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1.
JACS Au ; 4(3): 1243-1249, 2024 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-38559737

RESUMO

Integrating multiple functional components into vertically stacked heterostructures offers a prospective approach to manipulating the physicochemical properties of materials. The synthesis of vertically stacked heterogeneous noble metal oxides remains a challenge. Herein, we report a surface segregation approach to create vertically stacked amorphous Ir/Ru/Ir oxide nanosheets (NSs). Cross-sectional high-angle annular darkfield scanning transmission electron microscopy images demonstrate a three-layer heterostructure in the amorphous Ir/Ru/Ir oxide NSs, with IrOx layers located on the upper and lower surfaces, and a layer of RuOx sandwiched between the two IrOx layers. The vertically stacked heterostructure is a result of the diffusion of Ir atoms from the amorphous IrRuOx solid solution to the surface. The obtained A-Ir/Ru/Ir oxide NSs display an ultralow overpotential of 191 mV at 10 mA cm-2 toward acid oxygen evolution reaction and demonstrate excellent performance in a proton exchange membrane water electrolyzer, which requires only 1.63 V to achieve 1 A cm-2 at 60 °C, with virtually no activity decay observed after a 1300 h test.

2.
Nano Lett ; 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38624236

RESUMO

Phase transformation offers an alternative strategy for the synthesis of nanomaterials with unconventional phases, allowing us to further explore their unique properties and promising applications. Herein, we first observed the amorphization of Pt nanoparticles on the RuO2 surface by in situ scanning transmission electron microscopy. Density functional theory calculations demonstrate the low energy barrier and thermodynamic driving force for Pt atoms transferring from the Pt cluster to the RuO2 surface to form amorphous Pt. Remarkably, the as-synthesized amorphous Pt/RuO2 exhibits 14.2 times enhanced mass activity compared to commercial RuO2 catalysts for the oxygen evolution reaction (OER). Water electrolyzer with amorphous Pt/RuO2 achieves 1.0 A cm-2 at 1.70 V and remains stable at 200 mA cm-2 for over 80 h. The amorphous Pt layer not only optimized the *O binding but also enhanced the antioxidation ability of amorphous Pt/RuO2, thereby boosting the activity and stability for the OER.

3.
J Am Chem Soc ; 146(12): 8464-8471, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38483268

RESUMO

One-dimensional (1D) high-entropy compounds (HECs) with subnano diameters are highly attractive because long-range electron delocalization may occur along the high-entropy atomic chain, which results in extraordinary properties. Nevertheless, synthesizing such 1D HECs presents a substantial challenge, and the physicochemical attributes of these novel structures remain ambiguous. Herein, we developed a comelting-filling-freezing-modification (co-MFFM) method for synthesizing 1D high-entropy metal phosphide (HEP) by simultaneously encapsulating various metal cations within single-walled carbon nanotubes (SWCNTs) followed with a phosphorization process. The resulting 1D HEP nanowires confined within SWCNTs exhibit crucial features, including an ultrafine, high-entropy, and amorphous structure, along with a core-shell arrangement. The SWCNT as a shell could donate π electrons to 1D HEP for enhanced electron delocalization and protect 1D HEP as an atomically single-layered protective covering, thus boosting high electrocatalytic activity and stability. Moreover, the co-MFFM method demonstrates scalability for mass production and displays universal applicability to the synthesis of various 1D HECs.

4.
Small ; : e2401162, 2024 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-38511537

RESUMO

Constructing the pore structures in amorphous metal oxide nanosheets can enhance their electrocatalytic performance by efficiently increasing specific surface areas and facilitating mass transport in electrocatalysis. However, the accurate synthesis for porous amorphous metal oxide nanosheets remains a challenge. Herein, a facile nitrate-assisted oxidation strategy is reported for synthesizing amorphous mesoporous iridium oxide nanomeshes (a-m IrOx NMs) with a pore size of ∼4 nm. X-ray absorption characterizations indicate that a-m IrOx NMs possess stretched Ir─O bonds and weaker Ir-O interaction compared with commercial IrO2. Combining thermogravimetric-fourier transform infrared spectroscopy with differential scanning calorimetry measurements, it is demonstrated that sodium nitrate, acting as an oxidizing agent, is conducive to the formation of amorphous nanosheets, while the NO2 produced by the in situ decomposition of nitrates facilitates the generation of pores within the nanomeshes. As an anode electrocatalyst in proton exchange membrane water electrolyzer, a-m IrOx NMs exhibit superior performance, maintaining a cell voltage of 1.67 V at 1 A cm-2 for 120 h without obvious decay with a low loading (0.4 mgcatalyst cm-2). Furthermore, the nitrate-assisted method is demonstrated to be a general approach to prepare various amorphous metal oxide nanomeshes, including amorphous RhOx, TiOx, ZrOx, AlOx, and HfOx nanomeshes.

5.
Heliyon ; 10(6): e27523, 2024 Mar 30.
Artigo em Inglês | MEDLINE | ID: mdl-38510040

RESUMO

Fast and precise identification of microorganisms in the early diagnosis of sepsis is crucial for enhancing patient outcomes. Digital PCR (dPCR) is a highly sensitive approach for absolute quantification that can be utilized as a culture-independent molecular technique for diagnosing sepsis pathogens. We performed a retrospective investigation on 69 ICU patients suspected of sepsis. Our findings showed that a multiplex dPCR diagnostic kit outperformed blood culture in detecting the 15 most frequent bacteria that cause sepsis. Ninety-two bacterial strains were identified using dPCR at concentrations varying from 34 copies/mL to 105,800 copies/mL. The detection rate of dPCR was much greater than that of BC, with 27.53% (19/69) versus 73.91% (51/69). The sensitivity of dPCR was 63.2%. Our research indicated that dPCR outperforms blood culture in the early detection of sepsis-causing microorganisms. The diagnostic kit can detect a greater variety of pathogens with quantitative data, including polymicrobial infections, and has a quicker processing time. DPCR is a valuable technique that could aid in the proper management of sepsis.

6.
Biosci Rep ; 44(3)2024 Mar 29.
Artigo em Inglês | MEDLINE | ID: mdl-38372438

RESUMO

Eukaryotic cells coordinate growth under different environmental conditions via mechanistic target of rapamycin complex 1 (mTORC1). In the amino-acid-sensing signalling pathway, the GATOR2 complex, containing five evolutionarily conserved subunits (WDR59, Mios, WDR24, Seh1L and Sec13), is required to regulate mTORC1 activity by interacting with upstream CASTOR1 (arginine sensor) and Sestrin2 (leucine sensor and downstream GATOR1 complex). GATOR2 complex utilizes ß-propellers to engage with CASTOR1, Sestrin2 and GATOR1, removal of these ß-propellers results in substantial loss of mTORC1 capacity. However, structural information regarding the interface between amino acid sensors and GATOR2 remains elusive. With the recent progress of the AI-based tool AlphaFold2 (AF2) for protein structure prediction, structural models were predicted for Sentrin2-WDR24-Seh1L and CASTOR1-Mios ß-propeller. Furthermore, the effectiveness of relevant residues within the interface was examined using biochemical experiments combined with molecular dynamics (MD) simulations. Notably, fluorescence resonance energy transfer (FRET) analysis detected the structural transition of GATOR2 in response to amino acid signals, and the deletion of Mios ß-propeller severely impeded that change at distinct arginine levels. These findings provide structural perspectives on the association between GATOR2 and amino acid sensors and can facilitate future research on structure determination and function.


Assuntos
Aminoácidos , Serina-Treonina Quinases TOR , Aminoácidos/metabolismo , Serina-Treonina Quinases TOR/metabolismo , Complexos Multiproteicos/química , Alvo Mecanístico do Complexo 1 de Rapamicina , Arginina/metabolismo
7.
Appl Environ Microbiol ; 90(3): e0225523, 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38415602

RESUMO

Flavoprotein monooxygenases catalyze reactions, including hydroxylation and epoxidation, involved in the catabolism, detoxification, and biosynthesis of natural substrates and industrial contaminants. Among them, the 6-hydroxy-3-succinoyl-pyridine (HSP) monooxygenase (HspB) from Pseudomonas putida S16 facilitates the hydroxylation and C-C bond cleavage of the pyridine ring in nicotine. However, the mechanism for biodegradation remains elusive. Here, we refined the crystal structure of HspB and elucidated the detailed mechanism behind the oxidative hydroxylation and C-C cleavage processes. Leveraging structural information about domains for binding the cofactor flavin adenine dinucleotide (FAD) and HSP substrate, we used molecular dynamics simulations and quantum/molecular mechanics calculations to demonstrate that the transfer of an oxygen atom from the reactive FAD peroxide species (C4a-hydroperoxyflavin) to the C3 atom in the HSP substrate constitutes a rate-limiting step, with a calculated reaction barrier of about 20 kcal/mol. Subsequently, the hydrogen atom was rebounded to the FAD cofactor, forming C4a-hydroxyflavin. The residue Cys218 then catalyzed the subsequent hydrolytic process of C-C cleavage. Our findings contribute to a deeper understanding of the versatile functions of flavoproteins in the natural transformation of pyridine and HspB in nicotine degradation.IMPORTANCEPseudomonas putida S16 plays a pivotal role in degrading nicotine, a toxic pyridine derivative that poses significant environmental challenges. This study highlights a key enzyme, HspB (6-hydroxy-3-succinoyl-pyridine monooxygenase), in breaking down nicotine through the pyrrolidine pathway. Utilizing dioxygen and a flavin adenine dinucleotide cofactor, HspB hydroxylates and cleaves the substrate's side chain. Structural analysis of the refined HspB crystal structure, combined with state-of-the-art computations, reveals its distinctive mechanism. The crucial function of Cys218 was never discovered in its homologous enzymes. Our findings not only deepen our understanding of bacterial nicotine degradation but also open avenues for applications in both environmental cleanup and pharmaceutical development.


Assuntos
Oxigenases de Função Mista , Nicotina , Succinatos , Oxigenases de Função Mista/metabolismo , Nicotina/metabolismo , Flavina-Adenina Dinucleotídeo/metabolismo , Flavoproteínas/metabolismo , Hidroxilação , Piridinas/metabolismo
9.
Discov Med ; 35(179): 1123-1133, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-38058078

RESUMO

BACKGROUND: Ischemic stroke is an acute cerebrovascular disease with high mortality rates and poor prognoses. The influence of ischemic stroke includes a heavy economic burden to patients and society, making the exploration of new therapeutic targets for preventing and treating ischemic stroke urgent. This study aimed to explore the effect of phosphoglycerate mutase family member 5 (PGAM5) on oxidative stress and mitochondrial dysfunction in ischemic stroke. METHODS: The model of ischemic neuronal brain injury was established through culturing purchased human neuroblastoma cells (SH-SY5Y) by oxygen-glucose deprivation/reoxygenation (OGD/R). There were six experimental groups, including the OGD/R model group (SH-cells of OGD/R model), OE-NC group (cells of OGD/R model transfected with scramble cDNA), OE-PGAM5 group (cells of OGD/R model transfected with full-length sequence of PGAM5), si-NC group (cells of OGD/R model transfected with negative control small interference (si)RNA), si-PGAM5 group (cells of OGD/R model transfected with siRNA for PGAM5 knockdown), and a control group (cells cultured normally). Cell counting kit-8 (CCK-8) and flow cytometry were used to determine the activity and apoptosis of cells. Subsequently, the effects of PGAM5 expression on oxidative stress and mitochondrial dysfunction were analyzed. Mitochondrial morphology was observed by transmission electron microscopy (TEM), and mitochondrial membrane potential (MMP) was determined by JC-1 fluorescent probe. The levels of reactive oxygen species (ROS) were measured by flow cytometry, and levels of malondialdehyde (MDA) and superoxide dismutase (SOD) were measured by enzyme-linked immunosorbent assay (ELISA) assay. The expression of light chain (LC)3-II/I and autophagy-related gene 5 (ATG5) proteins were measured, and the regulation of PGAM5 expression on PTEN-induced putative protein kinase 1 (PINK1)/Parkin pathway was also explored. RESULTS: PGAM5 overexpression in OGD/R cells decreased the cell viability (p < 0.001) while increasing cell apoptosis (p < 0.01) compared to the OGD/R group. Inhibition of PGAM5 expression reversed the decreased cell viability (p < 0.001) and the increased cell apoptosis (p < 0.01). The JC-1 fluorescence showed that OGD/R treatment reduced mitochondrial membrane potential (p < 0.001) and TEM showed an obvious increase in phagosomes. In addition, OGD/R treatment enhanced oxidative stress (increased ROS, p < 0.01; increased MDA, p < 0.001; decreased SOD, p < 0.001), which could be further enhanced by overexpression of PGAM5 (ROS, p < 0.001; MDA, p < 0.001; SOD, p < 0.001) while reversed by the inhibition of PGAM5 (ROS, p < 0.01; MDA, p < 0.001; SOD, p < 0.001). The OGD/R-activated PINK1/Parkin pathway was inhibited by the knockdown of PGAM5 (p < 0.01) but promoted by the overexpression of PGAM5 (p < 0.05). CONCLUSIONS: PGAM5 stimulates oxidative stress and impairs mitochondrial function in ischemic stroke, and regulates the PINK1/Parkin signaling pathway. Therefore, PGAM5 is likely to be a target for the therapy of ischemic stroke.


Assuntos
AVC Isquêmico , Doenças Mitocondriais , Neuroblastoma , Humanos , Espécies Reativas de Oxigênio/metabolismo , Oxigênio/metabolismo , Oxigênio/farmacologia , Proteínas Quinases , Ubiquitina-Proteína Ligases/metabolismo , Ubiquitina-Proteína Ligases/farmacologia , Superóxido Dismutase/metabolismo , Superóxido Dismutase/farmacologia , Glucose/metabolismo , Apoptose/genética , Fosfoproteínas Fosfatases/farmacologia , Proteínas Mitocondriais/genética , Proteínas Mitocondriais/farmacologia
10.
Phys Chem Chem Phys ; 25(42): 29289-29302, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37876253

RESUMO

Bacterial DNA phosphorothioate (PT) modification provides a specific anchoring site for sulfur-binding proteins (SBDs). Besides, their recognition patterns include phosphate links and bases neighboring the PT-modified site, thereby bringing about genome sequence-dependent properties in PT-related epigenetics. Here, we analyze the contributions of the DNA backbone (phosphates and deoxyribose) and bases bound with two SBD proteins in Streptomyces pristinaespiralis and coelicolor (SBDSco and SBDSpr). The chalcogen-hydrophobic interactions remained constantly at the anchoring site while the adjacent bases formed conditional and distinctive non-covalent interactions. More importantly, SBD/PT-DNA interactions were not limited within the traditional "4-bp core" range from 5'-I to 3'-III but extended to upstream 5'-II and 5'-III bases and even 5''-I to 5''-III at the non-PT-modified complementary strand. From the epigenetic viewpoint, bases 3'-II, 5''-I, and 5''-III of SBDSpr and 3'-II, 5''-II, and 5''-III of SBDSco present remarkable differentiations in the molecular recognitions. From the protein viewpoint, H102 in SBDSpr and R191 in SBDSco contribute significantly while proline residues at the PT-bound site are strictly conserved for the PT-chalcogen bond. The mutual and make-up mutations are proposed to alter the SBD/PT-DNA recognition pattern, besides additional chiral phosphorothioate modifications on phosphates 5'-II, 5'-II, 3'-I, and 3'-II.


Assuntos
Calcogênios , DNA , DNA/química , DNA Bacteriano/química , Proteínas de Bactérias/metabolismo , Fosfatos/química
11.
Nano Lett ; 23(21): 10004-10012, 2023 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-37877790

RESUMO

Cation exchange (CE) in metal oxides under mild conditions remains an imperative yet challenging goal to tailor their composition and enable practical applications. Herein, we first develop an amorphization-induced strategy to achieve room-temperature CE for universally synthesizing single-atom doped In2O3 nanosheets (NSs). Density functional theory (DFT) calculations elucidate that the abundant coordination-unsaturated sites present in a-In2O3 NSs are instrumental in surmounting the energy barriers of CE reactions. Empirically, a-In2O3 NSs as the host materials successfully undergo exchange with unary cations (Cu2+, Co2+, Mn2+, Ni2+), binary cations (Co2+Mn2+, Co2+Ni2+, Mn2+Ni2+), and ternary cations (Co2+Mn2+Ni2+). Impressively, high-loading single-atom doped (over 10 atom %) In2O3 NSs were obtained. Additionally, Cu/a-In2O3 NSs exhibit an excellent ethanol yield (798.7 µmol g-1 h-1) with a high selectivity of 99.5% for the CO2 photoreduction. This work offers a new approach to induce CE reactions in metal oxides under mild conditions and constructs scalable single-atom doped catalysts for critical applications.

12.
Mol Immunol ; 163: 224-234, 2023 11.
Artigo em Inglês | MEDLINE | ID: mdl-37864932

RESUMO

Cigarette smoke is recognized as a major trigger for individuals with chronic obstructive pulmonary disease (COPD), leading to an amplified inflammatory response. The onset and progression of COPD are affected by multiple environmental and genetic risk factors, such as inflammatory mechanisms, oxidative stress, and an imbalance between proteinase and antiprotease. As a result, conventional drug therapies often have limited effectiveness. This study aimed to investigate the anti-inflammatory effect of sodium butyrate (SB) in COPD and explore its molecular mechanism, thereby deepening our understanding of the potential application of SB in the treatment of COPD. In our study, we observed an increase in the mRNA and protein expressions of inflammatory factors interleukin-1beta (IL-1ß), interleukin-6 (IL-6), tumor necrosis factor-alpha (TNF-α), Matrix metallopeptidase 9 (MMP9) and MMP12 in both NR8383 cell and rat models of COPD. However, these expressions were significantly reduced after SB treatment. Meanwhile, SB treatment effectively decreased the phosphorylation levels of nuclear transcription factor-kappa B (NF-κB) p65, c-Jun N-terminal kinase (JNK), and p38 mitogen-activated protein kinase (MAPK) and inhibited the nuclear translocation of these proteins in the COPD cells, leading to a reduction in the expression of various inflammatory cytokines. Additionally, SB also inhibited the expression level of the Nod-like receptor pyrin domain 3 (NLRP3) inflammasome, which consists of NLRP3, apoptosis-associated speck-like protein (ASC), and Caspase-1 in the cigeratte smoke extract (CSE)-stimulated cells. Our results showed that CSE down-regulated the mRNA levels of G-protein-coupled receptor 43 (GPR43) and GPR109A, while SB only up-regulated the expression of GPR43 and had no effect on GPR109A. Moreover, additional analysis demonstrated that the knockdown of GPR43 diminishes the anti-inflammatory effects of SB. It is evident that siRNA-mediated knockdown of GPR43 prevented the reduction in mRNA expression of IL-1ß, IL-6, TNF-α, MMP9, and MMP12, as well as the expression of phosphorylated proteins NF-κB p65, JNK, and p38 MAPKs with SB treatment. These findings revealed a SB/GPR43 mediated pathway essential for attenuating pulmonary inflammatory responses in COPD, which may offer potential new treatments for COPD.


Assuntos
Fumar Cigarros , Doença Pulmonar Obstrutiva Crônica , Ratos , Animais , NF-kappa B/metabolismo , Ácido Butírico/farmacologia , Ácido Butírico/uso terapêutico , Interleucina-6/metabolismo , Fator de Necrose Tumoral alfa/metabolismo , Proteína 3 que Contém Domínio de Pirina da Família NLR/metabolismo , Fumar Cigarros/efeitos adversos , Metaloproteinase 12 da Matriz/metabolismo , Metaloproteinase 12 da Matriz/uso terapêutico , Metaloproteinase 9 da Matriz/metabolismo , Doença Pulmonar Obstrutiva Crônica/metabolismo , Sistema de Sinalização das MAP Quinases , Inflamação/tratamento farmacológico , Inflamação/metabolismo , Anti-Inflamatórios/farmacologia , Anti-Inflamatórios/uso terapêutico , RNA Mensageiro/metabolismo
13.
Respir Med Case Rep ; 45: 101907, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37635732

RESUMO

Foreign body aspiration is a worldwide health problem that often results in life-threatening complications. Although flexible bronchoscopy is a safe procedure for removal of foreign bodies, it is usually unsuccessful in removing large foreign bodies from the airway. Gastrointestinal (GI) endoscopy, which is frequently used to remove foreign bodies from the gastrointestinal tract, has not been reported for retrieval of airway foreign bodies. In this report, we described three successful cases of removal of large airway foreign bodies by GI endoscopy. To avoid rigid bronchoscopy, GI endoscopy can be considered if flexible bronchoscopy has failed to remove a large or heavy airway foreign body in adult patients.

14.
Nat Commun ; 14(1): 5155, 2023 Aug 24.
Artigo em Inglês | MEDLINE | ID: mdl-37620303

RESUMO

Metasurfaces have promising potential to revolutionize a variety of photonic and electronic device technologies. However, metasurfaces that can simultaneously and independently control all electromagnetics (EM) waves' properties, including amplitude, phase, frequency, polarization, and momentum, with high integrability and programmability, are challenging and have not been successfully attempted. Here, we propose and demonstrate a microwave universal metasurface antenna (UMA) capable of dynamically, simultaneously, independently, and precisely manipulating all the constitutive properties of EM waves in a software-defined manner. Our UMA further facilitates the spatial- and time-varying wave properties, leading to more complicated waveform generation, beamforming, and direct information manipulations. In particular, the UMA can directly generate the modulated waveforms carrying digital information that can fundamentally simplify the architecture of information transmitter systems. The proposed UMA with unparalleled EM wave and information manipulation capabilities will spark a surge of applications from next-generation wireless systems, cognitive sensing, and imaging to quantum optics and quantum information science.

15.
Protein Sci ; 32(8): e4731, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37462942

RESUMO

The mTORC1 signaling pathway regulates cell growth and metabolism in a variety of organisms from yeast to human, and inhibition of the mTORC1 pathway has the prospect to treat cancer or achieve longevity. The tuberous sclerosis protein complex (TSCC) is a master negative regulator of the mTORC1 signaling pathway through hydrolyzing the GTP loaded on the small GTPase Rheb, which is a key activator of mTOR. However, the large size (~700 kDa) and complex structural organization of TSCC render it vulnerable to degradation and inactivation, thus limiting its potential application. In this work, based on thorough analysis and understanding of the structural mechanism of how the stabilization domain of TSC2 secures the association of TSC2-GAP with Rheb and thus enhances its GAP activity, we designed two proteins, namely SSG-MTM (short stabilization domain and GAP domain-membrane targeting motif) and SSG-TSC1N, which were able to function like TSCC to negatively regulate Rheb and mTORC1, but with much-reduced sizes (~1/15 and ~ 1/9 of the size of TSCC, respectively). Biochemical and cell biological assays demonstrated that these designed proteins indeed could promote the GTPase activity of Rheb to hydrolyze GTP, inhibit the kinase activity of mTORC1, and prevent mTORC1 from down-regulating catabolism and autophagy.


Assuntos
Alvo Mecanístico do Complexo 1 de Rapamicina , Neuropeptídeos , Proteína 2 do Complexo Esclerose Tuberosa , Esclerose Tuberosa , Humanos , Guanosina Trifosfato , Alvo Mecanístico do Complexo 1 de Rapamicina/metabolismo , Complexos Multiproteicos/metabolismo , Neuropeptídeos/genética , Neuropeptídeos/metabolismo , Proteína Enriquecida em Homólogo de Ras do Encéfalo/genética , Proteína Enriquecida em Homólogo de Ras do Encéfalo/metabolismo , Esclerose Tuberosa/genética , Esclerose Tuberosa/metabolismo , Proteína 2 do Complexo Esclerose Tuberosa/genética , Proteína 2 do Complexo Esclerose Tuberosa/metabolismo , Proteínas Supressoras de Tumor
16.
Small ; 19(45): e2302328, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37431211

RESUMO

The design of an efficient catalytic system with low Pt loading and excellent stability for the acidic oxygen reduction reaction is still a challenge for the extensive application of proton-exchange membrane fuel cells. Here, a gas-phase ordered alloying strategy is proposed to construct an effective synergistic catalytic system that blends PtM intermetallic compounds (PtM IMC, M = Fe, Cu, and Ni) and dense isolated transition metal sites (M-N4 ) on nitrogen-doped carbon (NC). This strategy enables Pt nanoparticles and defects on the NC support to timely trap flowing metal salt without partial aggregation, which is attributed to the good diffusivity of gaseous transition metal salts with low boiling points. In particular, the resulting Pt1 Fe1 IMC cooperating with Fe-N4 sites achieves cooperative oxygen reduction with a half-wave potential up to 0.94 V and leads to a high mass activity of 0.51 A  mgPt -1 and only 23.5% decay after 30 k cycles, both of which exceed DOE 2025 targets. This strategy provides a method for reducing Pt loading in fuel cells by integrating Pt-based intermetallics and single transition metal sites to produce an efficient synergistic catalytic system.

17.
Small ; 19(43): e2303360, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37381653

RESUMO

Transition metal oxides with high theoretical capacities are promising anode materials for lithium-ion batteries (LIBs). However, the sluggish reaction kinetics remain a bottleneck for fast-charging applications due to its slow Li+ migration rate. Herein, a strategy is reported of significantly reducing the Li+ diffusion barrier of amorphous vanadium oxide by constructing a specific ratio of the VO local polyhedron configuration in amorphous nanosheets. The optimized amorphous vanadium oxide nanosheets with a ratio ≈1:4 for octahedron sites (Oh ) to pyramidal sites (C4v ) revealed by Raman spectroscopy and X-ray absorption spectroscopy (XAS) demonstrate the highest rate capability (356.7 mA h g-1 at 10.0 A g-1 ) and long-term cycling life (455.6 mA h g-1 at 2.0 A g-1 over 1200 cycles). Density functional theory (DFT)calculations further verify that the local structure (Oh :C4v = 1:4) intrinsically changes the degree of orbital hybridization between V and O atoms and contributes to a higher intensity of electron occupied states near the Fermi level, thus resulting in a low Li+ diffusion barrier for favorable Li+ transport kinetics. Moreover, the amorphous vanadium oxide nanosheets possess a reversible VO vibration mode and volume expansion rate close to 0.3%, as determined through in situ Raman and in situ transmission electron microscopy.

18.
Opt Lett ; 48(12): 3223-3226, 2023 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-37319067

RESUMO

We report a thin-film circular polarizer consisting of three metal-grid layers to be used with a photoconductive antenna (PCA) to generate terahertz (THz) circularly polarized (CP) radiation. The polarizer has a high transmission with a measured 3 dB axial-ratio bandwidth of 54.7% from 0.57 to 1 THz. We further developed a generalized scattering matrix approach to provide insight into the underlying physical mechanism of the polarizer. We revealed that the Fabry-Pérot-like multi-reflection among gratings enables the high-efficiency polarization conversion. The successful realization of the CP PCA can find widespread application, such as THz circular dichroism spectroscopy, THz Mueller imaging, and ultrahigh-speed THz wireless communications.

19.
Environ Sci Technol ; 57(19): 7410-7420, 2023 05 16.
Artigo em Inglês | MEDLINE | ID: mdl-37134202

RESUMO

Hot springs represent a major source of arsenic release into the environment. Speciation is typically reported to be dominated by arsenite, arsenate, and inorganic thiolated arsenates. Much less is known about the relevance and formation of methylated thioarsenates, a group with species of high mobility and toxicity. In hot spring samples taken from the Tengchong volcanic region in China, methylated thioarsenates contributed up to 13% to total arsenic. Enrichment cultures were obtained from the corresponding sediment samples and incubated to assess their capability to convert arsenite into methylated thioarsenates over time and in the presence of different microbial inhibitors. In contrast to observations in other environmental systems (e.g., paddy soils), there was no solid evidence, supporting that the sulfate-reducing bacteria contributed to the arsenic methylation. Methanosarcina, the sole genus of methanogens detected in the enrichment cultures, as well as Methanosarcina thermophila TM-1, a pure strain within the genus, did methylate arsenic. We propose that methylated thioarsenates in a typical sulfide-rich hot spring environment like Tengchong form via a combination of biotic arsenic methylation driven by thermophilic methanogens and arsenic thiolation with either geogenic sulfide or sulfide produced by sulfate-reducing bacteria.


Assuntos
Arsênio , Arsenitos , Fontes Termais , Fontes Termais/microbiologia , Metilação , Sulfetos , Sulfatos
20.
J Am Chem Soc ; 145(22): 12148-12154, 2023 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-37224478

RESUMO

Spiral two-dimensional (2D) nanosheets exhibit unique physical and chemical phenomena due to their twisted structures. While self-assembly of clusters is an ideal strategy to form hierarchical 2D structures, it is challenging to form spiral nanosheets. Herein, we first report a screw dislocation involved assembled method to obtain 2D spiral cluster assembled nanosheets (CANs) with uniform square morphology. The 2D spiral Ru CANs with a length of approximately 4 µm and thickness of 20.7 ± 3.0 nm per layer were prepared via the assembly of 1-2 nm Ru clusters in the presence of molten block copolymer Pluronic F127. Cryo-electron microscopy (cryo-EM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) demonstrate the existence of screw dislocation in the spiral assembled structure. The X-ray absorption fine structure spectrum indicates that Ru clusters are Ru3+ species, and Ru atoms are mainly coordinated with Cl with a coordination number of 6.5. Fourier-transform infrared (FT-IR) spectra and solid-state nuclear magnetic resonance hydrogen spectra (1H NMR) indicate that the assembly process of Ru clusters is formed by noncovalent interactions, including hydrogen bonding and hydrophilic interactions. Additionally, the Ru-F127 CANs exhibit excellent photothermal conversion performance in the near-infrared (NIR) region.

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