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1.
Proc Natl Acad Sci U S A ; 121(30): e2404013121, 2024 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-39024111

RESUMO

Rechargeable zinc-air batteries (ZABs) are regarded as a remarkably promising alternative to current lithium-ion batteries, addressing the requirements for large-scale high-energy storage. Nevertheless, the sluggish kinetics involving oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) hamper the widespread application of ZABs, necessitating the development of high-efficiency and durable bifunctional electrocatalysts. Here, we report oxygen atom-bridged Fe, Co dual-metal dimers (FeOCo-SAD), in which the active site Fe-O-Co-N6 moiety boosts exceptional reversible activity toward ORR and OER in alkaline electrolytes. Specifically, FeOCo-SAD achieves a half-wave potential (E1/2) of 0.87 V for ORR and an overpotential of 310 mV at a current density of 10 mA cm-2 for OER, with a potential gap (ΔE) of only 0.67 V. Meanwhile, FeOCo-SAD manifests high performance with a peak power density of 241.24 mW cm-2 in realistic rechargeable ZABs. Theoretical calculations demonstrate that the introduction of an oxygen bridge in the Fe, Co dimer induced charge spatial redistribution around Fe and Co atoms. This enhances the activation of oxygen and optimizes the adsorption/desorption dynamics of reaction intermediates. Consequently, energy barriers are effectively reduced, leading to a strong promotion of intrinsic activity toward ORR and OER. This work suggests that oxygen-bridging dual-metal dimers offer promising prospects for significantly enhancing the performance of reversible oxygen electrocatalysis and for creating innovative catalysts that exhibit synergistic effects and electronic states.

2.
Proc Natl Acad Sci U S A ; 120(26): e2305378120, 2023 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-37339221

RESUMO

Hydrogen peroxide (H2O2) is an important green oxidant in the field of sewage treatment, and how to improve its activation efficiency and generate free radicals with stronger oxidation performance is a key issue in current research. Herein, we synthesized a Cu-doped α-Fe2O3 catalyst (7% Cu-Fe2O3) for activation of H2O2 under visible light for degradation of organic pollutants. The introduction of a Cu dopant changed the d-band center of Fe closer to the Fermi level, which enhanced the adsorption and activation of the Fe site for H2O2, and the cleavage pathway of H2O2 changed from heterolytic cleavage to homolytic cleavage, thereby improving the selectivity of •OH generation. In addition, Cu doping also promoted the light absorption ability of α-Fe2O3 and the separation of hole-electron pairs, which enhanced its photocatalytic activities. Benefiting from the high selectivity of •OH, 7% Cu-Fe2O3 exhibited efficient degradation activities against ciprofloxacin, the degradation rate was 3.6 times as much as that of α-Fe2O3, and it had good degradation efficiency for a variety of organic pollutants.

3.
Proc Natl Acad Sci U S A ; 120(13): e2300085120, 2023 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-36952382

RESUMO

The peroxymonosulfate (PMS)-triggered radical and nonradical active species can synergistically guarantee selectively removing micropollutants in complex wastewater; however, realizing this on heterogeneous metal-based catalysts with single active sites remains challenging due to insufficient electron cycle. Herein, we design asymmetric Co-O-Bi triple-atom sites in Co-doped Bi2O2CO3 to facilitate PMS oxidation and reduction simultaneously by enhancing the electron transfer between the active sites. We propose that the asymmetric Co-O-Bi sites result in an electron density increase in the Bi sites and decrease in the Co sites, thereby PMS undergoes a reduction reaction to generate SO4•- and •OH at the Bi site and an oxidation reaction to generate 1O2 at the Co site. We suggest that the synergistic effect of SO4•-, •OH, and 1O2 enables efficient removal and mineralization of micropollutants without interference from organic and inorganic compounds under the environmental background. As a result, the Co-doped Bi2O2CO3 achieves almost 99.3% sulfamethoxazole degradation in 3 min with a k-value as high as 82.95 min-1 M-1, which is superior to the existing catalysts reported so far. This work provides a structural regulation of the active sites approach to control the catalytic function, which will guide the rational design of Fenton-like catalysts.

4.
Proc Natl Acad Sci U S A ; 120(15): e2300281120, 2023 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-37011202

RESUMO

The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO2@Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N4 active sites were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. The AC-induced charge redistribution of single atoms (SAs) was verified, thus strengthening the interaction between SAs and PMS. In detail, the incorporation of ACs optimized the HSO5- oxidation and SO5·- desorption steps, accelerating the reaction progress. As a result, the Vis/TiFeAS/PMS system rapidly eliminated 90.81% of 45 mg/L tetracycline (TC) in 10 min. The reaction process characterization suggested that PMS as an electron donor would transfer electron to Fe species in TiFeAS, generating 1O2. Subsequently, the hVB+ can induce the generation of electron-deficient Fe species, promoting the reaction circulation. This work provides a strategy to construct catalysts with multiple atom assembly-enabled composite active sites for high-efficiency PMS-based advanced oxidation processes (AOPs).

5.
Environ Sci Technol ; 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38319346

RESUMO

Microplastics (MPs) are considered to influence fundamental biogeochemical processes, but the effects of plant residue-MP interactions on soil carbon turnover in urban greenspaces are virtually unknown. Here, an 84-day incubation experiment was constructed using four types of single-vegetation-covered soils (6 years), showing that polystyrene MP (PSMP) pollution caused an unexpectedly large increase in soil CO2 emissions. The additional CO2 originating from highly bioavailable active dissolved organic matter molecules (<380 °C, predominantly polysaccharides) was converted from persistent carbon (380-650 °C, predominantly aromatic compounds) rather than PSMP derivatives. However, the priming effect of PSMP derivatives was weakened in plant-driven soils (resistivity: shrub > tree > grass). This can be explained from two perspectives: (1) Plant residue-driven humification processes reduced the percentage of bioavailable active dissolved organic matter derived from the priming effects of PSMPs. (2) Plant residues accelerated bacterial community succession (dominated by plant residue types) but slowed fungal community demise (retained carbon turnover-related functional taxa), enabling specific enrichment of glycolysis, the citric acid cycle and the pentose phosphate pathway. These results provide a necessary theoretical basis to understand the role of plant residues in reducing PSMP harm at the ecological level and refresh knowledge about the importance of biodiversity for ecosystem stability.

6.
Environ Sci Technol ; 58(2): 1010-1021, 2024 Jan 16.
Artigo em Inglês | MEDLINE | ID: mdl-37934921

RESUMO

Despite the increasing prevalence of atmospheric nanoplastics (NPs), there remains limited research on their phytotoxicity, foliar absorption, and translocation in plants. In this study, we aimed to fill this knowledge gap by investigating the physiological effects of tomato leaves exposed to differently charged NPs and foliar absorption and translocation of NPs. We found that positively charged NPs caused more pronounced physiological effects, including growth inhibition, increased antioxidant enzyme activity, and altered gene expression and metabolite composition and even significantly changed the structure and composition of the phyllosphere microbial community. Also, differently charged NPs exhibited differential foliar absorption and translocation, with the positively charged NPs penetrating more into the leaves and dispersing uniformly within the mesophyll cells. Additionally, NPs absorbed by the leaves were able to translocate to the roots. These findings provide important insights into the interactions between atmospheric NPs and crop plants and demonstrate that NPs' accumulation in crops could negatively impact agricultural production and food safety.


Assuntos
Antioxidantes , Microplásticos
7.
Molecules ; 29(9)2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38731489

RESUMO

Gallic acid (GA) is a type of polyphenolic compound that can be found in a range of fruits, vegetables, and tea. Although it has been confirmed it improves non-alcoholic fatty liver disease (NAFLD), it is still unknown whether GA can improve the occurrence of NAFLD by increasing the low-density lipoprotein receptor (LDLR) accumulation and alleviating cholesterol metabolism disorders. Therefore, the present study explored the effect of GA on LDLR and its mechanism of action. The findings indicated that the increase in LDLR accumulation in HepG2 cells induced by GA was associated with the stimulation of the epidermal growth factor receptor-extracellular regulated protein kinase (EGFR-ERK1/2) signaling pathway. When the pathway was inhibited by EGFR mab cetuximab, it was observed that the activation of the EGFR-ERK1/2 signaling pathway induced by GA was also blocked. At the same time, the accumulation of LDLR protein and the uptake of LDL were also suppressed. Additionally, GA can also promote the accumulation of forkhead box O3 (FOXO3) and suppress the accumulation of hepatocyte nuclear factor-1α (HNF1α), leading to the inhibition of proprotein convertase subtilisin/kexin 9 (PCSK9) mRNA expression and protein accumulation. This ultimately results in increased LDLR protein accumulation and enhanced uptake of LDL in cells. In summary, the present study revealed the potential mechanism of GA's role in ameliorating NAFLD, with a view of providing a theoretical basis for the dietary supplementation of GA.


Assuntos
Ácido Gálico , Lipoproteínas LDL , Receptores de LDL , Humanos , Ácido Gálico/farmacologia , Receptores de LDL/metabolismo , Células Hep G2 , Lipoproteínas LDL/metabolismo , Receptores ErbB/metabolismo , Sistema de Sinalização das MAP Quinases/efeitos dos fármacos , Transdução de Sinais/efeitos dos fármacos , Pró-Proteína Convertase 9/metabolismo , Pró-Proteína Convertase 9/genética
8.
Chron Respir Dis ; 21: 14799731241236492, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38411460

RESUMO

OBJECTIVE: The aim of this study is to investigate how much intermittent hypoxemia and airflow limitation contribute to cognitive impairment in overlap syndrome (OS), which is the coexistence of two common diseases, obstructive sleep apnea hypopnea syndrome (OSAHS) and chronic obstructive pulmonary disease (COPD). METHODS: We conducted a cross-sectional study of patients with OSAHS, COPD or OS, compared with normal controls, to determine the association between sleep apnea/pulmonary function-related indicators and cognitive dysfunction in individuals with OSAHS, COPD or OS. RESULTS: A total of 157 participants were recruited. Both OSAHS and OS presented lower adjusted Montreal cognitive assessment (MoCA) scores compared with COPD group. In addition, the MoCA score was significantly lower in COPD group compared with control group. The incidence of cognitive impairment was 57.4% in OSAHS group, and 78% in OS group, which were significantly higher than COPD group (29%) and control group (8.8%). Furthermore, a broader range of cognitive domains were affected in OS group compared with OSAHS group. Elevated levels of oxygen desaturation index (ODI) and/or apnea hypopnea index (AHI) were positively correlated with increased Epworth sleeping scale (ESS) in OSAHS and OS. Forced vital capacity (FVC), forced expiratory volume in 1 s (FEV1) and peak expiratory flow (PEF) were positively correlated with cognitive scores in OSAHS but not in OS. Serum level of hypoxia-inducible factor-1α (HIF-1α) was significantly higher in OS. Logistic regression identified ODI as an independent risk factor for cognitive impairment in OS, while severity of snoring and PEF were independent risk factors in OSAHS. DISCUSSION: This study revealed significant cognitive impairment in OS, OSAHS and COPD. Sleep-related indicators are warranted in OS patients for detection, differentiation and grading of cognitive impairment, whereas pulmonary functions are warranted in OSAHS patients for detection and early intervention of cognitive impairment.


Assuntos
Doenças Autoimunes , Disfunção Cognitiva , Doenças do Tecido Conjuntivo , Doença Pulmonar Obstrutiva Crônica , Síndromes da Apneia do Sono , Apneia Obstrutiva do Sono , Humanos , Estudos Transversais , Doença Pulmonar Obstrutiva Crônica/complicações , Apneia Obstrutiva do Sono/complicações , Disfunção Cognitiva/diagnóstico
9.
Small ; 19(28): e2301324, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37005337

RESUMO

The design of economical, efficient, and robust bifunctional oxygen electrocatalysts is greatly imperative for the large-scale commercialization of rechargeable Zn-air battery (ZAB) technology. Herein, the neoteric design of an advanced bifunctional electrocatalyst composed of CoN/Co3 O4 heterojunction hollow nanoparticles in situ encapsulated in porous N-doped carbon nanowires (denoted as CoN/Co3 O4 HNPs@NCNWs hereafter) is reported. The simultaneous implementation of interfacial engineering, nanoscale hollowing design, and carbon-support hybridization renders the synthesized CoN/Co3 O4 HNPs@NCNWs with modified electronic structure, improved electric conductivity, enriched active sites, and shortened electron/reactant transport pathways. Density functional theory computations further demonstrate that the construction of a CoN/Co3 O4 heterojunction can optimize the reaction pathways and reduce the overall reaction barriers. Thanks to the composition and architectural superiorities, the CoN/Co3 O4 HNPs@NCNWs exhibit distinguished oxygen reduction reaction and oxygen evolution reaction performance with a low reversible overpotential of 0.725 V and outstanding stability in KOH medium. More encouragingly, the homemade rechargeable liquid and flexible all-solid-state ZABs utilizing CoN/Co3 O4 HNPs@NCNWs as the air-cathode deliver higher peak power densities, larger specific capacities, and robust cycling stability, exceeding the commercial Pt/C + RuO2 benchmark counterparts. The concept of heterostructure-induced electronic modification herein may shed light on the rational design of advanced electrocatalysts for sustainable energy applications.

10.
Small ; 19(45): e2303329, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37438567

RESUMO

The development of atomically dispersed iron-nitrogen-carbon (Fe─N─C) catalysts as an alternative to precious platinum holds great potential for the substantial progress of a variety of oxygen reduction reaction (ORR)-associated energy conversion technologies. Nevertheless, the precise synthesis of Fe─N─C single atomic catalysts (SACs) with a high density of accessible active sites and pronounced electrocatalytic performance still remains an enormous challenge. Herein, an innovative extended Stöber method is designed for the controllable preparation of monodisperse small-sized N-doped carbon colloidal nanospheres (≈40 nm) anchoring atomically isolated Fe─N4 sites (abbreviated as Fe-SA@N-CNSs hereafter) with a narrow size distribution and high uniformity. Benefiting from the single Fe─N4 moieties and the unique spherical carbon substrate, the resultant Fe-SA@N-CNSs exhibit excellent ORR activity, outstanding long-term durability, and methanol tolerance in KOH electrolyte. More impressively, when further assembled into a flexible solid-state rechargeable zinc-air battery (ZAB), the Fe-SA@N-CNSs-driven ZAB delivers a higher open circuit voltage, a larger power density, and robust cycling/mechanical stability, outperforming the state-of-the-art Pt/C-based counterpart and further testifying the great potential of the as-prepared Fe-SA@N-CNSs in diverse ORR-related practical energy devices. The developed extended Stöber method provides an efficient and versatile avenue toward the preparation of a series of well-defined SACs for diverse electrocatalytic systems.

11.
Environ Sci Technol ; 57(24): 9005-9017, 2023 06 20.
Artigo em Inglês | MEDLINE | ID: mdl-37289192

RESUMO

Ocean warming (OW) caused by anthropogenic activities threatens ocean ecosystems. Moreover, microplastic (MP) pollution in the global ocean is also increasing. However, the combined effects of OW and MPs on marine phytoplankton are unclear. Synechococcus sp., the most ubiquitous autotrophic cyanobacterium, was used to evaluate the response to OW + MPs under two warming scenarios (28 and 32 °C compared to 24 °C). The enhancement of the cell growth rate and carbon fixation under OW were weakened by MP exposure. Specifically, OW + MPs reduced carbon fixation by 10.9 and 15.4% at 28 and 32 °C, respectively. In addition, reduction in photosynthesis pigment contents of Synechococcus sp. under OW was intensified under OW + MPs, supporting the lower growth rate and carbon fixation under OW + MPs. Transcriptome plasticity (the evolutionary and adaptive potential of gene expression in response to changing environments) enabled Synechococcus sp. to develop a warming-adaptive transcriptional profile (downregulation of photosynthesis and CO2 fixation) under OW. Nevertheless, the downregulation of photosynthesis and CO2 fixation were alleviated under OW + MPs to increase responsiveness to the adverse effect. Due to the high abundances of Synechococcus sp. and its contributions to primary production, these findings are important for understanding the effects of MPs on carbon fixation and ocean carbon fluxes under global warming.


Assuntos
Synechococcus , Synechococcus/genética , Synechococcus/metabolismo , Plásticos , Microplásticos , Ecossistema , Dióxido de Carbono , Oceanos e Mares
12.
Environ Sci Technol ; 57(1): 428-439, 2023 01 10.
Artigo em Inglês | MEDLINE | ID: mdl-36546883

RESUMO

To gather enough energy to respond to harmful stimuli, most immune cells quickly shift their metabolic profile. This process of immunometabolism plays a critical role in the regulation of immune cell function. Triclosan, a synthetic antibacterial component present in a wide range of consumer items, has been shown to cause immunotoxicity in a number of organisms. However, it is unclear whether and how triclosan impacts immunometabolism. Here, human macrophages were used as model cells to explore the modulatory effect of triclosan on immunometabolism. Untargeted metabolomics using integrated liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS) revealed that triclosan changed the global metabolic profile of macrophages. Furthermore, Seahorse energy analysis and 13C isotope-based metabolic flux analysis revealed that triclosan decreased mitochondrial respiratory activity and promoted a metabolic transition from oxidative phosphorylation to glycolysis. Triclosan also polarizes macrophages to the proinflammatory M1 phenotype and activates the nucleotide-binding oligomerization domain-like receptor family pyrin domain-containing receptor 3 (NLRP3) inflammasome, which is consistent with triclosan-induced metabolic phenotypic modifications. Collectively, these findings showed that triclosan exposure at micromolar concentrations caused metabolic reprogramming in macrophages, which triggered an inflammatory response. These findings are important for understanding the immunotoxicity caused by triclosan, which is necessary for determining the risk posed by triclosan in the environment.


Assuntos
Inflamassomos , Triclosan , Humanos , Inflamassomos/metabolismo , Inflamassomos/farmacologia , Triclosan/toxicidade , Macrófagos/metabolismo , Antibacterianos/farmacologia , Metabolômica
13.
Environ Sci Technol ; 57(20): 7743-7752, 2023 05 23.
Artigo em Inglês | MEDLINE | ID: mdl-37171176

RESUMO

Electroactive microbes can conduct extracellular electron transfer and have the potential to be applied as a bioresource to regulate soil geochemical properties and microbial communities. In this study, we incubated Fe-limited and Fe-enriched farmland soil together with electroactive microbes for 30 days; both soils were incubated with electroactive microbes and a common iron mineral, ferrihydrite. Our results indicated that the exogenous electroactive microbes decreased soil pH, total organic carbon (TOC), and total nitrogen (TN) but increased soil conductivity and promoted Fe(III) reduction. The addition of electroactive microbes also changed the soil microbial community from Firmicutes-dominated to Proteobacteria-dominated. Moreover, the total number of detected microbial species in the soil decreased from over 700 to less than 500. Importantly, the coexistence of N-transforming bacteria, Fe(III)-reducing bacteria and methanogens was also observed with the addition of electroactive microbes in Fe-rich soil, indicating the accelerated interspecies electron transfer of functional microflora.


Assuntos
Compostos Férricos , Microbiota , Solo/química , Microbiologia do Solo , Minerais/química , Oxirredução
14.
Environ Res ; 234: 116569, 2023 10 01.
Artigo em Inglês | MEDLINE | ID: mdl-37422116

RESUMO

Urban lakes represent important land-water and nature-human dual interfaces that promote the cycling of elements from terrestrials to sediments and consequently modulating the stabilization of regional climate. However, whether disturbances caused by extreme weather events can have substantial effects on carbon-nitrogen (C-N) cycling in these ecosystems are vague. To explore the impact of phytoplankton on the ecological retention time of C-N, two kinds of freshwater (natural and landscape) were collected and conducted a microcosm experiment using a freshwater algal species Chlorella vulgaris. Sandstorm events increased dissolved inorganic carbon in freshwater (65.55 ± 3.09 and 39.46 ± 2.51 mg·L-1 for samples from Jinyang and Nankai, respectively) and significantly affected the relevant pathways of photosynthesis in Chlorella vulgaris, including enhancing chlorophyll fluorescence (The effective quantum yield of PSII at the fifth day of incubation was 0.34 and 0.35 for Nankai and Jinyang, respectively), promoting the synthesis of sugars and inhibiting the synthesis of glycine and serine related proteins. Besides, carbon from plant biomass accumulation and cellular metabolism (fulvic acid-like, polyaromatic-type humic acid and polycarboxylate-type humic acid, etc.) was enriched into residues and become a kind of energy source for the decomposer (TC mass increased by 1.63-2.13 times after 21 days of incubation). This means that the accumulation and consumption of carbon and nitrogen in the residue can be used to track the processes controlling the long-term C-N cycle. Our findings shed light on the plant residues were key factors contributing to the formation of water carbon pool, breaks the traditional theory that dissolved carbonates cannot produce carbon sinks.


Assuntos
Carbono , Chlorella vulgaris , Humanos , Carbono/química , Ecossistema , Chlorella vulgaris/metabolismo , Substâncias Húmicas , Nitrogênio/metabolismo , Biomassa , Lagos , Água
15.
Proc Natl Acad Sci U S A ; 117(19): 10492-10499, 2020 05 12.
Artigo em Inglês | MEDLINE | ID: mdl-32332167

RESUMO

Protein corona formation is critical for the design of ideal and safe nanoparticles (NPs) for nanomedicine, biosensing, organ targeting, and other applications, but methods to quantitatively predict the formation of the protein corona, especially for functional compositions, remain unavailable. The traditional linear regression model performs poorly for the protein corona, as measured by R2 (less than 0.40). Here, the performance with R2 over 0.75 in the prediction of the protein corona was achieved by integrating a machine learning model and meta-analysis. NPs without modification and surface modification were identified as the two most important factors determining protein corona formation. According to experimental verification, the functional protein compositions (e.g., immune proteins, complement proteins, and apolipoproteins) in complex coronas were precisely predicted with good R2 (most over 0.80). Moreover, the method successfully predicted the cellular recognition (e.g., cellular uptake by macrophages and cytokine release) mediated by functional corona proteins. This workflow provides a method to accurately and quantitatively predict the functional composition of the protein corona that determines cellular recognition and nanotoxicity to guide the synthesis and applications of a wide range of NPs by overcoming limitations and uncertainty.


Assuntos
Previsões/métodos , Nanopartículas/metabolismo , Coroa de Proteína/metabolismo , Animais , Humanos , Aprendizado de Máquina , Macrófagos , Camundongos , Modelos Teóricos , Proteínas , Células RAW 264.7
16.
J Environ Manage ; 348: 119378, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-37883833

RESUMO

With the development of fermentation technology and the improvement of efficiency, anaerobic digestion (AD) has been playing an increasingly primary role in waste treatment and resource recovery. Temperature is undoubtedly the most important factor because it shapes microbial habitats, changes the composition of the microbial community structure, and even affects the expression of related functional genes. More than half of the biosphere is in a long-term or seasonal low-temperature environment (<20 °C), which makes psychrophilic AD have broad application prospects. Therefore, this review discusses the influencing factors and enhancement strategies of psychrophilic AD, which may provide a corresponding reference for future research on low-temperature fermentation. First, the occurrence of AD has been discussed. Then, the adaptation of microorganisms to the low-temperature environment was analyzed. Moreover, the challenges of psychrophilic AD have been reviewed. Meanwhile, the strategies for improving psychrophilic AD are presented. Further, from technology to application, the current situation of psychrophilic AD in pilot-scale tests is described. Finally, the economic and environmental feasibility of psychrophilic AD has been highlighted. In summary, psychrophilic AD is technically feasible, while economic analysis shows that the output benefits cannot fully cover the input costs, and the large-scale practical application of psychrophilic AD is still in its infancy. More research should focus on how to improve fermentation efficiency and reduce the investment cost of psychrophilic AD.


Assuntos
Reatores Biológicos , Temperatura Baixa , Anaerobiose , Fermentação , Temperatura , Metano
17.
Angew Chem Int Ed Engl ; 62(41): e202307504, 2023 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-37345265

RESUMO

The past decade has witnessed the great potential of Fe-based single-atom electrocatalysis in catalyzing oxygen reduction reaction (ORR). However, it remains a grand challenge to substantially improve their intrinsic activity and long-term stability in acidic electrolytes. Herein, we report a facile chemical vapor deposition strategy, by which high-density Fe atoms (3.97 wt%) are coordinated with square-planar para-positioned nitrogen and phosphorus atoms in a hierarchical carbon framework. The as-crafted atomically dispersed Fe catalyst (denoted Fe-SA/PNC) manifests an outstanding activity towards ORR over the entire pH range. Specifically, the half-wave potential of 0.92 V, 0.83 V, and 0.86 V vs. reversible hydrogen electrode (RHE) are attained in alkaline, neutral, and acidic electrolytes, respectively, representing the high performance among reported catalysts to date. Furthermore, after 30,000 durability cycles, the Fe-SA/PNC remains to be stable with no visible performance decay when tested in 0.1 M KOH and 0.5 M H2 SO4 , and only a minor negative shift of 40 mV detected in 0.1 M HClO4 , significantly outperforming commercial Pt/C counterpart. The coordination motif of Fe-SA/PNC is validated by density functional theory (DFT) calculations. This work provides atomic-level insight into improving the activity and stability of non-noble metal ORR catalysts, opening up an avenue to craft the desired single-atom electrocatalysts.

18.
Environ Sci Technol ; 56(17): 12368-12379, 2022 09 06.
Artigo em Inglês | MEDLINE | ID: mdl-35984995

RESUMO

Fine particulate matter (PM2.5) exposure causes respiratory diseases by inducing inflammation and oxidative stress. However, the correlation between the pulmonary microbiota and the progression of pulmonary inflammation and oxidative stress caused by PM2.5 is poorly understood. This study tested the hypothesis that the lung microbiota affects pulmonary inflammation and oxidative stress induced by PM2.5 exposure. Mice were exposed to PM2.5 intranasally for 12 days. Then, pulmonary microbiota transfer and antibiotic intervention were performed. Histological examinations, biomarker index detection, and transcriptome analyses were conducted. Characterization of the pulmonary microbiota using 16S rRNA gene sequencing showed that its diversity decreased by 75.2% in PM2.5-exposed mice, with increased abundance of Proteobacteria and decreased abundance of Bacteroidota. The altered composition of the microbiota was significantly correlated with pulmonary inflammation and oxidative stress-related indicators. Intranasal transfer of the pulmonary microbiota from PM2.5-exposed mice affected pulmonary inflammation and oxidative stress caused by PM2.5, as shown by increased proinflammatory cytokine levels and dysregulated oxidative damage-related biomarkers. Antibiotic intervention during PM2.5 exposure alleviated pulmonary inflammation and oxidative damage in mice. The pulmonary microbiota also showed substantial changes after antibiotic treatment, as reflected by the increased microbiota diversity, decreased abundance of Proteobacteria and increased abundance of Bacteroidota. These results suggest that pulmonary microbial dysbiosis can promote and affect pulmonary inflammation and oxidative stress during PM2.5 exposure.


Assuntos
Microbiota , Pneumonia , Animais , Antibacterianos/farmacologia , Biomarcadores , Inflamação/patologia , Pulmão , Camundongos , Estresse Oxidativo , Material Particulado/toxicidade , Pneumonia/induzido quimicamente , Pneumonia/patologia , RNA Ribossômico 16S
19.
Environ Sci Technol ; 56(13): 9556-9568, 2022 07 05.
Artigo em Inglês | MEDLINE | ID: mdl-35576172

RESUMO

Thorough investigations of the environmental fate and risks are necessary for the safe application of engineered nanomaterials. Nevertheless, the current understanding of potential transformations of MoS2 (an intensively studied two-dimensional nanosheet) upon interactions with ubiquitous environmentally relevant thiols (ERTs) in water is limited. This study revealed that two ERTs, l-cysteine and mercaptoacetic acid, could modify MoS2 by covalently grafting thiol groups on S atoms of 1T phases, improving the colloidal persistence and chemical stability of MoS2. Compared with the pristine form, MoS2-thiols with higher dispersity exhibited significantly mitigated envelopment and ultrastructural damage to microalgae. MoS2-triggered growth inhibition, upregulation of reactive oxygen species, photosynthetic injury, and metabolic perturbation in algae were remarkably attenuated by ERTs. The diminished capability for MoS2 to generate reactive intermediates and glutathione oxidation driven by ERTs caused the weakness of oxidative stress and negative effects. Additionally, molecular dynamics simulations demonstrated that ERTs altered the extent of the influence of MoS2 on the secondary structures and functions of adsorbed intracellular proteins, which also contributed to the lower phytotoxicity of MoS2. Our findings provide evidence for the crucial role of specific organic ligands in the risk of MoS2 in aquatic environments.


Assuntos
Molibdênio , Nanoestruturas , Dissulfetos , Nanoestruturas/química , Nanoestruturas/toxicidade , Compostos de Sulfidrila
20.
Environ Sci Technol ; 56(9): 5910-5919, 2022 05 03.
Artigo em Inglês | MEDLINE | ID: mdl-35389635

RESUMO

As extremely active sites processing terrestrially derived dissolved organic matter (DOM), lakes deserve sufficient attention. Because of high-complexity interactions between DOM and the surrounding environment, the natural and anthropogenic drivers controlling the composition and chemodiversity of DOM molecules in lakes remain unclear. Here, 13,952 DOM molecules were identified and assessed in 45 lakes across China via ultrahigh-resolution mass spectrometry. Furthermore, the effects of both natural and anthropogenic factors on the DOM composition, DOM chemodiversity, and greenhouse gas emissions were investigated. The majority of the variations in DOM chemical composition could be attributed to the differences in the hydrology and nutrient concentrations of the lakes, and human activities also played a role, mainly through atmospheric pollution. Environmental factors mainly influenced DOM chemodiversity in the form of S-containing compounds. N-containing compounds exhibited a positive correlation with CO2 emissions, while N- and S-free compounds exhibited a positive correlation with N2O emissions. These results facilitate a comprehensive understanding of the interactions between lake DOM and the surrounding environment, thereby providing a reference for the formulation of strategies aimed at the harmonious development of human and natural environments.


Assuntos
Lagos , Efeitos Antropogênicos , Matéria Orgânica Dissolvida , Atividades Humanas , Humanos , Lagos/química , Espectrometria de Massas
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