ABSTRACT
The development of Cu-based atomic dispersed catalysts with tailored coordination environments represents a significant step forward in enhancing the electrocatalytic reduction of nitrate to ammonia. By precisely modulating the electronic structures of Cu active centers, the binding strength of the *NO3 intermediates is successfully tuned, thereby substantially improving the catalytic activity toward electrochemical nitrate reduction reaction (eNO3RR). This study reveals that the N4-coordinated Cu single-atom catalyst (Cu-SAC) exhibits superior performance due to its robust interaction with coordinating atoms. Notably, this optimized catalyst achieves a low limiting potential of -0.38 V, while the dual-atom system further reduces this value to -0.32 V, demonstrating exceptional activity. Detailed electronic structure analysis, including the examination of d-band centers, Bader charges, and projected density of states (PDOS), provides a comprehensive understanding of the origin of this high activity. Specifically, the high and concentrated density of states near the Fermi level plays a crucial role in facilitating the electrocatalytic nitrate reduction process. This work not only offers crucial insights into the underlying mechanisms of eNO3RR but also provides valuable guidelines for the rational design of highly efficient electrocatalysts for this important reaction.
ABSTRACT
Ammonia (NH3) electrosynthesis from nitrogen (N2) provides a promising strategy for carbon neutrality, circumventing the energy-intensive and carbon-emitting Haber-Bosch process. However, the current system still presents unsatisfactory performance, and the bottleneck lies in the rational synthesis of catalytic centers with efficient N2 chemisorption ability. Herein, a heteroatom ensemble effect is deliberately triggered over RuFe alloy with spatial proximity of metal sites to promote electrocatalytic nitrogen reduction. The heteronuclear RuFe ensemble with increased surface polarization and modulated electronic structure offers the feasibility to optimize the adsorption configuration of electroactive substances and facilitate chemical bond scission. The promotion of N2 chemisorption and the following hydrogenation are demonstrated by the in situ Fourier transform infrared spectroscopy characterizations. The catalyst thus permits significantly enhanced conversion of N2 to NH3 in a 0.1 M HCl environment, with a maximum ammonia yield rate of 75.45 µg h-1 mg-1 and a high Faradaic efficiency of 35.49%.
ABSTRACT
The development of a low-cost and efficient oxygen evolution reaction (OER) electrode is of critical importance for water electrolysis technologies. The general approach to achieving a high-efficiency OER electrode is to regulate catalytic material structures by synthetic control. Here we reported an orthogonal approach to obtaining the OER electrode without intentional design and synthesis, namely, recycling MnO2 cathodes from failed rechargeable aqueous batteries and investigating them as ready-made catalytic electrodes. The recycled MnO2 cathode showed very little Zn2+ storage capacity but surprisingly high OER activity with a low overpotential of 307 mV at 10 mA cm-2 and a small Tafel slope of 77.9 mV dec-1, comparable to the state-of-the-art RuO2 catalyst (310 mV, 86.9 mV dec-1). In situ electrochemical and theoretical studies jointly revealed that the accelerated OER kinetics of the recycled MnO2 electrode was attributed to the enlarged active surface area of MnO2 and optimized electronic structure of Mn sites. This work suggests failed battery cathodes as successful catalysis electrodes for sustainable energy development.
ABSTRACT
Ferroptosis is an iron-dependent cell death form characterized by reactive oxygen species (ROS) overgeneration and lipid peroxidation. Myricetin, a flavonoid that exists in numerous plants, exhibits potent antioxidant capacity. Given that iron accumulation and ROS-provoked dopaminergic neuron death are the two main pathological hallmarks of Parkinson's disease (PD), we aimed to investigate whether myricetin decreases neuronal death through suppressing ferroptosis. The PD models were established by intraperitoneally injecting 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) into rats and by treating SH-SY5Y cells with 1-methyl-4-phenylpyridinium (MPP+), respectively. Ferroptosis was identified by assessing the levels of Fe2+, ROS, malondialdehyde (MDA), and glutathione (GSH). The results demonstrated that myricetin treatment effectively mitigated MPTP-triggered motor impairment, dopamine neuronal death, and α-synuclein (α-Syn) accumulation in PD models. Myricetin also alleviated MPTP-induced ferroptosis, as evidenced by decreased levels of Fe2+, ROS, and MDA and increased levels of GSH in the substantia nigra (SN) and serum in PD models. All these changes were reversed by erastin, a ferroptosis activator. In vitro, myricetin treatment restored SH-SY5Y cell viability and alleviated MPP+-induced SH-SY5Y cell ferroptosis. Mechanistically, myricetin accelerated nuclear translocation of nuclear factor E2-related factor 2 (Nrf2) and subsequent glutathione peroxidase 4 (Gpx4) expression in MPP+-treated SH-SY5Y cells, two critical inhibitors of ferroptosis. Collectively, these data demonstrate that myricetin may be a potential agent for decreasing dopaminergic neuron death by inhibiting ferroptosis in PD.
Subject(s)
Disease Models, Animal , Dopaminergic Neurons , Ferroptosis , Flavonoids , Reactive Oxygen Species , Ferroptosis/drug effects , Animals , Flavonoids/pharmacology , Rats , Male , Reactive Oxygen Species/metabolism , Dopaminergic Neurons/drug effects , Dopaminergic Neurons/metabolism , Humans , Parkinson Disease/metabolism , Parkinson Disease/drug therapy , Cell Line, Tumor , Iron/metabolism , alpha-Synuclein/metabolism , Rats, Sprague-Dawley , Glutathione/metabolism , Lipid Peroxidation/drug effects , 1-Methyl-4-phenyl-1,2,3,6-tetrahydropyridine/adverse effects , NF-E2-Related Factor 2/metabolismABSTRACT
A finely controlled concentration polarization environment was deliberately created to fabricate a three-dimensional ordered Zn metal anode with (002)-dominated planes, which enabled a high-rate aqueous Ni-Zn pouch cell with a high discharge capacity of 187.3 mA h g-1 at 50 C, and a capacity retention of 94.7% and an average Coulombic efficiency of 99.8% for 500 charge/discharge cycles.
ABSTRACT
Background: The association between body mass index (BMI) and rapid eye-movement (REM) sleep-related behavioral disorder (RBD) in Parkinson's disease (PD) remains unknown. Our study was to investigate the association of BMI with RBD in PD patients. Methods: In this cross-sectional study, a total of 1,115 PD participants were enrolled from Parkinson's Progression Markers Initiative (PPMI) database. BMI was calculated as weight divided by height squared. RBD was defined as the RBD questionnaire (RBDSQ) score with the cutoff of 5 or more assessed. Univariable and multivariable logistic regression models were performed to examine the associations between BMI and the prevalence of RBD. Non-linear correlations were explored with use of restricted cubic spline (RCS) analysis. And the inflection point was determined by the two-line piecewise linear models. Results: We identified 426 (38.2%) RBD. The proportion of underweight, normal, overweight and obese was 2.61, 36.59, 40.36, and 20.44%, respectively. In the multivariate logistic regression model with full adjustment for confounding variables, obese individuals had an odds ratio of 1.77 (95% confidence interval: 1.21 to 2.59) with RBD compared with those of normal weight. In the RCS models with three knots, BMI showed a non-linear association with RBD. The turning points of BMI estimated from piecewise linear models were of 28.16 kg/m2, 28.10 kg/m2, and 28.23 kg/m2 derived from univariable and multivariable adjusted logistic regression models. The effect modification by depression on the association between BMI and RBD in PD was also found in this study. Furthermore, the sensitivity analyses linked with cognition, education, and ethnic groups indicated the robustness of our results. Conclusion: The current study found a significant dose-response association between BMI and RBD with a depression-based difference in the impact of BMI on RBD in PD patients.
ABSTRACT
Single-atom catalysts (SACs) have been widely studied in a variety of electrocatalysis. However, its application in the electrocatalytic nitrogen reduction reaction (NRR) field still suffers from unsatisfactory performance, due to the sluggish mass transfer and significant kinetic barriers. Herein, a novel rare-earth-lanthanum-evoked optimization strategy is proposed to boost ambient NRR over SACs. The incorporation of La with a large atomic radius tends to break the atomic long-range order and trigger the amorphization of SACs, endowing a greater density of dangling bonds that could modify affinity for reactants and adsorbates. Moreover, with unique 5d16s2 valence-electron configurations, its presence could further enrich the electron density and enhance the intrinsic activity of single-metal center via the valence orbital coupling. As expected, the La-modified catalyst presents excellent activity toward the electrochemical NRR, delivering a maximum ammonia yield rate of 33.91 µg h-1 mg-1 and a remarkable Faradaic efficiency of 53.82%.
ABSTRACT
Seawater electrolysis presents a promising avenue for green hydrogen production toward a carbon-free society. However, the electrode materials face significant challenges including severe chlorine-induced corrosion and high reaction overpotential, resulting in low energy conversion efficiency and low current density operation. Herein, we put forward a nanoporous nickel (npNi) cathode with high chlorine corrosion resistance for energy-efficient seawater electrolysis at industrial current densities (0.4-1 A cm-2). With the merits of an electrostatic chlorine-resistant surface, modulated Ni active sites, and a robust three-dimensional open structure, the npNi electrode showed a low hydrogen evolution reaction overpotential of 310 mV and a high electricity-hydrogen conversion efficiency of 59.7% at 400 mA cm-2 in real seawater and outperformed most Ni-based seawater electrolysis cathodes in recent publications and the commercial Ni foam electrode (459 mV, 46.4%) under the same test condition. In situ electrochemical impedance spectroscopy, high-frame-rate optical microscopy, and first-principles calculation revealed that the improved corrosion resistance, enhanced intrinsic activity, and mass transfer were responsible for the lowered electrocatalytic overpotential and enhanced energy efficiency.
ABSTRACT
Accounting for one third of global energy-related carbon emissions, the construction and operation of buildings are crucial for mitigating climate change. Decarbonization potentials of embodied and operational energy use in buildings are worth exploring from a life-cycle perspective. This paper focuses on the individual building level and collects the latest cases, to offer a comprehensive and timely understanding of the assessment and reduction of building life cycle carbon emissions (LCCEs). As for the collected cases, the operational process accounts for the largest share of building LCCEs, averaging 67%, followed by the production and construction phase, averaging 31%. Carbon emissions from the demolition process are relatively low, averaging 2%. The most commonly used method for assessing LCCEs is process-based, combining the activity level and carbon emission factors. Advanced technologies such as building information modelling and building performance simulation have been employed in recent years to assess embodied and operational carbon emissions effectively. Different approaches are proposed for the decarbonization of each stage in the building life cycle. In the production stage, the effective approaches could be optimizing the building structure, improving the material performance, and using bio-based materials, etc. Prefabrication technology is helpful to decarbonize the construction process. Energy conservation and electrification, renewable energy integration, and smart energy management can effectively reduce the building's operational carbon emissions. Beyond the life cycle, recycling waste materials is proven to have great environmental benefits. Further studies are suggested to trade off the embodied and operational carbon, to fully explore building life-cycle decarbonization potentials.
ABSTRACT
Carbon-supported Pd-based clusters are one of the most promising anodic catalysts for ethanol oxidation reaction (EOR) due to their encouraging activity and practical applications. However, unclear growth mechanism of Pd-based clusters on the carbon-based materials has hindered their extensive applications. Herein, we first introduce multi-void spherical PdBi cluster/carbon cloth (PdBi/CC) composites by an electrodeposition routine. The growth mechanism of PdBi clusters on the CC supports has been systemically investigated by evaluating the selected samples and tuning their compositions, which involve the big difference in standard redox potential between Pd2+/Pd and Bi3+/Bi and easy adsorption of Bi3+ on the surface of Pd-rich seeds. Benefitting from the ensembles of many nanocrystal subunits, multi-void spherical PdBi clusters can present collective properties and novel functionalities. In addition, the outstanding characteristics of CC supports enable PdBi clusters with stable nanostructures. Thanks to the unique structure, Pd20Bi/CC catalysts manifest higher EOR activity and better stability compared to Pd/CC. Systematic characterizations and a series of CO poisoning tests further confirm that the dramatically enhanced EOR activity and stability can be attributed to the incorporation of Bi species and the strong coupling of the structure between PdBi clusters and CC supports.
ABSTRACT
BACKGROUND: Preeclampsia is a placentally induced syndrome with diverse clinical presentation that currently has no cure. Oxidative stress is a potent inducer of placental dysfunction. The apelin receptor (APJ) system is a pleiotropic pathway with a potential for therapeutic targeting in preeclampsia. This study examines the alteration of circulating apelin levels and placental APJ expression in preeclampsia and investigates whether apelin/APJ system can protect placental trophoblast from hypoxia-induced oxidative stress injury through PI3K/AKT signaling pathway. RESULTS: Our results confirmed that maternal apelin concentration was increased in women with preeclampsia, but APJ expression was reduced in the preeclamptic placentas. Apelin-13 treatment not only specifically attenuated CoCl2-induced superoxide production, but also prevented CoCl2-induced reduction of SOD activity and SOD1 expression. In addition, apelin-13 suppressed CoCl2-induced apoptosis by increasing the expression of bcl-2/bax ratio and by decreasing the expression of active caspase-3 in placental trophoblasts. Furthermore, we found that apelin-13 binding APJ activated the PI3K and AKT kinases and inhibition of PI3K kinase significantly blocked the anti-oxidative effects of apelin-13 in placental trophoblasts. CONCLUSIONS: Decrease of placental APJ expression is associated with oxidative stress-induced placental dysfunction in preeclampsia, and increased circulating apelin could be a moderately successful marker to differentiate subjects with preeclampsia from healthy pregnant women. Inhibition of superoxide production and caspase-3 cleavage, together with upregulation of SOD activity/expression and bcl-2/bax ratio, could be the potential molecular mechanisms by which apelin-13/APJ protects placental trophoblasts from oxidative stress injury.
Subject(s)
Oxidative Stress , Pre-Eclampsia , Trophoblasts , Female , Humans , Pregnancy , Apelin/genetics , Apelin/metabolism , Apelin/pharmacology , bcl-2-Associated X Protein/metabolism , Caspase 3/metabolism , Hypoxia/metabolism , Phosphatidylinositol 3-Kinases/genetics , Phosphatidylinositol 3-Kinases/metabolism , Pre-Eclampsia/metabolism , Proto-Oncogene Proteins c-akt/genetics , Proto-Oncogene Proteins c-akt/metabolism , Signal Transduction , Superoxide Dismutase/metabolism , Superoxides/metabolism , Trophoblasts/metabolismABSTRACT
Autonomic symptoms (AS) are critical in Parkinson's disease (PD). We aimed to determine the relative significance of clinical factors allowing predictions about incidence of AS, and examine AS profiles among PD patients by motor subtype and its relation to AS. The cross-sectional data of a multicentre sample, including 714 PD patients and 194 healthy controls from Parkinson's Progression Marker Initiative study and Pingchan granule study were analyzed, stratified by PD subtypes [postural instability and gait disturbances (PIGD), tremor dominant (TD), and indeterminate] and domain autonomic dysfunction. Compared with healthy controls, PD patients scored higher in the total Scales for Outcomes in Parkinson's Disease-Autonomic dysfunction score and in several domain scores in particular, and there was a significant overlap in domain AS. Risk factors of individual domain autonomic dysfunction were heterogeneous. PIGD and indeterminate were the predominant subtypes in pupillomotor and thermoregulatory symptoms. TD and indeterminate were more likely to suffer from cardiovascular problem. The odd in sexual dysfunction was significant for PIGD. Gastrointestinal and urinary symptoms seemed not to be associated with a specific subtype. Our study demonstrated that AS were highly heterogeneous and 3 subtypes differed in autonomic performance, providing clues to understand mechanisms underlying AS in PD.
Subject(s)
Parkinson Disease , Primary Dysautonomias , Humans , Cross-Sectional Studies , Tremor , Autonomic Nervous SystemABSTRACT
Confinement effects in highly porous nanostructures can effectively adjust the selectivity and kinetics of electrochemical reactions, which can boost the methanol oxidation reaction (MOR). In this work, carbonized ZIF-8-confined hollow PtCo nanospheres (PtCo@carbonized ZIF-8) were fabricated using a facile strategy. A monodisperse confined region was successfully prepared, and the dispersion of the PtCo nanoparticles (NPs) could be precisely regulated, allowing for the effective tuning of the confined region. Thus, the precise regulation of the catalytic reaction was achieved. Importantly, hollow PtCo NPs were prepared using a method based on the Kirkendall effect, and their forming mechanism was systematically investigated. Because of the confinement effects of carbonized zeolitic imidazolate framework-8 (ZIF-8), the crystal and electronic structures of the PtCo NPs were able to be effectively tuned. Our electrochemical results show that PtCo@carbonized ZIF-8 composites manifest a higher mass activity (1.4 A mgPt-1) and better stability compared to commercial Pt/C.
ABSTRACT
In this paper, we develop a general rectangular multiple-relaxation-time lattice Boltzmann (RMRT-LB) method for the Navier-Stokes equations (NSEs) and nonlinear convection-diffusion equation (NCDE) by extending our recent unified framework of the multiple-relaxation-time lattice Boltzmann (MRT-LB) method [Chai and Shi, Phys. Rev. E 102, 023306 (2020)10.1103/PhysRevE.102.023306], where an equilibrium distribution function (EDF) [Lu et al., Philos. Trans. R. Soc. A 369, 2311 (2011)10.1098/rsta.2011.0022] on a rectangular lattice is utilized. The anisotropy of the lattice tensor on a rectangular lattice leads to anisotropy of the third-order moment of the EDF, which is inconsistent with the isotropy of the viscous stress tensor of the NSEs. To eliminate this inconsistency, we extend the relaxation matrix related to the dynamic and bulk viscosities. As a result, the macroscopic NSEs can be recovered from the RMRT-LB method through the direct Taylor expansion method. Whereas the rectangular lattice does not lead to the change of the zero-, first- and second-order moments of the EDF, the unified framework of the MRT-LB method can be directly applied to the NCDE. It should be noted that the RMRT-LB model for NSEs can be derived on the rDdQq (q discrete velocities in d-dimensional space, d≥1) lattice, including rD2Q9, rD3Q19, and rD3Q27 lattices, while there are no rectangular D3Q13 and D3Q15 lattices within this framework of the RMRT-LB method. Thanks to the block-lower triangular relaxation matrix introduced in the unified framework, the RMRT-LB versions (if existing) of the previous MRT-LB models can be obtained, including those based on raw (natural) moment, central moment, Hermite moment, and central Hermite moment. It is also found that when the parameter c_{s} is an adjustable parameter in the standard or rectangular lattice, the present RMRT-LB method becomes a kind of MRT-LB method for the NSEs and NCDE, and the commonly used MRT-LB models on the DdQq lattice are only its special cases. We also perform some numerical simulations, and the results show that the present RMRT-LB method can give accurate results and also have a good numerical stability.
ABSTRACT
Coordinated ligands play crucial roles in tuning the electrochemical nitrate reduction performance of phthalocyanine (Pc)-based dual atom catalysts. With the assistance of axial O ligands, fast NO to NH3 conversion can be realized on O-Ni2-Pc and O-Cu2-Pc. A 2-N product, N2O, can be synthesized on Co2-Pc, Cr2-Pc, O-Co2-Pc, and O-Fe2-Pc through N-N coupling with high NO coverage. ΔENO can be identified as a valid descriptor to support rational M2-Pc design.
ABSTRACT
The practical application of Li-S batteries has been greatly hindered by severe shuttle effects and sluggish kinetics. Anchoring soluble lithium polysulfides (LiPSs) onto host materials by chemisorption is an effective strategy for extending battery life. In this work, we performed systematic density functional theory calculations to evaluate the anchoring performance of O/F-covered MXene (M2TC2) in lithium-sulfur batteries. Our results indicate that the moderate anchoring strength (â¼2.5 eV), outstanding sulfur reduction performance (UL > -0.6 V), and low lithium ion diffusion barrier (<0.2 eV) of Mo2CF2 and V2CF2 make them promising host materials for LiPSs. We further revealed the determinants of the strength of binding of LiPSs to M2CT2. On the basis of the strong correlation among QM, χO/F, and Ea, we established a "structure-property" equation to reveal the active origin of M2CT2. We expect that the framework established in this work will accelerate the development of Li-S batteries.
ABSTRACT
While tuning the electronic structure of Pt can thermodynamically alleviate CO poisoning in direct methanol fuel cells, the impact of interactions between intermediates on the reaction pathway is seldom studied. Herein, we contrive a PtBi model catalyst and realize a complete inhibition of the CO pathway and concurrent enhancement of the formate pathway in the alkaline methanol electrooxidation. The key role of Bi is enriching OH adsorbates (OHad) on the catalyst surface. The competitive adsorption of CO adsorbates (COad) and OHad at Pt sites, complementing the thermodynamic contribution from alloying Bi with Pt, switches the intermediate from COad to formate that circumvents CO poisoning. Hence, 8% Bi brings an approximately 6-fold increase in activity compared to pure Pt nanoparticles. This notion can be generalized to modify commercially available Pt/C catalysts by a microwave-assisted method, offering opportunities for the design and practical production of CO-tolerance electrocatalysts in an industrial setting.
ABSTRACT
BACKGROUND: Pingchan granule (PCG) is a traditional Chinese medicine for Parkinson's disease (PD). HYPOTHESIS/PURPOSE: This was the first study aiming to evaluate the efficacy and safety of PCG for motor symptoms, gait impairments and quality of life in PD. STUDY DESIGN AND METHODS: In this multicenter, randomized, double-blind, placebo-controlled trial, 292 participants were included and followed for 9 months, randomly assigned at a 1:1 ratio to receive PCG or placebo. The primary outcome was the severity of motor symptoms assessed by Movement Disorder Society Unified Parkinson's Rating Scale III (MDS-UPDRS-III) motor score. Secondary outcomes included timed up and go test (TUG), functional gait assessment (FGA), freezing of gait (FOG), and quality of life assessed by Parkinson's disease questionnaire (PDQ-39). Assessments were done at baseline (T0), 3 months (T1), 6 months (T2) and 9 months (T3). TRIAL REGISTRATION: Chinese Clinical Trial Register, ChiCTR-INR-1,701,194. RESULTS: Generalized estimating equation analyses revealed that PCG group had significantly better improvement in MDS-UPDRS-III motor score than placebo group, as well as its domain scores of axial symptoms, bradykinesia, rigidity, and tremor. Improvements of TUG time, FGA, FOG questionnaire (FOGQ), and PDQ39 scores were also observed. CONCLUSION: PCG had a long-lasting efficacy for motor symptoms and function in PD with good tolerance, supporting that PCG might be a viable alternative in the management of PD.
Subject(s)
Gait Disorders, Neurologic , Parkinson Disease , Humans , Parkinson Disease/drug therapy , Gait Disorders, Neurologic/complications , Medicine, Chinese Traditional , Quality of Life , Postural Balance , Time and Motion StudiesABSTRACT
PdPb nanocrystals have drawn considerable attention due to their excellent catalytic properties, while their practical applications have been impeded by the severe degradation of activity, which is caused by the adsorption of intermediates (especially CO) during the operation. Herein, we first present porous PdPb alloys with the incorporation of amorphous Pb(OH)2 species as highly active and stable electrocatalysts. Alloying Pd with Pb species is initially proposed to optimize the Pd-Pd interatomic distance and adjust the d-band center of Pd. Importantly, the amorphous Pb(OH)2 species are beneficial to promoting the formation of OHad and the removal of COad. Therefore, PdPb-Pb(OH)2 catalysts show a mass activity of 3.18 A mgPd -1 and keep excellent stability for the ethanol oxidation reaction (EOR). In addition, further CO stripping and a series of CO poisoning experiments indicate that PdPb-Pb(OH)2 composites possess much better CO tolerance benefiting from the tuned electronic structure of Pd and surface incorporation of Pb(OH)2 species.