speed, sensitivity, and ease of use to biological systems. Most fluorescent probes used for this purpose are based on heavy metal ions like Pd, with a few using elements like Ru, Rh, Ir, Os, Tb, and Eu. However, these metals can be expensive and toxic to cells. There is a need for more affordable and biologically safe fluorescent probes for CO detection. Drawing inspiration from the robust affinity exhibited by heme iron toward CO, in this work, a rhodamine derivative called RBF was developed for imaging CO in living cells by binding to Fe(III) and could be used for CO sensing. A Fe(III)-based fluorescent probe for CO imaging in living cells offers advantages of cost effectiveness, low toxicity, and ease of use. The fluorescence detection using the RBF-Fe system showed a direct correlation with increasing levels of CORM-3 (LOD = 146 nM) or the exposure time of CO gas, displaying reduced fluorescence. A CO test paper based on RBF-Fe was created for simple on-site CO detection, where fluorescence would diminish in response to CO exposure, allowing rapid (2 min) visual identification. Imaging of CO in living cells was successfully conducted using the probe system, showing a decrease in fluorescence intensity as CORM-3 concentrations increased, indicating its effectiveness in monitoring CO levels accurately within living cells.


Assuntos
Monóxido de Carbono , Compostos Férricos , Corantes Fluorescentes , Monóxido de Carbono/análise , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Humanos , Compostos Férricos/química , Compostos Férricos/análise , Imagem Óptica , Rodaminas/química , Células HeLa
7.
Nat Commun ; 15(1): 5518, 2024 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-38951539

RESUMO

Determining short-lived intermediate structures in chemical reactions is challenging. Although ultrafast spectroscopic methods can detect the formation of transient intermediates, real-space structures cannot be determined directly from such studies. Time-resolved serial femtosecond crystallography (TR-SFX) has recently proven to be a powerful method for capturing molecular changes in proteins on femtosecond timescales. However, the methodology has been mostly applied to natural proteins/enzymes and limited to reactions promoted by synthetic molecules due to structure determination challenges. This work demonstrates the applicability of TR-SFX for investigations of chemical reaction mechanisms of synthetic metal complexes. We fix a light-induced CO-releasing Mn(CO)3 reaction center in porous hen egg white lysozyme (HEWL) microcrystals. By controlling light exposure and time, we capture the real-time formation of Mn-carbonyl intermediates during the CO release reaction. The asymmetric protein environment is found to influence the order of CO release. The experimentally-observed reaction path agrees with quantum mechanical calculations. Therefore, our demonstration offers a new approach to visualize atomic-level reactions of small molecules using TR-SFX with real-space structure determination. This advance holds the potential to facilitate design of artificial metalloenzymes with precise mechanisms, empowering design, control and development of innovative reactions.


Assuntos
Manganês , Muramidase , Muramidase/química , Manganês/química , Cristalografia por Raios X , Porosidade , Complexos de Coordenação/química , Modelos Moleculares , Animais , Monóxido de Carbono/química , Fatores de Tempo , Galinhas
8.
Artif Cells Nanomed Biotechnol ; 52(1): 370-383, 2024 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-39017642

RESUMO

OBJECTIVE: The objective of this study was to test the therapeutic effect of carbon monoxide polyhemoglobin (polyCOHb) in haemorrhagic shock/resuscitation and its underlying mechanisms. METHODS: 48 rats were divided into two experimental parts, and 36 rats in the first experiment and 12 rats in the second experiment. In the first experimental part, 36 animals were randomly assigned to the following groups: hydroxyethyl starch group (HES group, n = 12), polyhemoglobin group (polyHb group, n = 12), and carbon monoxide polyhemoglobin group (polyCOHb group, n = 12). In the second experimental part, 12 animals were randomly assigned to the following groups: polyHb group (n = 6), and polyCOHb group (n = 6). Then the anaesthetised rats were haemorrhaged by withdrawing 50% of the animal's blood volume (BV), and resuscitated to the same volume of the animal's withdrawing BV with HES, polyHb, polyCOHb. In the first experimental part, the 72h survival rates of each groups animals were measured. In the second experimental part, the rats' mean arterial pressure (MAP), heart rate (HR), blood gas levels and other indicators were dynamically monitored in baseline, haemorrhagic shock (HS), at 0point resuscitation (RS 0h) and after 1 h resuscitation (RS 1h). The concentrations of malondialdehyde (MDA), superoxide dismutase (SOD), tumour necrosis factor-alpha (TNF-alpha) and interleukin-6 (IL-6) were measured by ELISA kits in both groups of rats at RS 1h. Changes in pathological sections were examined by haematoxylin-eosin (HE) staining. Nuclear factor erythroid 2-related factor 2 (Nrf2) and haem oxygenase-1 (HO-1) levels were detected by immunohistochemical analysis, while myeloperoxidase (MPO) levels were detected by immunofluorescence. DHE staining was used to determine reactive oxygen species (ROS) levels. RESULTS: The 72h survival rates of the polyHb and polyCOHb groups were 50.00% (6/12) and 58.33% (7/12) respectively, which were significantly higher than that of the 8.33% (1/12) in the HES group (p < 0.05). At RS 0h and RS 1h, the HbCO content of rats in the polyCOHb group (1.90 ± 0.21, 0.80 ± 0.21) g/L were higher than those in the polyHb group (0.40 ± 0.09, 0.50 ± 0.12)g/L (p < 0.05); At RS 1h, the MDA (41.47 ± 3.89 vs 34.17 ± 3.87 nmol/ml) in the plasma, Nrf2 and HO-1 content in the colon of rats in the polyCOHb group were lower than the polyHb group. And the SOD in the plasma (605.01 ± 24.46 vs 678.64 ± 36.37) U/mg and colon (115.72 ± 21.17 vs 156.70 ± 21.34) U/mg and the MPO content in the colon in the polyCOHb group were higher than the polyHb group (p < 0.05). CONCLUSIONS: In these haemorrhagic shock/resuscitation models, both polyCOHb and polyHb show similar therapeutic effects, and polyCOHb has more effective effects in maintaining MAP, correcting acidosis, reducing inflammatory responses than that in polyHb.


Assuntos
Ratos Sprague-Dawley , Ressuscitação , Choque Hemorrágico , Animais , Choque Hemorrágico/tratamento farmacológico , Choque Hemorrágico/terapia , Choque Hemorrágico/metabolismo , Ratos , Ressuscitação/métodos , Masculino , Colo/efeitos dos fármacos , Colo/patologia , Colo/metabolismo , Inflamação/tratamento farmacológico , Monóxido de Carbono/farmacologia , Monóxido de Carbono/metabolismo , Hemoglobinas , Estresse Oxidativo/efeitos dos fármacos
9.
J Nanobiotechnology ; 22(1): 416, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-39014402

RESUMO

Reactive oxygen species (ROS)-associated anticancer approaches usually suffer from two limitations, i.e., insufficient ROS level and short ROS half-life. Nevertheless, no report has synchronously addressed both concerns yet. Herein, a multichannel actions-enabled nanotherapeutic platform using hollow manganese dioxide (H-MnO2) carriers to load chlorin e6 (Ce6) sonosensitizer and CO donor (e.g., Mn2(CO)10) has been constructed to maximumly elevate ROS level and trigger cascade catalysis to produce CO. Therein, intratumoral H2O2 and ultrasound as endogenous and exogeneous triggers stimulate H-MnO2 and Ce6 to produce •OH and 1O2, respectively. The further cascade reaction between ROS and Mn2(CO)10 proceeds to release CO, converting short-lived ROS into long-lived CO. Contributed by them, such a maximumly-elevated ROS accumulation and long-lived CO release successfully suppresses the progression, recurrence and metastasis of lung cancer with a prolonged survival rate. More significantly, proteomic and genomic investigations uncover that the CO-induced activation of AKT signaling pathway, NRF-2 phosphorylation and HMOX-1 overexpression induce mitochondrial dysfunction to boost anti-tumor consequences. Thus, this cascade catalysis strategy can behave as a general means to enrich ROS and trigger CO release against refractory cancers.


Assuntos
Monóxido de Carbono , Neoplasias Pulmonares , Compostos de Manganês , Óxidos , Porfirinas , Espécies Reativas de Oxigênio , Espécies Reativas de Oxigênio/metabolismo , Neoplasias Pulmonares/metabolismo , Neoplasias Pulmonares/tratamento farmacológico , Humanos , Monóxido de Carbono/farmacologia , Monóxido de Carbono/metabolismo , Monóxido de Carbono/química , Animais , Compostos de Manganês/química , Compostos de Manganês/farmacologia , Óxidos/química , Óxidos/farmacologia , Camundongos , Porfirinas/química , Porfirinas/farmacologia , Clorofilídeos , Linhagem Celular Tumoral , Camundongos Endogâmicos BALB C , Peróxido de Hidrogênio/metabolismo , Camundongos Nus , Células A549
10.
Nat Commun ; 15(1): 5424, 2024 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-38926344

RESUMO

Anaerobic, acetogenic bacteria are well known for their ability to convert various one-carbon compounds, promising feedstocks for a future, sustainable biotechnology, to products such as acetate and biofuels. The model acetogen Acetobacterium woodii can grow on CO2, formate or methanol, but not on carbon monoxide, an important industrial waste product. Since hydrogenases are targets of CO inhibition, here, we genetically delete the two [FeFe] hydrogenases HydA2 and HydBA in A. woodii. We show that the ∆hydBA/hydA2 mutant indeed grows on CO and produces acetate, but only after a long adaptation period. SNP analyzes of CO-adapted cells reveal a mutation in the HycB2 subunit of the HydA2/HydB2/HydB3/Fdh-containing hydrogen-dependent CO2 reductase (HDCR). We observe an increase in ferredoxin-dependent CO2 reduction and vice versa by the HDCR in the absence of the HydA2 module and speculate that this is caused by the mutation in HycB2. In addition, the CO-adapted ∆hydBA/hydA2 mutant growing on formate has a final biomass twice of that of the wild type.


Assuntos
Acetobacterium , Proteínas de Bactérias , Monóxido de Carbono , Formiatos , Acetobacterium/genética , Acetobacterium/metabolismo , Acetobacterium/crescimento & desenvolvimento , Formiatos/metabolismo , Monóxido de Carbono/metabolismo , Proteínas de Bactérias/metabolismo , Proteínas de Bactérias/genética , Hidrogenase/metabolismo , Hidrogenase/genética , Mutação , Dióxido de Carbono/metabolismo , Transporte de Elétrons , Biomassa , Acetatos/metabolismo , Polimorfismo de Nucleotídeo Único
11.
Anal Chim Acta ; 1312: 342749, 2024 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-38834263

RESUMO

Carbon monoxide (CO) is an innate signaling molecule that can regulate immune responses and interact with crucial elements of the circadian clock. Moreover, pharmacologically, CO has been substantiated for its therapeutic advantages in animal models of diverse pathological conditions. Given that an excessive level of CO can be toxic, it is imperative to quantify the necessary amount for therapeutic use accurately. However, estimating gaseous CO is notably challenging. Therefore, novel techniques are essential to quantify CO in therapeutic applications and overcome this obstacle precisely. The classical Myoglobin (Mb) assay technique has been extensively used to determine the amount of CO-release from CO-releasing molecules (CORMs) within therapeutic contexts. Nevertheless, specific challenges arise when applying the Mb assay to evaluate CORMs featuring innovative molecular architectures. Here, we report a fluorinated photo-CORM (CORM-FBS) for the photo-induced CO-release. We employed the 19F NMR spectroscopy approach to monitor the release of CO as well as quantitative evaluation of CO release. This new 19F NMR approach opens immense opportunities for researchers to develop reliable techniques for identifying molecular structures, quantitative studies of drug metabolism, and monitoring the reaction process.


Assuntos
Monóxido de Carbono , Luz , Mioglobina , Monóxido de Carbono/análise , Mioglobina/química , Espectroscopia de Ressonância Magnética/métodos , Flúor/química , Animais , Processos Fotoquímicos
12.
Phys Chem Chem Phys ; 26(23): 16579-16588, 2024 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-38832404

RESUMO

The transsulfuration pathway plays a key role in mammals for maintaining the balance between cysteine and homocysteine, whose concentrations are critical in several biochemical processes. Human cystathionine ß-synthase is a heme-containing, pyridoxal 5'-phosphate (PLP)-dependent enzyme found in this pathway. The heme group does not participate directly in catalysis, but has a regulatory function, whereby CO or NO binding inhibits the PLP-dependent reactions. In this study, we explore the detailed structural changes responsible for inhibition using quantum chemical calculations to validate the experimentally observed bonding patterns associated with heme CO and NO binding and molecular dynamics simulations to explore the medium-range structural changes triggered by gas binding and propagating to the PLP active site, which is more than 20 Å distant from the heme group. Our results support a previously proposed mechanical signaling model, whereby the cysteine decoordination associated with gas ligand binding leads to breaking of a hydrogen bond with an arginine residue on a neighbouring helix. In turn, this leads to a shift in position of the helix, and hence also of the PLP cofactor, ultimately disrupting a key hydrogen bond that stabilizes the PLP in its catalytically active form.


Assuntos
Cistationina beta-Sintase , Simulação de Dinâmica Molecular , Fosfato de Piridoxal , Cistationina beta-Sintase/metabolismo , Cistationina beta-Sintase/química , Humanos , Fosfato de Piridoxal/metabolismo , Fosfato de Piridoxal/química , Gases/química , Gases/metabolismo , Óxido Nítrico/metabolismo , Óxido Nítrico/química , Ligação de Hidrogênio , Monóxido de Carbono/química , Monóxido de Carbono/metabolismo , Heme/química , Heme/metabolismo , Domínio Catalítico , Teoria Quântica , Cisteína/química , Cisteína/metabolismo
13.
Environ Sci Pollut Res Int ; 31(27): 39678-39689, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38831145

RESUMO

Carbon monoxide (CO) is a prominent air pollutant in cities, with far-reaching implications for both local air quality and global atmospheric chemistry. The long-term change in atmospheric CO levels at a specific location is influenced by a complex interplay of local emissions, atmospheric transport, and photochemical processes, making it a subject of considerable interest. This study presents an 8-year analysis (2014-2021) of in situ CO observations using a cutting-edge laser-based analyzer at an urban site in Ahmedabad, western India. The long-term observations reveal a subtle trend in CO levels, masked by contrasting year-to-year variations, particular after 2018, across distinct diurnal time windows. Mid-afternoon (12:00-16:00 h) CO levels, reflecting background and regional conditions, remained relatively stable over the study period. In contrast, evening (18:00-21:00 h) CO levels, influenced by local emissions, exhibited substantial inter-annual variability without discernible trends from 2014 to 2018. However, post-2018, evening CO levels showed a consistent decline, predating COVID-19 lockdown measures. This decline coincided with the nationwide adoption of Bharat stage IV emission standards and other measures aimed at reducing vehicular emissions. The COVID-19 lockdown in 2020 further resulted in a noteworthy 29% reduction in evening CO levels compared to the pre-lockdown (2014-2019) period, highlighting the potential for substantial CO reduction through stringent vehicular emission controls. The observed long-term changes in CO levels do not align with the decreasing emission estimated by various inventories from 2014 to 2018, suggesting a need for improved emission statistics in Indian urban regions. This study underscores the importance of ongoing continuous CO measurements in urban areas to inform policy efforts aimed at controlling atmospheric pollutants.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Monóxido de Carbono , Cidades , Monitoramento Ambiental , Monóxido de Carbono/análise , Índia , Poluentes Atmosféricos/análise , COVID-19 , Emissões de Veículos/análise
14.
Spectrochim Acta A Mol Biomol Spectrosc ; 320: 124644, 2024 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-38901235

RESUMO

Reaction between the polymeric [RuCl2(CO)2]n and the N,N-bidentate ligand, 8-amino-quinoline (Quin), in methanol, afforded the photoactivated CO releasing molecule with the formula of trans-(Cl,Cl)-[RuCl2(CO)2Quin]. In the presence of biomolecules or in solvents with varying polarity and coordinating abilities, the solvatochromic characteristics and dark stability were investigated. A new board band emerged in the visible spectrum during the illumination, and its position varies according to the type of solvent used, indicating the role of the solvent in controlling the nature of the CO-depleted species. Spectral methods were used in combination with density functional theory simulations to get insight into the local minimum structure and the electronic properties of the Ru(II) complex. The results of the myoglobin assay showed that within the first two hours of illumination, one of the two CO molecules was released. The cytotoxic properties of the Ru(II)-based complex were investigated against normal mice bone marrow stromal cells and malignant human acute monocytic leukaemia cells.


Assuntos
Aminoquinolinas , Monóxido de Carbono , Complexos de Coordenação , Rutênio , Animais , Camundongos , Humanos , Complexos de Coordenação/química , Complexos de Coordenação/farmacologia , Aminoquinolinas/química , Aminoquinolinas/farmacologia , Rutênio/química , Rutênio/farmacologia , Ligantes , Monóxido de Carbono/química , Mioglobina/química , Teoria da Densidade Funcional , Luz
16.
Environ Sci Technol ; 58(27): 12082-12090, 2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-38888120

RESUMO

Selective catalytic reduction using CO as a reducing agent (CO-SCR) has exhibited its application potential in coal-fired, steel, and other industrial sectors. In comparison to NH3-SCR, CO-SCR can achieve synergistic control of CO and NO pollutants, making it a powerful denitrification technology that treats waste with waste. Unfortunately, the competitive adsorption of O2 and NO on CO-SCR catalysts inhibits efficient conversion of NOx under O2-containing conditions. In this work, we obtained two Ir sites with different electron densities, Ir1 single atoms in the oxidized Irδ+ state and Ir0 nanoparticles in the metallic state, by controlled pretreatment of the Ir/ZSM-5 catalyst with H2 at 200 °C. The coexistence of Ir1 single atoms and Ir0 nanoparticles on ZSM-5 creates a synergistic effect, which facilitates the reduction of NO through CO in the presence of O2, following the Langmuir-Hinshelwood mechanism. The ONNO dimer is formed on the Ir1 single atom sites and then spills over to the neighboring Ir0 nanoparticles for subsequent reduction to N2 by CO. Specifically, this tandem reaction enables 83% NO conversion and 100% CO conversion on an Ir-based catalyst at 250 °C under 3% O2.


Assuntos
Monóxido de Carbono , Catálise , Monóxido de Carbono/química , Óxido Nítrico/química , Oxirredução , Adsorção
17.
Environ Monit Assess ; 196(7): 659, 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38916809

RESUMO

First-ever measurements of particulate matter (PM2.5, PM10, and TSP) along with gaseous pollutants (CO, NO2, and SO2) were performed from June 2019 to April 2020 in Faisalabad, Metropolitan, Pakistan, to assess their seasonal variations; Summer 2019, Autumn 2019, Winter 2019-2020, and Spring 2020. Pollutant measurements were carried out at 30 locations with a 3-km grid distance from the Sitara Chemical Industry in District Faisalabad to Bhianwala, Sargodha Road, Tehsil Lalian, District Chiniot. ArcGIS 10.8 was used to interpolate pollutant concentrations using the inverse distance weightage method. PM2.5, PM10, and TSP concentrations were highest in summer, and lowest in autumn or winter. CO, NO2, and SO2 concentrations were highest in summer or spring and lowest in winter. Seasonal average NO2 and SO2 concentrations exceeded WHO annual air quality guide values. For all 4 seasons, some sites had better air quality than others. Even in these cleaner sites air quality index (AQI) was unhealthy for sensitive groups and the less good sites showed Very critical AQI (> 500). Dust-bound carbon and sulfur contents were higher in spring (64 mg g-1) and summer (1.17 mg g-1) and lower in autumn (55 mg g-1) and winter (1.08 mg g-1). Venous blood analysis of 20 individuals showed cadmium and lead concentrations higher than WHO permissible limits. Those individuals exposed to direct roadside pollution for longer periods because of their occupation tended to show higher Pb and Cd blood concentrations. It is concluded that air quality along the roadside is extremely poor and potentially damaging to the health of exposed workers.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Monitoramento Ambiental , Material Particulado , Paquistão , Humanos , Poluentes Atmosféricos/análise , Material Particulado/análise , Poluição do Ar/estatística & dados numéricos , Estações do Ano , Organização Mundial da Saúde , Dióxido de Enxofre/análise , Cidades , Dióxido de Nitrogênio/análise , Exposição Ambiental/estatística & dados numéricos , Monóxido de Carbono/análise
18.
Dalton Trans ; 53(26): 11009-11020, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38874948

RESUMO

The toxicity profile of fac-[Re(CO)3(N-N)L]+ complexes against microbial and tumoral cells has been extensively studied, primarily focusing on modifications to the bidentate diimine (N-N) ligand. However, less attention has been paid to modifications of the axial ligand L, which is perpendicular to the Re-N-N plane. This study reveals that the high toxicity of the fac-[Re(CO)3(bpy)(Ctz)]+ complex may be attributed to the structural effect of the trityl (CPh3) group present in clotrimazole, as removal of phenyl rings causes a significant decrease in the activity against Staphylococcus aureus (S. aureus). Moreover, substitution of the 1-tritylimidazole ligand by the structurally related ligands PPh3 and PCy3 maintains similarly high activity levels. These findings contribute to understanding the interactions of toxic complexes with bacterial membranes, suggesting that the ligand structures play a crucial role in inhibiting cell wall synthesis processes, potentially including Lipid II synthesis. Compounds with Ph3E (E = C-imidazole; P) groups also showed to be 10 times more toxic than cisplatin against three mammalian cell lines (IC50: 2-4 µM). In contrast, the analogue 1-benzylimidazole and 1-tert-butylimidazole derivatives were as toxic as cisplatin. We observed that the decomposition of the [Re(I)(CO)3] fragment inside mammalian cell lines liberates CO, which is expected to exert biological effects. Therefore, compounds of this family possessing the structural motif Ph3E seem to combine high antimicrobial and antitumoral activities, the latter being much higher than that of cisplatin.


Assuntos
Antineoplásicos , Monóxido de Carbono , Complexos de Coordenação , Testes de Sensibilidade Microbiana , Rênio , Staphylococcus aureus , Humanos , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Complexos de Coordenação/síntese química , Staphylococcus aureus/efeitos dos fármacos , Monóxido de Carbono/química , Monóxido de Carbono/farmacologia , Rênio/química , Rênio/farmacologia , Antibacterianos/farmacologia , Antibacterianos/química , Antibacterianos/síntese química , Linhagem Celular Tumoral , Estrutura Molecular , Ligantes , Ensaios de Seleção de Medicamentos Antitumorais , Sobrevivência Celular/efeitos dos fármacos , Relação Estrutura-Atividade , Proliferação de Células/efeitos dos fármacos
19.
Environ Sci Technol ; 58(27): 12201-12211, 2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-38934498

RESUMO

The elevation of the low-temperature oxidation activity for Pt/CeO2 catalysts is challenging to meet the increasingly stringent requirements for effectively eliminating carbon monoxide (CO) from automobile exhaust. Although reducing activation is a facile strategy for boosting reactivity, past research has mainly concentrated on applying H2 as the reductant, ignoring the reduction capabilities of CO itself, a prevalent component of automobile exhaust. Herein, atomically dispersed Pt/CeO2 was fabricated and activated by CO, which could lower the 90% conversion temperature (T90) by 256 °C and achieve a 20-fold higher CO consumption rate at 200 °C. The activated Pt/CeO2 catalysts showed exceptional catalytic oxidation activity and robust hydrothermal stability under the simulated working conditions for gasoline or diesel exhausts. Characterization results illustrated that the CO activation triggered the formation of a large portion of Pt0 terrace sites, acting as inherent active sites for CO oxidation. Besides, CO activation weakened the Pt-O-Ce bond strength to generate a surface oxygen vacancy (Vo). It served as the oxygen reservoir to store the dissociated oxygen and convert it into active dioxygen intermediates. Conversely, H2 activation failed to stimulate Vo, but triggered a deactivating transformation of the Pt nanocluster into inactive PtxOy in the presence of oxygen. The present work offers coherent insight into the upsurging effect of CO activation on Pt/CeO2, aiming to set up a valuable avenue in elevating the efficiency of eliminating CO, C3H6, and NH3 from automobile exhaust.


Assuntos
Monóxido de Carbono , Oxirredução , Catálise , Monóxido de Carbono/química , Emissões de Veículos , Platina/química , Cério/química
20.
J Med Chem ; 67(12): 9789-9815, 2024 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-38864348

RESUMO

Carbon monoxide (CO) is endogenously produced in mammals, with blood concentrations in the high micromolar range in the hemoglobin-bound form. Further, CO has shown therapeutic effects in various animal models. Despite its reputation as a poisonous gas at high concentrations, we show that CO should have a wide enough safety margin for therapeutic applications. The analysis considers a large number of factors including levels of endogenous CO, its safety margin in comparison to commonly encountered biomolecules or drugs, anticipated enhanced safety profiles when delivered via a noninhalation mode, and the large amount of safety data from human clinical trials. It should be emphasized that having a wide enough safety margin for therapeutic use does not mean that it is benign or safe to the general public, even at low doses. We defer the latter to public health experts. Importantly, this Perspective is written for drug discovery professionals and not the general public.


Assuntos
Monóxido de Carbono , Monóxido de Carbono/metabolismo , Humanos , Animais
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