Study on exosomes for identifying bipolar disorder in early stage: A cross-sectional and validation study protocol.

BACKGROUND: The difficulty is remained to accurately distinguish bipolar disorder (BD) from major depressive disorder (MDD) in early stage, with a delayed diagnosis for 5-10 years. BD patients are often treated with antidepressants systematically due to being diagnosed with MDD, affecting the disease course and clinical outcomes. The current study aims to explore the role of plasma exosomes as biomarker to distinguish BD from MDD in early stage. METHODS: Two stages are included. The first stage is a cross-sectional study, comparing the concentrations of plasma exosome microRNA and related proteins among BD group, MDD group, and healthy controls (HC) group (n = 40 respectively), to identify target biomarkers preliminarily. The "Latent Class Analysis" and "Receiver Operating Characteristic" analysis will be performed to determine the optimal concentration range for each biomarker. The second stage is to validate target markers in subjects, coming from an ongoing study focusing on patients with a first depressive episode. All target biomarkers will be test in plasma samples reserved at the initial stage to detect whether the diagnosis indicated by biomarker level is consistent with the diagnosis by DSM-5. Furthermore, the correlation between specific biomarkers and the manic episode, suicidal ideation, and adverse reactions will also be observed. DISCUSSION: Exosome-derived microRNA and related proteins have potential in serving as a good medium for exploring mental disorders because it can pass through the blood-brain barrier bidirectionally and convey a large amount of information stably. Improving the early diagnosis of BD would help implement appropriate intervention strategy as early as possible and significantly reduce the burden of disease.

Self-Zincophilic Dual Protection Host of 3D ZnO/Zn⊂CF to Enhance Zn Anode Cyclability.

Zn dendrite growth and side reactions restrict the practical use of Zn anode. Herein, the design of a novel 3D hierarchical structure is demonstrated with self-zincophilic dual-protection constructed by ZnO and Zn nanoparticles immobilized on carbon fibers (ZnO/Zn⊂CF) as a versatile host on the Zn surface. The unique 3D frameworks with abundant zinc nucleation storage sites can alleviate the structural stress during the plating/stripping process and overpower Zn dendrite growth by moderating Zn2+ flux. Moreover, given the dual protection design, it can reduce the contact area between active zinc and electrolyte, inhibiting hydrogen evolution reactions. Importantly, density functional theory calculations and experimental results confirm that the introduced O atoms in ZnO/Zn⊂CF enhance the interaction between Zn2+ and the host and reduce Zn nucleation overpotential. As expected, the ZnO/Zn⊂CF-Zn electrode exhibits stable Zn plating/stripping with low polarization for 4200 h at 0.2 mA cm-2 and 0.2 mAh cm-2 . Furthermore, the symmetrical cell displays a significantly long cycling life of over 1800 h, even at 30 mA cm-2 . The fabricated full cells also show impressive cycling performance when coupled with V2 O3 cathodes.

One-step growth of ultrathin CoSe2 nanobelts on N-doped MXene nanosheets for dendrite-inhibited and kinetic-accelerated lithium-sulfur chemistry.

The practical application of lithium-sulfur (Li-S) batteries is inhibited by the shuttle effect of lithium polysulfides (LiPSs) and slow polysulfide redox kinetics on the S cathode as well as the uncontrollable growth of dendrites on the Li metal anode. Therefore, both cathode and anode sides must be considered when modifying Li-S batteries. Herein, two-dimensional (2D) ultrathin CoSe2 nanobelts are in situ grown on 2D N-doped MXene nanosheets (CoSe2@N-MXene) via one-step solvothermal process for the first time. Owing to its unique 2D/2D structure, CoSe2@N-MXene can be processed to crumpled nanosheets by freeze-drying and flexible and freestanding films by vacuum filtration. These crumpled CoSe2@N-MXene nanosheets with abundant active sites and inner spaces can act as S hosts to accelerate polysulfide redox kinetics and suppress the shuttle effect of LiPSs owing to their strong adsorption ability and catalytic conversion effect with LiPSs. Meanwhile, the CoSe2@N-MXene film (CoSe2@NMF) can act as a current collector to promote uniform Li deposition because it contains lithiophilic CoSe2 and N sites. Under the systematic effect of CoSe2@N-MXene on S cathode and Li metal anode, the electrochemical and safety performance of Li-S batteries are improved. CoSe2@NMF also shows excellent storage performances in flexible energy storage devices.

Internal Vanadium Doping and External Modification Design of P2-Type Layered Mn-Based Oxides as Competitive Cathodes toward Sodium-Ion Batteries.

P2-type layered manganese-based oxides have attracted considerable interest as economical, cathode materials with high energy density for sodium-ion batteries (SIBs). Despite their potential, these materials still face challenges related to sluggish kinetics and structural instability. In this study, a composite cathode material, Na0.67 Ni0.23 Mn0.67 V0.1 O2 @Na3 V2 O2 (PO4 )2 F was developed by surface-coating P2-type Na0.67 Ni0.23 Mn0.67 V0.1 O2 with a thin layer of Na3 V2 O2 (PO4 )2 F to enhance both the electrochemical sodium storage and material air stability. The optimized Na0.67 Ni0.23 Mn0.67 V0.1 O2 @5wt %Na3 V2 O2 (PO4 )2 F exhibited a high discharge capacity of 176 mA h g-1 within the 1.5-4.1 V range at a low current density of 17 mA g-1 . At an increased current density of 850 mA g-1 within the same voltage window, it still delivered a substantial initial discharge capacity of 112 mAh g-1 . These findings validate the significant enhancement of ion diffusion capabilities and rate performance in the P2-type Na0.67 Ni0.33 Mn0.67 O2 material conferred by the composite cathode.

Modulating Coordination of Iron Atom Clusters on N,P,S Triply-Doped Hollow Carbon Support towards Enhanced Electrocatalytic Oxygen Reduction.

Constructing atom-clusters (ACs) with in situ modulation of coordination environment and simultaneously hollowing carbon support are critical yet challenging for improving electrocatalytic efficiency of atomically dispersed catalysts (ADCs). Herein, a general diffusion-controlled strategy based on spatial confining and Kirkendall effect is proposed to construct metallic ACs in N,P,S triply-doped hollow carbon matrix (MACs /NPS-HC, M=Mn, Fe, Co, Ni, Cu). Thereinto, FeACs /NPS-HC with the best catalytic activity for oxygen reduction reaction (ORR) is thoroughly investigated. Unlike the benchmark sample of symmetrical N-surrounded iron single-atoms in N-doped carbon (FeSAs /N-C), FeACs /NPS-HC comprises bi-/tri-atomic Fe centers with engineered S/N coordination. Theoretical calculation reveals that proper Fe gathering and coordination modulation could mildly delocalize the electron distribution and optimize the free energy pathways of ORR. In addition, the triple doping and hollow structure of carbon matrix could further regulate the local environment and allow sufficient exposure of active sites, resulting in more enhanced ORR kinetics on FeACs /NPS-HC. The zinc-air battery assembled with FeACs /NPS-HC as cathodic catalyst exhibits all-round superiority to Pt/C and most Fe-based ADCs. This work provides an exemplary method for establishing atomic-cluster catalysts with engineered S-dominated coordination and hollowed carbon matrix, which paves a new avenue for the fabrication and optimization of advanced ADCs.

NiMoO4 nanorods with oxygen vacancies self-supported on Ni foam towards high-efficiency electrocatalytic conversion of nitrite to ammonia.

As an eco-friendly and sustainable strategy, the electrochemical reduction of nitrite (NO2-) can simultaneous generation of NH3 and treatment of NO2- contamination in the environment. Herein, monoclinic NiMoO4 nanorods with abundant oxygen vacancies self-supported on Ni foam (NiMoO4/NF) are considered high-performance electrocatalysts for ambient NH3 synthesis by reduction of NO2-, which can deliver an outstanding yield of 18089.39 ± 227.98 µg h-1 cm-2 and a preferable FE of 94.49 ± 0.42% at -0.8 V. Additionally, its performance remains relatively stable during long-term operation as well as cycling tests. Furthermore, density functional theory calculations unveil the vital role of oxygen vacancies in promoting nitrite adsorption and activation, ensuring efficient NO2-RR towards NH3. A Zn-NO2- battery with NiMoO4/NF as the cathode shows high battery performance as well.

Binary Sulfiphilic Nickel Boride on Boron-Doped Graphene with Beneficial Interfacial Charge for Accelerated Li-S Dynamics.

The "shuttle effect" and slow conversion kinetics of lithium polysulfides (LiPSs) are stumbling block for high-energy-density lithium-sulfur batteries (LSBs), which can be effectively evaded by advanced catalytic materials. Transition metal borides possess binary LiPSs interactions sites, aggrandizing the density of chemical anchoring sites. Herein, a novel core-shelled heterostructure consisting of nickel boride nanoparticles on boron-doped graphene (Ni3 B/BG), is synthesized through a graphene spontaneously couple derived spatially confined strategy. The integration of Li2 S precipitation/dissociation experiments and density functional theory computations demonstrate that the favorable interfacial charge state between Ni3 B and BG provides smooth electron/charge transport channel, which promotes the charge transfer between Li2 S4 -Ni3 B/BG and Li2 S-Ni3 B/BG systems. Benefitting from these, the facilitated solid-liquid conversion kinetics of LiPSs and reduced energy barrier of Li2 S decomposition are achieved. Consequently, the LSBs employed the Ni3 B/BG modified PP separator deliver conspicuously improved electrochemical performances with excellent cycling stability (decay of 0.07% per cycle for 600 cycles at 2 C) and remarkable rate capability of 650 mAh g-1 at 10 C. This study provides a facile strategy for transition metal borides and reveals the effect of heterostructure on catalytic and adsorption activity for LiPSs, offering a new viewpoint to apply boride in LSBs.

Copper-based catalysts for the electrochemical reduction of carbon dioxide: progress and future prospects.

There is an urgent need for the development of high performance electrocatalysts for the CO2 reduction reaction (CO2RR) to address environmental issues such as global warming and achieve carbon neutral energy systems. In recent years, Cu-based electrocatalysts have attracted significant attention in this regard. The present review introduces fundamental aspects of the electrocatalytic CO2RR process together with a systematic examination of recent developments in Cu-based electrocatalysts for the electroreduction of CO2 to various high-value multicarbon products. Current challenges and future trends in the development of advanced Cu-based CO2RR electrocatalysts providing high activity and selectivity are also discussed.

Enhanced cycling stability and storage performance of Na0.67Ni0.33Mn0.67-xTixO1.9F0.1 cathode materials by Mn-rich shells and Ti doping.

We propose a synergistic strategy of titanium doping and surface coating with a Mn-rich shell to modify the Na-rich manganese-oxide-based cathode material Na0.67Ni0.33Mn0.67-xTixO1.9F0.1 in sodium-ion batteries and elucidate the underlying mechanism for enhanced material performance. First, it is found that the electrochemical performance of the proposed cathode material can be effectively improved when the Ti doping amount is x = 0.3. In addition to doping, the cathode material coated with a manganese-rich shell was prepared by a liquid coating method. The as-prepared Mn@Ti-doped-Na0.67Ni0.33Mn0.37Ti0.3O1.9F0.1 exhibited excellent electrochemical performance, delivering 169 mAh/g discharge capacity. The charge-discharge cycle test was carried out at a current density of 2C, and the sample not only provides a reversible capacity of 119 mAh/g but also has a capacity retention rate of 71 % after 500 charge-discharge cycles. The Ti doping and surface coating with a Mn-rich shell are shown to improve the specific discharge capacity, cycling stability and rate capability of the cathode material and mitigate voltage decay. These results validate our design principle and provide a novel approach to enhance the performance of cathode materials in sodium-ion batteries.

Dual-Functional Hosts for Polysulfides Conversion and Lithium Plating/Stripping towards Lithium-Sulfur Full Cells.

The practical application of lithium-sulfur (Li-S) batteries is greatly hindered by the shuttle effect of dissolved polysulfides in the sulfur cathode and the severe dendritic growth in the lithium anode. Adopting one type of effective host with dual-functions including both inhibiting polysulfide dissolution and regulating Li plating/stripping, is recently an emerging research highlight in Li-S battery. This review focuses on such dual-functional hosts and systematically summarizes the recent research progress and application scenarios. Firstly, this review briefly describes the stubborn issues in Li-S battery operations and the sophisticated counter measurements over the challenges by dual-functional behaviors. Then, the latest advances on dual-functional hosts for both cathode and anode in Li-S full cells are catalogued as species, including metal chalcogenides, metal carbides, metal nitrides, heterostuctures, and the possible mechanisms during the process. Besides, we also outlined the theoretical calculation tools for the dual-functional host based on the first principles. Finally, several sound perspectives are also rationally proposed for fundamental research and practical development as guidelines.

Morphology-Controlled Synthesis of V1.11S2 for Electrocatalytic Hydrogen Evolution Reaction in Acid Media.

High-performance low-cost catalysts are in high demand for the hydrogen evolution reaction (HER). In the present study, we reported that V1.11S2 materials with flower-like, flake-like, and porous morphologies were successfully synthesized by hydrothermal synthesis and subsequent calcination. The effects of morphology on hydrogen evolution performance were studied. Results show that flower-like V1.11S2 exhibits the best electrocatalytic activity for HER, achieving both high activity and preferable stability in 0.5 M H2SO4 solution. The main reason can be ascribed to the abundance of catalytically active sites and low charge transfer resistance.

Defective nanomaterials for electrocatalysis oxygen reduction reaction.

The difficulties in O2 molecule adsorption/activation, the cleavage of the O-O bond, and the desorption of the reaction intermediates at the surface of the electrodes make the cathodic oxygen reduction reaction (ORR) for fuel cells show extremely sluggish kinetics. Thus, it is important to the exploitation of highly active and stable electrocatalysts for the ORR to promote the performance and commercialization of fuel cells. Many studies have found that the defects affect the electron and the geometrical structure of the catalyst. The catalytic performance is enhanced by constructing defects to optimize the adsorption energy of substrates or intermediates. Unfortunately, still many issues are poorly recognized, such as the effect of defects (types, contents, and locations) in catalytic performance is unclear, and the catalytic mechanism of defective nanomaterials is lacking. In this review, the defective electrocatalysts divided into noble and non-noble metals for the ORR are highlighted and summarized. With the assistance of experimental results and theoretical calculations, the structure-activity relationships between defect engineering and catalytic performance have been clarified. Finally, after a deeper understanding of defect engineering, a rational design for efficient and robust ORR catalysts for PEMFCs is further guided.

Multifunctional Atomic Molybdenum on Graphene with Distinctive Coordination to Solve Li and S Electrochemistry.

The improvement of lithium-sulfur batteries is still impeded by notorious shuttling effect and sluggish kinetics on the S cathode, and rampant Li dendrite formation on the Li anode makes it worse. Herein, a type of single-atom dispersed Mo on nitrogen-doped graphene (Mo/NG) with a distinctive Mo-N2 O2 -C coordination structure first serving as a multifunctional material is designed by a structure-oriented strategy to solve Li and S electrochemistry. Mo/NG with superior intrinsic properties endowed by the unique coordination configuration adsorbs soluble polysulfides and promotes bidirectional conversion of LiPSs at the cathode side. Meanwhile, the suitable binding strength of Mo/NG with lithium ions endows it with an attractive lithiophilic feature. Specifically, Mo/NG is able to work as the adaptor to redistribute lithium ions on the interface of separator and homogenize the lithium ion flux. Due to the suitable binding ability with Li+ , it does not interfere with the diffusion of lithium ions across and provides tunnels exclusive to lithium ions to generate fast and homogeneous flux. Ascribed to such unique multifunctionality, Li-S batteries assembled with Mo/NG exhibit excellent electrochemical performance including long cycling stability over 1000 cycles and high areal capacities under high sulfur mass loading.

Molybdenum Oxynitride Atomic Nanoclusters Bonded in Nanosheets of N-Doped Carbon Hierarchical Microspheres for Efficient Sodium Storage.

Transition metal nitrides have attracted considerable attention as great potential anode materials due to their excellent metallic conductivity and high theoretical specific capacity. However, their cycling performance is impeded by their instability caused by the reaction mechanism. Herein, we report the engineering and synthesis of a novel hybrid architecture composed of MoO2.0N0.5 atomic nanoclusters bonded in nanosheets of N-doped carbon hierarchical hollow microspheres (MoO2.0N0.5/NC) as an anode material for sodium-ion batteries. The facile self-templating strategy for the synthesis of MoO2.0N0.5/NC involves chemical polymerization and subsequent one-step calcination treatments. The design is beneficial to improve the electrochemical kinetics, buffer the volume variation of electrodes during cycling, and provide more interfacial active sites for sodium uptake. Due to these unique structural and compositional merits, these MoO2.0N0.5/NC exhibits excellent sodium storage performance in terms of superior rate capability and stable long cycle life. The work shows a feasible and effective way to design novel host candidates and solve the long-term cycling stability issues for sodium-ion batteries.

High-Efficiency Ammonia Electrosynthesis on Anatase TiO2-x Nanobelt Arrays with Oxygen Vacancies by Selective Reduction of Nitrite.

Electrocatalytic reduction of nitrite to NH3 provides a new route for the treatment of nitrite in wastewater, as well as an attractive alternative to NH3 synthesis. Here, we report that an oxygen vacancy-rich TiO2-x nanoarray with different crystal structures self-supported on the Ti plate can be prepared by hydrothermal synthesis and by subsequently annealing it in an Ar/H2 atmosphere. Anatase TiO2-x (A-TiO2-x) can be a superb catalyst for the efficient conversion of NO2- to NH3; a high NH3 yield of 12,230.1 ± 406.9 µg h-1 cm-2 along with a Faradaic efficiency of 91.1 ± 5.5% can be achieved in a 0.1 M NaOH solution containing 0.1 M NaNO2 at -0.8 V, which also exhibits preferable durability with almost no decay of catalytic performances after cycling tests and long-term electrolysis. Furthermore, a Zn-NO2- battery with such A-TiO2-x as a cathode delivers a power density of 2.38 mW cm-2 as well as a NH3 yield of 885 µg h-1 cm-2.

Construction of V1.11S2 flower spheres for efficient aqueous Zn-ion batteries.

Aqueous zinc-ion batteries (AZIBs) have become a focus due to their high safety, low cost, and environmental protection. Vanadium-based materials are commonly used as cathodes in AZIBs. As technology improves, more types of vanadium-based materials are successfully synthesized and applied. To find more suitable cathode materials, we first investigated the utility of V1.11S2 spheres for AZIB cathodes, which were synthesized by a facile solvothermal method. Benefiting from the excellent morphology and stable chemical system, the electrode exhibits continuous capacity growth during the cycling process and maintains stability over a long period of time. In addition, it has an outstanding rate capability. Specifically, the capacity reaches 224.8 mAh g-1 at 0.1 A g-1 and increases from 39.1 to 51.4 mAh g-1 at 2 A g-1 after 2000 cycles. Such characteristics can be attributed to the continuous and slow activation of the electrode and the growth of the specific surface area due to the scattered nanosheets, which allows the electrolyte to fully penetrate into the material and expose more active sites. Meanwhile, the increased V1.11S2 layer spacing due to the embedding of water molecules can provide a wide channel for ion transport. This work may provide new ideas for the synthesis and development of vanadium-based materials used in AZIBs.

Fabrication of Ni-Cu-W Graded Coatings by Plasma Spray Deposition and Laser Remelting.

In this study, Ni-Cu-W graded coatings are produced by atmospheric plasma spraying and subsequently remelted by laser. The surface morphology, hardness, compositional fluctuations and corrosion resistance of the Ni-Cu-W coating are investigated. The coatings after laser remelting are densified and become more homogenous with an excellent corrosion resistance and high hardness, which can be used to explore the new materials.

Boosting electrochemical nitrite-ammonia conversion properties by a Cu foam@Cu2O catalyst.

Electrocatalytic reduction of nitrite (NO2-) to ammonia (NH3) can simultaneously achieve wastewater treatment and ammonia production, but it needs efficient catalysts. Herein, Cu2O particles self-supported on Cu foam with enriched oxygen vacancies are developed to enable selective NO2- reduction to NH3, exhibiting a maximum NH3 yield rate of 7510.73 µg h-1 cm-2 and high faradaic efficiency of 94.21% at -0.6 V in 0.1 M PBS containing 0.1 M NaNO2. Density functional theory calculations reveal the vital role of oxygen vacancies during the nitrite reduction process, as well as the reaction mechanisms and the potential limiting step involved. This work provides a new avenue to the rational design of Cu-based catalysts for NH3 electrosynthesis.

Ni2P nanosheet array for high-efficiency electrohydrogenation of nitrite to ammonia at ambient conditions.

Ammonia (NH3) plays an important role in agriculture and industry. The industry-scale production mainly depends on the Haber-Bosch process suffering from issues of environment pollution and energy consumption. Electrochemical reduction can degrade nitrite (NO2-) pollutants in the environment and convert it into more valuable NH3. Here, Ni2P nanosheet array on nickel foam is proposed as a 3D electrocatalyst for high-efficiency electrohydrogenation of NO2- to NH3 under ambient reaction conditions. When tested in 0.1 M phosphate buffer saline with 200 ppm NO2-, such Ni2P/NF is able to obtain a large NH3 yield rate of 2692.2 ± 92.1 µg h-1 cm-2 (3282.9 ± 112.3 µg h-1 mgcat.-1), a high Faradic efficiency of 90.2 ± 3.0%, and selectivity of 87.0 ± 1.7% at -0.3 V versus a reversible hydrogen electrode. After 10 h of electrocatalytic reduction, the conversion rate of NO2- achieves near 100%. The catalytic mechanism is further investigated by density functional theory calculations.

Effects of Fe-Ions Irradiation on the Microstructure and Mechanical Properties of FeCrAl-1.5wt.% ZrC Alloys.

Fe-13Cr-3.5Al-2.0Mo-1.5wt.% ZrC alloy was irradiated by 400 keV Fe+ at 400 °C at different doses ranging from 6.35 × 1014 to 1.27 × 1016 ions/cm2 with a corresponding damage of 1.0-20.0 dpa, respectively, to investigate the effects of different radiation doses on the hardness and microstructure of the reinforced FeCrAl alloys in detail by nanoindentation, transmission electron microscopy (TEM), and atom probe tomography (APT). The results show that the hardness at 1.0 dpa increases from 5.68 to 6.81 GPa, which is 19.9% higher than a non-irradiated specimen. With an increase in dose from 1.0 to 20.0 dpa, the hardness increases from 6.81 to 8.01 GPa, which is an increase of only 17.6%, indicating that the hardness has reached saturation. TEM and APT results show that high-density nano-precipitates and low-density dislocation loops forme in the 1.0 dpa region, compared to the non-irradiated region. Compared with 1.0 dpa region, the density and size of nano-precipitates in the 20.0 dpa region have no significant change, while the density of dislocation loops increases. Irradiation results in a decrease of molybdenum and carbon in the strengthening precipitates (Zr, Mo) (C, N), and the proportionate decrease of molybdenum and carbon is more obvious with the increase in damage.