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1.
ChemSusChem ; : e202400683, 2024 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-38769898

RESUMO

The efficient acetate conversion from CO electroreduction is challenging due to the poor selectivity at high reaction rate, which requires the competition with H2 and other C2+ (i.e., ethylene, ethanol, n-propanol) reduction products. Electrolyte engineering is one of the efficient strategies to regulate the reaction microenvironment. In this work, the adding of sulfite (SO32-) with high nucleophilicity in KOH electrolytes was demonstrated to enable improving the CO-to-acetate conversion via generating a S-O chemical bond between SO32- and oxygenated *C2 intermediates (i.e., *CO-CO, *CO-COH) compared with that in pure KOH system on both synthesized Cu(200)- and normal commercial Cu(111)-facets-exposed metallic Cu catalysts. As a result, the prepared Cu(200)-facets-exposed metallic Cu catalyst with surface ions modification showed an superior Faradaic efficiency of 63.6% at -0.6 A·cm-2, and extraordinary absolute value of peak partial current density as high as 1.52 A·cm-2 with adding SO32- in KOH electrolytes, compared to the best reported values in both CO and CO2 electroreduction. Our work suggests an attractive strategy to introduce the oxyanion with high nucleophilicity in electrolytes to regulate the microenvironment for industrial-current-density electrosynthesis of acetate from CO electroreduction.

2.
Nat Struct Mol Biol ; 31(5): 801-809, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38267598

RESUMO

Regulation of the assembly and turnover of branched actin filament networks nucleated by the Arp2/3 complex is essential during many cellular processes, including cell migration and membrane trafficking. Cortactin is important for actin branch stabilization, but the mechanism by which this occurs is unclear. Given this, we determined the structure of vertebrate cortactin-stabilized Arp2/3 actin branches using cryogenic electron microscopy. We find that cortactin interacts with the new daughter filament nucleated by the Arp2/3 complex at the branch site, rather than the initial mother actin filament. Cortactin preferentially binds activated Arp3. It also stabilizes the F-actin-like interface of activated Arp3 with the first actin subunit of the new filament, and its central repeats extend along successive daughter-filament subunits. The preference of cortactin for activated Arp3 explains its retention at the actin branch and accounts for its synergy with other nucleation-promoting factors in regulating branched actin network dynamics.


Assuntos
Citoesqueleto de Actina , Complexo 2-3 de Proteínas Relacionadas à Actina , Actinas , Cortactina , Cortactina/metabolismo , Cortactina/química , Complexo 2-3 de Proteínas Relacionadas à Actina/metabolismo , Complexo 2-3 de Proteínas Relacionadas à Actina/química , Actinas/metabolismo , Actinas/química , Citoesqueleto de Actina/metabolismo , Animais , Microscopia Crioeletrônica , Modelos Moleculares , Humanos , Ligação Proteica , Proteína 3 Relacionada a Actina/metabolismo
3.
Nat Biotechnol ; 42(2): 247-252, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37169966

RESUMO

We present a statistical simulator, scDesign3, to generate realistic single-cell and spatial omics data, including various cell states, experimental designs and feature modalities, by learning interpretable parameters from real data. Using a unified probabilistic model for single-cell and spatial omics data, scDesign3 infers biologically meaningful parameters; assesses the goodness-of-fit of inferred cell clusters, trajectories and spatial locations; and generates in silico negative and positive controls for benchmarking computational tools.


Assuntos
Benchmarking , Modelos Estatísticos , Projetos de Pesquisa
4.
Angew Chem Int Ed Engl ; 63(7): e202315157, 2024 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-38143245

RESUMO

Methanol steam reforming (MSR) provides an alternative way for efficient production and safe transportation of hydrogen but requires harsh conditions and complicated purification processes. In this work, an efficient electrochemical-assisted MSR reaction for pure H2 production at lower temperature (~140 °C) is developed by coupling the electrocatalysis reaction into the MSR in a polymer electrolyte membrane electrolysis reactor. By electrochemically assisted, the two critical steps including the methanol dehydrogenation and water-gas shift reaction are accelerated, which is attributed to decreasing the methanol dehydrogenation energy and promoting the dissociation of H2 O to OH* by the applied potential. Furthermore, the reduced H2 partial pressure by the hydrogen oxidation and reduction process further promotes MSR. The combination of these advantages not only efficiently decreases the MSR temperature but also achieves the high rate of hydrogen production of 505 mmol H2 g Pt -1 h-1 with exceptionally high H2 selectivity (99 %) at 180 °C and a low voltage (0.4 V), and the productivity is about 30-fold than that of traditional MSR. This study opens up a new avenue to design novel electrolysis cells for hydrogen production.

5.
RSC Adv ; 13(49): 34724-34732, 2023 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-38035235

RESUMO

Searching for electrode materials with good electrical conductivity, fast charge/discharge rates and high storage capacity is essential for the development of high-performance metal ion batteries. Here, by performing first principles calculations, we have explored the feasibility of using two dimensional (2D) covalent organic frameworks (COFs) constructed by tri-quinazoline, triquinoxalinylene and benzoquinone, and tribenzoquinoxaline-5,10-dione and benzoquinone (BQ2), as electrode materials for lithium and sodium ion batteries. All the designed 2D COFs show good structure stability and are semiconductors with a band gap of 1.63-2.93 eV because of the high electron conjugation of the skeletons. The pyrazine N and carbonyl groups are revealed to be the active sites to combine Li/Na, while the Li-/Na-binding strength can be highly enhanced when the pyrazine N and the carbonyl group are located in adjacent sites. The designed 2D COFs show a low Li and Na diffusion barrier in the range of 0.28-0.56 eV to guarantee high rate performance for LIBs/SIBs. With abundant redox active sites, 2D BQ2-COF shows a high theoretical capacity of 1030 mA h g-1 with an average open circuit voltage of 0.80 and 0.67 V for LIBs and SIBs, respectively, which is comparable to that of the most advanced inorganic anode materials. Composed of only light elements, the designed 2D COFs are predicted to be promising anode materials with high energy density, good conductivity and high-rate performance for sustainable LIBs and SIBs.

6.
Angew Chem Int Ed Engl ; 62(49): e202313954, 2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-37867149

RESUMO

Due to the robust oxidation conditions in strong acid oxygen evolution reaction (OER), developing an OER electrocatalyst with high efficiency remains challenging in polymer electrolyte membrane (PEM) water electrolyzer. Recent theoretical research suggested that reducing the coordination number of Ir-O is feasible to reduce the energy barrier of the rate-determination step, potentially accelerating the OER. Inspired by this, we experimentally verified the Ir-O coordination number's role at model catalysts, then synthesized low-coordinated IrOx nanoparticles toward a durable PEM water electrolyzer. We first conducted model studies on commercial rutile-IrO2 using plasma-based defect engineering. The combined in situ X-ray absorption spectroscopy (XAS) analysis and computational studies clarify why the decreased coordination numbers increase catalytic activity. Next, under the model studies' guidelines, we explored a low-coordinated Ir-based catalyst with a lower overpotential of 231 mV@10 mA cm-2 accompanied by long durability (100 h) in an acidic OER. Finally, the assembled PEM water electrolyzer delivers a low voltage (1.72 V@1 A cm-2 ) as well as excellent stability exceeding 1200 h (@1 A cm-2 ) without obvious decay. This work provides a unique insight into the role of coordination numbers, paving the way for designing Ir-based catalysts for PEM water electrolyzers.

7.
Xi Bao Yu Fen Zi Mian Yi Xue Za Zhi ; 39(10): 904-909, 2023 Oct.
Artigo em Chinês | MEDLINE | ID: mdl-37882714

RESUMO

Objective To investigate the effect of SMAD family member 3(SMAD3) silenced by small interfering RNA (siRNA) on macrophage polarization and transforming growth factor ß1 (TGF-ß1)/ SMAD family signaling pathway in rheumatoid arthritis (RA). Methods RA macrophages co-cultured with rheumatoid arthritis fibroblast-like synoviocytes (RA-FLS) were used as a cell model. TGF-ß1 was used to stimulate macrophages, and SMAD3-specific siRNA (si-SMAD3) and negative control siRNA (si-NC) were transfected into human RA macrophages co-cultured in TranswellTM chamber. The expression of SMAD3 mRNA was detected by real-time fluorescence quantitative PCR, and the expression of TGF-ß1, SMAD3 and SMAD7 protein was detected by Western blot analysis. The contents of TGF-ß1 and IL-23 in cell culture supernatant were determined by ELISA. Cell proliferation was detected by CCK-8 assay. TranswellTM chamber was used to measure cell migration. Results Compared with the model group and the si-NC group, the expression of TGF-ß1, SMAD3 mRNA and protein in RA macrophages decreased significantly after silencing SMAD3. In addition, the secretion of IL-23 decreased significantly, and the cell proliferation activity and cell migration were inhibited, with high expression of SMAD7. Conclusion Knockdown of SMAD3 can promote M2 polarization and SMAD7 expression in RA macrophages.


Assuntos
Artrite Reumatoide , Proteína Smad3 , Proteína Smad7 , Humanos , Artrite Reumatoide/genética , Interleucina-23 , Macrófagos , RNA Mensageiro , RNA Interferente Pequeno/genética , Proteína Smad7/genética , Fator de Crescimento Transformador beta1/genética , Proteína Smad3/genética , Inativação Gênica
8.
Pharmaceutics ; 15(5)2023 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-37242686

RESUMO

Real-time measurement is important in modern dissolution testing to aid in parallel drug characterisation and quality control (QC). The development of a real-time monitoring platform (microfluidic system, a novel eye movement platform with temperature sensors and accelerometers and a concentration probe setup) in conjunction with an in vitro model of the human eye (PK-Eye™) is reported. The importance of surface membrane permeability when modelling the PK-Eye™ was determined with a "pursing model" (a simplified setup of the hyaloid membrane). Parallel microfluidic control of PK-Eye™ models from a single source of pressure was performed with a ratio of 1:6 (pressure source:models) demonstrating scalability and reproducibility of pressure-flow data. Pore size and exposed surface area helped obtain a physiological range of intraocular pressure (IOP) within the models, demonstrating the need to reproduce in vitro dimensions as closely as possible to the real eye. Variation of aqueous humour flow rate throughout the day was demonstrated with a developed circadian rhythm program. Capabilities of different eye movements were programmed and achieved with an in-house eye movement platform. A concentration probe recorded the real-time concentration monitoring of injected albumin-conjugated Alexa Fluor 488 (Alexa albumin), which displayed constant release profiles. These results demonstrate the possibility of real-time monitoring of a pharmaceutical model for preclinical testing of ocular formulations.

9.
JACS Au ; 3(3): 943-952, 2023 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-37006764

RESUMO

Metal-nitrogen-carbon single-atom catalysts (SACs) have exhibited substantial potential for CO2 electroreduction. Unfortunately, the SACs generally cannot generate chemicals other than CO, while deep reduction products are more appealing because of their higher market potential, and the origin of governing CO reduction (COR) remains elusive. Here, by using constant-potential/hybrid-solvent modeling and revisiting Cu catalysts, we show that the Langmuir-Hinshelwood mechanism is of importance for *CO hydrogenation, and the pristine SACs lack another site to place *H, thus preventing their COR. Then, we propose a regulation strategy to enable COR on the SACs: (I) the metal site has a moderate CO adsorption affinity; (II) the graphene skeleton is doped by a heteroatom to allow *H formation; and (III) the distance between the heteroatom and the metal atom is appropriate to facilitate *H migration. We discover a P-doped Fe-N-C SAC with promising COR reactivity and further extend this model to other SACs. This work provides mechanistic insight into the limiting factors of COR and highlights the rational design of the local structures of active centers in electrocatalysis.

10.
Sci Rep ; 13(1): 6070, 2023 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-37055423

RESUMO

Internal solitary waves (ISWs) in the South China Sea (SCS) are considerably modulated by the background currents. In this study, a three-dimensional high-resolution non-hydrostatic model is configured to investigate how the Kuroshio influences the generation and evolution of ISWs in the northern SCS. Three runs are conducted, including one control experiment without the Kuroshio and two sensitivity experiments with the Kuroshio in different paths. In the Luzon Strait (LS), the Kuroshio reduces the westward baroclinic energy flux radiated into the SCS, resulting in weakened ISWs. In the SCS basin, the background currents further refract the ISWs. With the leaping Kuroshio, the A-waves have longer crest lines but lower amplitudes compared with those in the control run. In contrast, the B-waves are less affected by the leaping Kuroshio. In the presence of looping Kuroshio, the wave refraction caused by the intrusion currents in the SCS basin results in the weakest amplitudes and energy but the widest crest lines of ISWs. Moreover, the energy of the A-waves exhibits double-peak structure along the crest lines. The crest lines of the B-waves extend to 19.5° N, which are more south than those in summer. These results highlight the importance of the Kuroshio on the 3D features of ISWs in the SCS.

11.
Oral Oncol ; 140: 106367, 2023 05.
Artigo em Inglês | MEDLINE | ID: mdl-36996606

RESUMO

OBJECTIVES: Human papillomavirus (HPV) positive head and neck squamous cell carcinoma (HNSCC) showed a considerably better prognosis with greater cisplatin sensitivity compared to their HPV-negative counterparts. Deciphering the underlying molecular mechanisms for HPV-induced cisplatin sensitivity is imperative to improve the prognosis of HPV-negative HNSCC. MATERIALS AND METHODS: The Fanconi anemia (FA) pathway status in HNSCC cells was analysed by detecting the cell cycle and chromosomal aberrations. XPF expression was validated using PCR, western blot, and immunohistochemistry. Droplet digital PCR and GFP expressing reporter assay were used to analyse the changes in alternative end-joining (alt-EJ) levels. The cisplatin sensitization was verified by cell proliferation assay, clonogenic cell survival assay, and TUNEL. RESULTS: HPV-positive HNSCC cells showed significant prolonged G2-M cell cycle arrest and aberrant chromosome formation under interstrand crosslinker treatment. Both mRNA and protein expression of XPF were considerably decreased in HPV-positive HNSCC, according to the analysis of cellular and clinical data. XPF inhibition upregulated the activity of the alt-EJ pathway in HPV-negative HNSCC cells by 32.02% (P < 0.001) but had little effect on HPV-positive HNSCC. Consistent with this, simultaneous suppression of XPF and alt-EJ enhanced cisplatin sensitivity of HPV-negative HNSCC in vitro and in vivo. CONCLUSION: HPV-positive HNSCC cells exhibit a profound FA pathway deficiency associated with reduced XPF expression. HNSCC cells with compromised XPF function are more reliant on the alt-EJ pathway for genomic stability. Combining FA and alt-EJ inhibition may be used to cope with the hard-to-treat HPV-negative HNSCC.


Assuntos
Carcinoma de Células Escamosas , Neoplasias de Cabeça e Pescoço , Infecções por Papillomavirus , Humanos , Carcinoma de Células Escamosas de Cabeça e Pescoço/tratamento farmacológico , Carcinoma de Células Escamosas de Cabeça e Pescoço/complicações , Cisplatino/farmacologia , Cisplatino/uso terapêutico , Papillomavirus Humano , Neoplasias de Cabeça e Pescoço/tratamento farmacológico , Neoplasias de Cabeça e Pescoço/complicações , Infecções por Papillomavirus/complicações , Linhagem Celular Tumoral , Carcinoma de Células Escamosas/tratamento farmacológico , Carcinoma de Células Escamosas/genética , Carcinoma de Células Escamosas/metabolismo , Papillomaviridae/fisiologia
12.
J Immunol Res ; 2023: 4743975, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36910905

RESUMO

Diffuse alveolar haemorrhage (DAH) is a rapidly developing condition owing to a lack of effective treatment and resulting in a high mortality rate in systemic lupus erythematosus (SLE). Neutrophil extracellular traps (NETs) contain numerous antigens and proinflammatory substances that directly damage the vascular endothelium and aggravate vascular inflammation, which is considered an important pathogenic factor of DAH in SLE. Therefore, blocking the release of NETs from neutrophils is an important target for the treatment of DAH in SLE. In this study, we investigated whether the inhibition of neutrophils releasing NETs could relieve DAH in SLE. Necrostatin-1 (Nec-1), a small molecule, has been reported to inhibit the release of NETs by neutrophils. In vitro experiments revealed that Nec-1 inhibited alveolar epithelial cell damage by preventing the release of NETs. Furthermore, vivo studies showed that Nec-1 alleviated lupus pulmonary haemorrhage in mice by reducing lung pathology severity, body weight, and serum inflammatory cytokine levels. Mechanistically, Nec-1 prevented NET release by inhibiting neutrophil elastase (NE) activation and N-Gasdermin D (N-GSDMD) expression. Additionally, immunohistochemistry and immunofluorescence findings showed that Nec-1 decreased NE expression in the lung tissues of mice with lupus pulmonary haemorrhage. Thus, NETs released by neutrophils contributed to the pathogenesis of DAH in SLE, and Nec-1 showed protective effects by the inhibition of NET production via the reduction of NE activation and N-GSDMD expression.


Assuntos
Armadilhas Extracelulares , Lúpus Eritematoso Sistêmico , Animais , Camundongos , Elastase de Leucócito/metabolismo , Neutrófilos , Hemorragia/metabolismo , Hemorragia/patologia
13.
Ann Transl Med ; 11(2): 94, 2023 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-36819530

RESUMO

Background: This study sought to assess the relationship between suppressor of cytokine signaling 3 (SOCS3) expression, SOCS3 promoter methylation status, and platinum-based chemotherapy responses in advanced non-small cell lung cancer (NSCLC) patients. Methods: A total of 400 advanced NSCLC patients with inoperable disease were enrolled in this study. All the patients underwent platinum-based chemotherapy treatment, and the clinical and prognostic outcomes of these patients were analyzed. The SOCS3 protein expression and SOCS3 promoter methylation status of the tumor tissues in these patients were also tested by immunohistochemistry and polymerase chain reaction (PCR), respectively. In addition, we knocked down SOCS3 expression via small-interfering RNA (siRNA) in the lung cancer cell lines and conducted in vitro analyses to examine cell viability and apoptosis. Results: Patients with higher expression levels of SOCS3 were found to have a lower average tumor stage, higher average tumor differentiation, and higher rates of positive chemotherapy responses than those with lower expression levels of SOCS3. SOCS3 promoter methylation was also found to be correlated with chemotherapy responses in these patients. In the prognostic analyses, only SOCS3 expression, but not SOCS3 promoter methylation, was found to be predictive of outcomes in advanced NSCLC patients. We also found that the pro-apoptotic effects of SOCS3 were mediated by the Janus kinase 2 (JAK2)/signal transducer and activator of transcription 3 (STAT3) signaling pathways in the lung cancer cells. Conclusions: Currently, there is a lack of reliable biomarkers for predicting the responses of NSCLC patients to chemotherapy. Our results may aid in clinical evaluations of NSCLC patients.

15.
J Am Chem Soc ; 145(4): 2195-2206, 2023 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-36629383

RESUMO

Copper-based catalysts are widely explored in electrochemical CO2 reduction (CO2RR) because of their ability to convert CO2 into high-value-added multicarbon products. However, the poor stability and low selectivity limit the practical applications of these catalysts. Here, we proposed a simple and efficient asymmetric low-frequency pulsed strategy (ALPS) to significantly enhance the stability and the selectivity of the Cu-dimethylpyrazole complex Cu3(DMPz)3 catalyst in CO2RR. Under traditional potentiostatic conditions, Cu3(DMPz)3 exhibited poor CO2RR performance with the Faradaic efficiency (FE) of 34.5% for C2H4 and FE of 5.9% for CH4 as well as the low stability for less than 1 h. We optimized two distinguished ALPS methods toward CH4 and C2H4, correspondingly. The high selectivities of catalytic product CH4 (FECH4 = 80.3% and above 76.6% within 24 h) and C2H4 (FEC2H4 = 70.7% and above 66.8% within 24 h) can be obtained, respectively. The ultralong stability for 300 h (FECH4 > 60%) and 145 h (FEC2H4 > 50%) was also recorded with the ALPS method. Microscopy (HRTEM, SAED, and HAADF) measurements revealed that the ALPS method in situ generated and stabilized extremely dispersive and active Cu-based clusters (∼2.7 nm) from Cu3(DMPz)3. Meanwhile, ex situ spectroscopies (XPS, AES, and XANES) and in situ XANES indicated that this ALPS method modulated the Cu oxidation states, such as Cu(0 and I) with C2H4 selectivity and Cu(I and II) with CH4 selectivity. The mechanism under the ALPS methods was explored by in situ ATR-FTIR, in situ Raman, and DFT computation. The ALPS methods provide a new opportunity to boost the selectivity and stability of CO2RR.

16.
Front Microbiol ; 14: 1341564, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-38249472

RESUMO

Here we investigated the potential impacts of soil inorganic nitrogen (SIN) content on the phylogenetic characteristics and ecological functions of soil bacterial communities in estuarine intertidal zones in China, aiming to comprehend the response mechanism of soil microorganisms to variations in SIN content within estuarine wetlands. Our results show that SIN in estuarine areas has a significant spatiotemporal variation on spatial and seasonal scales, in this study and is significantly associated with the phylogenetic diversity and phylogenetic turnover of soil bacterial communities. In addition, the results of the metagenomic analysis showed that the relative abundance of nitrogen-cycling functional genes in bacterial communities did not differ significantly in sampling sites and seasons, and weakly correlated with SIN content. Further, the results based on structural equation modeling (SEM) analysis showed that SIN directly and significantly regulated the phylogenetic characteristics of bacterial communities, thereby indirectly affecting the potential of bacterial nitrogen metabolism. This study emphasizes the key influence of SIN variations on the phylogenetic dissimilarity in soil bacterial communities. Moreover, although there was a weak direct relationship between the functional characteristics of the bacterial nitrogen metabolism and SIN content, the spatiotemporal variation of bacterial nitrogen metabolic potential may be indirectly regulated by SIN content by influencing the phylogenetic diversity in bacterial communities. Our study unravels the pivotal mechanisms through which SIN content influences bacterial communities, thereby offering novel insights into the microbial intricacies governing nitrogen metabolism within estuaries.

17.
Nat Commun ; 13(1): 6988, 2022 11 16.
Artigo em Inglês | MEDLINE | ID: mdl-36384964

RESUMO

Plasmodium species cause malaria and kill hundreds of thousands annually. The microtubule-based motor kinesin-8B is required for development of the flagellated Plasmodium male gamete, and its absence completely blocks parasite transmission. To understand the molecular basis of kinesin-8B's essential role, we characterised the in vitro properties of kinesin-8B motor domains from P. berghei and P. falciparum. Both motors drive ATP-dependent microtubule gliding, but also catalyse ATP-dependent microtubule depolymerisation. We determined these motors' microtubule-bound structures using cryo-electron microscopy, which showed very similar modes of microtubule interaction in which Plasmodium-distinct sequences at the microtubule-kinesin interface influence motor function. Intriguingly however, P. berghei kinesin-8B exhibits a non-canonical structural response to ATP analogue binding such that neck linker docking is not induced. Nevertheless, the neck linker region is required for motility and depolymerisation activities of these motors. These data suggest that the mechanochemistry of Plasmodium kinesin-8Bs is functionally tuned to support flagella formation.


Assuntos
Malária , Parasitos , Plasmodium , Masculino , Animais , Cinesinas , Parasitos/metabolismo , Microscopia Crioeletrônica , Ligação Proteica/fisiologia , Plasmodium/metabolismo , Trifosfato de Adenosina/metabolismo
18.
J Chin Polit Sci ; : 1-33, 2022 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-36193056

RESUMO

With the advent of the 'age of conspiracism', the harmfulness of conspiratorial narratives and mindsets on individuals' mentalities, on social relations, and on democracy, has been widely researched by political scientists and psychologists. One known negative effect of conspiracy theories is the escalation toward political radicalism. This study goes beyond the exploration of mechanisms underpinning the relationship between conspiracy theory and radicalization to focus on possible approaches to mitigating them. This study sheds light on the role of counter-conspiracy approaches in the process of deradicalization, adopting the case study of anti-China sentiment and racial prejudice amid the Covid-19 pandemic, through conducting an experiment (N = 300). The results suggest that, during critical events such as the Covid-19 pandemic, exposure to countermeasures to conspiracist information can reduce individual acceptance of radicalism. We investigated two methods of countering conspiracy theory, and found that: (1) a content-targeted 'inoculation' approach to countering conspiracy theory can prevent the intensification of radicalization, but does not produce a significant deradicalization effect; and (2) an audience-focused 'disenchantment' method can enable cognitive deradicalization, effectively reducing the perception of competitive victimhood, and of real and symbolic threats. This study is one of the first attempts to address causality between deradicalization and countermeasures to conspiracy theories in the US-China relations.

19.
Small ; 18(44): e2204015, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-36123142

RESUMO

The catalytic activity and selectivity of single-atom sites catalysts is strongly dependent on the supports structure and central metal coordination environment. However, the further optimization of electronic configuration to improve the catalytic performance is usually hampered by the strong coordination effect between the support and metal atoms. Herein, it is discovered that enzyme-mimicking catalytic performance can be enhanced at the fixed coordination single-atom Fe sites by regulating the Fe spin states. The X-ray absorption fine structure, 57 Fe Mössbauer spectrum, and temperature-dependent magnetization measurements reveal that the spin states of Fe in single FeN4  sites can be well manipulated via changing the pyrolysis temperature. The intermediate-spin Fe sites catalyst (t2g 4 eg 1) demonstrates a much higher peroxidase-mimicking activity in comparison with high-spin structure (t2g 3 eg 2). More importantly, the based enzymes system realizes sensitive detection of H2 O2  and glucose by colorimetric sensors with high catalytic activity and selectivity. Furthermore, theoretical calculations unveil that the intermediate-spin FeN4  promotes the OH* desorption process, thus greatly reducing the reaction energy barrier. These findings provide a route to design highly active enzyme-mimicking catalysts and an engineering approach for regulating spin states of metal sites to enhance their catalytic performance.


Assuntos
Ferro , Peroxidase , Ferro/química , Oxirredução , Catálise , Oxirredutases , Peroxidases
20.
Adv Mater ; 34(50): e2206528, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-36120846

RESUMO

Crystal phase engineering is an important strategy for designing noble-metal-based catalysts with optimized activity and stability. From the thermodynamic point of view, it remains a great challenge to synthesize unconventional phases of noble metals. Here, a new class of Pd-based nanostructure with unconventional rhombohedral Pd20 Sb7 phase is successfully synthesized. Benefiting from the high proportion of the unique exposed Pd20 Sb7 (003) surface, Pd20 Sb7 rhombohedra display much enhanced ethanol oxidation reaction (EOR) and oxygen reduction reaction performance compared with commercial Pd/C. Moreover, Pd20 Sb7 rhombohedra are also demonstrated as an effective air cathode in non-aqueous Li-air batteries with an overpotential of only 0.24 V. Density functional theory calculations reveal that the unique exposed facets of Pd20 Sb7 rhombohedra can not only reduce the excessive adsorption of CH3 CO* to CH3 COOH on Pd for promoting EOR process, but also weaken CO binding and CO poisoning. This work provides a new class of unconventional intermetallic nanomaterials with enhanced electrocatalytic activity.

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