Theoretical investigation of synergistically boosting the anchoring and electrochemical performance of lithiophilic/sulfiphilic transition metal carbides for lithium-sulfur batteries.

Lithium-sulfur (Li-S) battery is one of the most promising next-generation energy-storage systems with a high energy density and low cost. However, their commercial applications face several challenges, such as the shuttle effect caused by the soluble lithium polysulfide (LiPSs) intermediates and the sluggish sulfur redox reaction. In this article, we systematically investigated the anchoring and electrochemical performance of a series of transition metal carbides (TMCs: TiC, VC, ZrC, NbC, HfC, TaC) as cathode materials for Li-S batteries by theoretical calculations. The lithiophilic/sulfiphilic non-polar (001) surfaces of TMCs can offer moderate binding strength with LiPS intermediates, ensuring good performance of sulfur immobilization. These TMCs can also facilitate lithium diffusion, indicating the good rate performance of Li-S batteries. We also demonstrated that the studied TMCs can be classified into two classes according to their catalytic activity for Li2S decomposition which originated from their different electronic structural features. Furthermore, TiC, ZrC, and HfC exhibited excellent bifunctional electrochemical activity through reducing the Gibbs free energy for sulfur reduction reactions (SRRs) and lowering the barrier for Li2S decomposition which facilitates accelerating electrode kinetics and elevating utilization of sulfur. Our results offer a systematic approach to designing and screening non-polar materials for high-performance Li-S batteries, based on the rational electronic structure and lattice match strategy.

Construction of Co1-x S Nanoparticles Embedding in N-Doped Amorphous Carbon@Graphene with Enhanced Li-Ion Storage.

Cobalt sulfide is deemed a promising anode material, owing to its high theoretical capacity (630 mAh g-1 ). Due to its low conductivity, fast energy decay, and the huge volume change during the lithiation process limits its practical application. In this work, a simple and large-scale method are developed to prepare Co1-x S nanoparticles embedding in N-doped carbon/graphene (CSCG). At a current density of 0.2 C, the reversible discharge capacity of CSCG maintains 937 mAh g-1 after 200 cycles. The discharge capacity of CSCG maintains at 596 mAh g-1 after 500 cycles at the high current density of 2.0 C. The excellent performance of CSCG is due to its unique structural features. The addition of rGO buffered volume changes while preventing Co1-x S from crushing/aggregating during the cycle, resulting in multiplier charge-discharge and long cycle life. The N-doped carbon provides a simple and easy way to achieve excellent performance in practical applications. Combined with density functional theory calculation, the presence of Co-vacancies(Co1-x ) increases more active site. Moreover, N-doping carbon is beneficial to the improve adsorption energy. This work presents a simple and effective structural engineering strategy and also provides a new idea to improve the performance of Li-ion batteries.

Theoretical identification of the superior anchoring effect and electrochemical performance of Ti2CS2 by single atom Zn doping for lithium-sulfur batteries.

As one of the promising next-generation energy storage systems, lithium-sulfur (Li-S) batteries have been the subject of much recent attention. However, the polysulfide shuttle effect remains problematic owing to the dissolution of intermediate polysulfide species in the electrolyte and the sluggish reaction dynamics in Li-S batteries. To overcome these issues, this work reports an effective strategy for enhancing the electrochemical performance of Li-S batteries using single atom Zn doping on the S-terminated Ti2C MXenes (Ti2-xZnxCS2). Spin-polarized density functional theory (DFT) calculations were performed to elucidate the interactions of lithium polysulfides (LiPSs) and the Ti2-xZnxCS2 surface in terms of geometric and electronic properties, as well as the delithiation process of Li2S on the Ti2-xZnxCS2 surface. It is found that doping single atom Zn could induce a new Lewis acid-based sites, which could provide proper affinity toward LiPSs. Combined with the metallic character, a low Li diffusion barrier and high catalytic activity for the delithiation process of Li2S, makes Ti2-xZnxCS2 a promising cathode material for Li-S batteries. The results demonstrate the importance of surface chemistry and the electronic structure of MXenes in LiPSs' adsorption and catalysis capability. We believe that our findings provide insights into the recent experimental results and guidance for the preparation and practical application of MXenes in Li-S batteries.

Evolution and Discovery of Matrine Derivatives as a New Class of Anti-Hepatic Fibrosis Agents Targeting Ewing Sarcoma Breakpoint Region 1 (EWSR1).

A series of new tricyclic matrinane derivatives were continuously synthesized and evaluated for their inhibitory effects on genes and proteins related to hepatic fibrosis at the cellular level, including collagen type I α1 chain (COL1A1), α smooth muscle actin (α-SMA), connective tissue growth factor (CTGF), and matrix metalloprotein 2 (MMP-2). Among them, compound 6k exerted an appealing potency and significantly reduced liver injury and fibrosis in both bile duct ligation (BDL) rats and Mdr2 knockout mice. An activity-based protein profiling (ABPP) assay indicated that 6k might directly bind to Ewing sarcoma breakpoint region 1 (EWSR1) to inhibit its function and affect the expression of downstream liver fibrosis-related genes and thus regulate liver fibrosis. These results provided a potential novel target for the treatment of liver fibrosis and powerful information for the development of tricyclic matrinanes into promising anti-hepatic fibrosis agents.

Synthesis of CoP@B,N,P co-doped porous carbon by a supramolecular gel self-assembly method for lithium-sulfur battery separator modification.

Lithium-sulfur batteries (LSBs) are regarded as promising next-generation batteries due to their high abundance and high theoretical energy density. However, the commercial application of LSBs is hindered by the shuttle effect of soluble lithium polysulfides (LiPSs). Hence, we synthesised B, N, P co-doped three-dimensional hierarchical porous carbon materials, uniformly dispersed with CoP nanoparticles, and utilized them as the coating material for the PE separator. The catalytic and adsorption capacity of the composite material was significantly enhanced by CoP. Both experimental and theoretical calculations show that the LiPS adsorption capacity of the composite material is significantly enhanced after the introduction of B atoms. As a result, the assembled LSBs with the CoP@BNPC/PE separator show excellent long-term stability (940.8 mA h g-1 after 500 cycles at 1.0 C, and only a 0.026% decay rate per cycle) and superior rate performance (613.6 mA h g-1 at 5.0 C). Our work further proves that a modified separator is an effective strategy to promote the commercialization of LSBs.

Printed Electronics Based on 2D Material Inks: Preparation, Properties, and Applications toward Memristors.

Printed electronics, which fabricate electrical components and circuits on various substrates by leveraging functional inks and advanced printing technologies, have recently attracted tremendous attention due to their capability of large-scale, high-speed, and cost-effective manufacturing and also their great potential in flexible and wearable devices. To further achieve multifunctional, practical, and commercial applications, various printing technologies toward smarter pattern-design, higher resolution, greater production flexibility, and novel ink formulations toward multi-functionalities and high quality have been insensitively investigated. 2D materials, possessing atomically thin thickness, unique properties and excellent solution-processable ability, hold great potential for high-quality inks. Besides, the great variety of 2D materials ranging from metals, semiconductors to insulators offers great freedom to formulate versatile inks to construct various printed electronics. Here, a detailed review of the progress on 2D material inks formulation and its printed applications has been provided, specifically with an emphasis on emerging printed memristors. Finally, the challenges facing the field and prospects of 2D material inks and printed electronics are discussed.

Ultrafast Kinetics in a PAN/MgFe2O4 Flexible Free-Standing Anode Induced by Heterojunction and Oxygen Vacancies.

Flexibility and power density are key factors restricting the development of flexible lithium-ion batteries (FLIBs). Interface and defect engineering can modify the intrinsic ion/electron kinetics by regulating the electronic structure. Herein, a polyacrylonitrile/MgFe2O4 (PAN-MFO) electrode with heterojunction and oxygen vacancies was first designed and synthesized as a flexible free-standing anode of FLIBs by electrostatic spinning technology. The PAN carbon nanofiber (PAN-CNF) as the skeleton structure provides fast conductive channels, buffers the volume expansion, and enhances the cycle stability. The heterostructure constructs the internal electric field, facilitates the Li+/charge transfer, intensifies the Li+ adsorption energy, and enhances the interfacial lithium storage. Oxygen vacancies improve the intrinsic conductivity, lower the Li+ diffusion barrier, weaken the Fe-O bonding, and facilitate the conversion reaction. Because of the synergistic effect of the multifunctional structure, the PAN-MFO shows superior cycle and rate performance with ultrafast kinetics. Flexible LiCoO2/PAN-MFO full pouch cells were also assembled that demonstrated a stable cycle performance and power supply in both the plain and bent states.

Structure-Activity Relationship of Aloperine Derivatives as New Anti-Liver Fibrogenic Agents.

Twenty-seven novel 12N-substituted aloperine derivatives were synthesized and investigated for their inhibitory effects on collagen α1 (I) (COL1A1) promotor in human hepatic stellate LX-2 cells, taking aloperine (1) as the hit. A structure-activity relationship (SAR) study disclosed that the introduction of suitable substituents on the 12N atom might enhance the activity. Compound 4p exhibited a good promise on down-regulating COL1A1 expression with the IC50 value of 16.5 µM. Its inhibitory activity against COL1A1 was further confirmed on both mRNA and protein levels. Meanwhile, it effectively inhibited the expression of other fibrogenic proteins, such as transforming growth factor ß1 (TGF-ß1) and smooth muscle actin (α-SMA). It also exhibited good in vivo safety profile with the oral LD50 value of 400 mg kg-1 in mice. The results initiated the anti-liver fibrogenic study of aloperine derivatives, and the key compound 4p was selected as a novel lead for further investigation against liver fibrogenesis.

Structure-activity relationship and hypoglycemic activity of tricyclic matrines with advantage of treating diabetic nephropathy.

Forty-three tricyclic matrinic derivatives with a unique scaffold were prepared and evaluated for their stimulation effects on glucose consumption in HepG2 cells. The structure-activity relationship was systematically elucidated for the first time. Among them, compound 17a exhibited the most promising potency, and dose-dependently increased glucose consumption in L6 myotubes. It significantly lowered blood glucose, glucosylated haemoglobin and AGE level, and improved glucose tolerance and insulin resistance in KK-Ay mice as well. More importantly, 17a effectively ameliorated diabetic nephropathy (DN), as indicated by the improvement of renal function and pathological changes, and decrease of urinary protein. Furthermore, 17a could induce glycolysis but suppressed aerobic oxidation of glucose, in a similar mechanism to Metform. Our results indicated that in addition to hyperglycemia, 17a may be developed to treat diabetic complication such as DN.

12N-Substituted Matrinol Derivatives Inhibited the Expression of Fibrogenic Genes via Repressing Integrin/FAK/PI3K/Akt Pathway in Hepatic Stellate Cells.

Twenty new 12N-substituted matrinol derivatives were synthesized and evaluated for their inhibitory effects on collagen α1 (I) (COL1A1) promotor in human hepatic stellate LX-2 cells. The structure-activity relationship (SAR) revealed that introducing a 12N-benzeneaminoacylmethyl substitution might significantly enhance the activity. Compound 8a exhibited the highest inhibitory potency against COL1A1, and its inhibition activity against COL1A1 was further confirmed on both the mRNA and protein levels. It also effectively inhibited the expression of α smooth muscle actin (α-SMA), fibronectin and transforming growth factor ß1 (TGFß1), indicating an extensive inhibitory effect on the expression of fibrogenic genes. The primary mechanism study indicated that it might take action via the Integrin/FAK/PI3K/Akt signaling pathway. The results provided powerful information for further structure optimization, and compound 8a was selected as a novel anti-fibrogenic lead for further investigation.