Fine nanostructure design of metal chalcogenide conversion-based cathode materials for rechargeable magnesium batteries.

Magnesium-ion batteries (MIBs) a strong candidate to set off the second-generation energy storage boom due to their double charge transfer and dendrite-free advantages. However, the strong coulombic force and the huge diffusion energy barrier between Mg2+ and the electrode material have led to need for a cathode material that can enable the rapid and reversible de-insertion of Mg2+. So far, researchers have found that the sulfur-converted cathode materials have a greater application prospect due to the advantages of low price and high specific capacity, etc. Based on these advantages, it is possible to achieve the goal of increasing the magnesium storage capacity and cycling stability by reasonable modification of crystal or morphology. In this review, we focus on the application of a variety of sulfur-converted cathode materials in MIBs in recent years from the perspective of microstructural design, and provide an outlook on current challenges and future development.

Modulating the D-π-A Interactions in Metal-Covalent Organic Frameworks for Efficient Electroreduction of CO2 into Formate.

Crystalline porous framework materials have attracted tremendous interest in electrocatalytic CO2 reduction owing to their ordered structures and high specific surface areas as well as rich designability, however, still suffer from a lack of accuracy in regulating the binding strength between the catalytic sites and intermediates, which is crucial for optimizing the electrocatalytic activity and expanding the product types. Herein, we report three new kinds of vinylene-linked metal-covalent organic frameworks (TMT-CH3-MCOF, TMP-CH3-MCOF and TMP-MCOF) with continuously tunable D-π-A interactions by adjusting the structure of the monomers at the molecular level for realizing efficient electroreduction of CO2 to formate for the first time. Interestingly, compared with TMT-CH3-MCOF and TMP-MCOF, the TMP-CH3-MCOF exhibited the highest HCOO- Faradaic efficiency (FEHCOO-) of 95.6% at -1.0 V vs RHE and displayed the FEHCOO- above 90% at the voltage range of -1.0 to -1.2 V vs. RHE, which is one of the highest among various kinds of reported electrocatalysts. Theoretical calculations further reveal that the catalytic sites in TMP-CH3-MCOF with unique moderate D-π-A interactions have suitable binding ability towards the reaction intermediate, which is beneficial for the formation of *HCOO and desorption of *HCOOH, thus effectively promoting the electroreduction of CO2 to formate.

Self-Assembled Interlayer Enables High-Performance Organic Photovoltaics with Power Conversion Efficiency Exceeding 20.

Interfacial layers (ILs) are prerequisites to form the selective charge transport for high-performance organic photovoltaics (OPVs) but mostly result in considerable parasitic absorption loss. Trimming the ILs down to a mono-molecular level via the self-assembled monolayer is an effective strategy to mitigate parasitic absorption loss. However, such a strategy suffers from inferior electrical contact with low surface coverage on rough surfaces and poor producibility. To address these issues, here, the self-assembled interlayer (SAI) strategy is developed, which involves a thin layer of 2-6 nm to form a full coverage on the substrate via both covalent and van der Waals bonds by using a self-assembled molecule of 2-(9H-carbazol-9-yl) (2PACz). Via the facile spin coating without further rinsing and annealing process, it not only optimizes the electrical and optical properties of OPVs, which enables a world-record efficiency of 20.17% (19.79% certified) but also simplifies the tedious processing procedure. Moreover, the SAI strategy is especially useful in improving the absorbing selectivity for semi-transparent OPVs, which enables a record light utilization efficiency of 5.34%. This work provides an effective strategy of SAI to optimize the optical and electrical properties of OPVs for high-performance and solar window applications.

Recent advances in two-dimensional polymers: synthesis, assembly and energy-related applications.

Two-dimensional polymers (2DPs) are a class of 2D crystalline polymer materials with definite structures, which have outstanding physical-chemical and electronic properties. They cleverly link organic building units through strong covalent bonds and can construct functional 2DPs through reasonable design and selection of different monomer units to meet various application requirements. As promising energy materials, 2DPs have developed rapidly in recent years. This review first introduces the basic overview of 2DPs, such as their historical development, inherent 2D characteristics and diversified topological advantages, followed by the summary of the typical 2DP synthesis methods recently (including "top-down" and "bottom-up" methods). The latest research progress in assembly and processing of 2DPs and the energy-related applications in energy storage and conversion are also discussed. Finally, we summarize and prospect the current research status, existing challenges, and future research directions of 2DPs.

Water immersion ultrasound can improve the repeatability of ultrasonic measurement of dorsalis pedis artery diameter and hemodynamic parameters.

OBJECTIVE: In comparing the repeatability of the internal diameter and hemodynamic parameters of the dorsalis pedis artery measured by immersion ultrasound and contact ultrasound, the factors affecting the accuracy and repeatability of measurement were analyzed. This study aimed to provide a better method for ultrasound evaluation of the dorsalis pedis artery before flap transplantation. METHODS: Two senior sonographers measured the diameter of the dorsalis pedis artery (D) of 56 healthy volunteers, measuring at the same location and at different time points using water immersion and contact ultrasound. Color Doppler ultrasound was used to measure the hemodynamics of the dorsalis pedis artery, including peak systolic velocity (PSV), end diastolic velocity (EDV), and resistance index (RI). The interclass correlation coefficient (ICC) was used to evaluate the intraobserver and interobserver repeatability for each group's measurements. RESULTS: The intraobserver and interobserver reproducibility of D, PSV, EDV, and RI measurements by water immersion ultrasound was very good. The intraobserver and interobserver reproducibility of the contact ultrasound measurements of D, PSV, EDV, and RI was good. CONCLUSION: The repeatability of water immersion ultrasound is better than that of contact ultrasound in the measurement of the dorsalis pedis artery. Water immersion ultrasound can improve the near-field resolution of superficial tissues and increase the display of the lengths of blood vessels in images, thereby suggesting its superiority in ultrasound examination of dorsalis pedis arteries.

Crystalline Dual-Porous Covalent Triazine Frameworks as a New Platform for Efficient Electrocatalysis.

Crystalline covalent triazine frameworks (CTFs) have gained considerable interest in energy and catalysis owing to their well-defined nitrogen-rich π-conjugated porosity and superior physicochemical properties, however, suffer from very limited molecular structures. Herein we report a novel solvent-free FeCl3 -catalyzed polymerization of 2, 6-pyridinedicarbonitrile (DCP) to achieve the first synthesis of crystalline, dual-porous, pyridine-based CTF (Fe-CTF). The FeCl3 could not only act as a highly active Lewis acid catalyst for promoting the two-dimensional ordered polymerization of DCP monomers, but also in situ coordinate with the tridentate chelators generated between pyridine and triazine groups to yield unique Fe-N3 single-atom active sites in Fe-CTF. Abundant few-layer crystalline nanosheets (Fe-CTF NSs) could be prepared through simple ball-milling exfoliation of the bulk layered Fe-CTF and exhibited remarkable electrocatalytic performance for oxygen reduction reaction (ORR) with a half-wave potential and onset potential up to 0.902 and 1.02 V respectively, and extraordinary Zn-air battery performance with an ultrahigh specific capacity and power density of 811 mAh g-1 and 230 mW cm-2 respectively. By combining operando X-ray absorption spectroscopy with density functional theory calculations, we revealed a dynamic and reversible evolution of Fe-N3 to Fe-N2 during the electrocatalytic process, which could further accelerate the electrocatalytic reaction.

Covalent Organic Frameworks as Electrode Materials for Alkali Metal-ion Batteries.

Covalent organic frameworks (COFs) are a class of porous crystalline polymeric materials constructed by linking organic small molecules through covalent bonds. COFs have the advantages of strong covalent bond network, adjustable pore structure, large specific surface area and excellent thermal stability, and have broad application prospects in various fields. Based on these advantages, rational COFs design strategies such as the introduction of active sites, construction of conjugated structures, and carbon material composite, etc. can effectively improve the conductivity and stability of the electrode materials in the field of batteries. This paper introduces the latest research results of high-performance COFs electrode materials in alkali metal-ion batteries (LIBs, SIBs, PIBs and LSBs) and other advanced batteries. The current challenges and future design directions of COFs-based electrode are discussed. It provides useful insights for the design of novel COFs structures and the development of high-performance alkali metal-ion batteries.

In Situ Gelled Covalent Organic Frameworks Electrolyte with Long-Range Interconnected Skeletons for Superior Ionic Conductivity.

Covalent organic frameworks (COFs) present an ideal platform for ion transport owing to their tunable and ordered nanochannels at the single-digit scale. However, achieving superior COF-based electrolytes remains challenging because of the mismatch between the intricate synthesis processes of COFs and the battery preparation environment, which makes it difficult to build continuous ion channels and low-impedance electrochemical interfaces for devices. Here, we present an in situ gelation method to produce COF gel electrolytes (CGEs) within liquid carbonate electrolyte, integrating COF synthesis with their applicability in batteries. This method leads to long-range interconnected and highly crystalline skeletons of COFs from a robust precoordination structure between lithium salts of liquid electrolyte and building blocks. By incorporating the lithium affinity groups in the COFs, the developed CGEs show a remarkable 3-fold enhancement in ionic conductivity, reaching up to 10.5 mS cm-1 compared to the corresponding liquid carbonate electrolytes. Furthermore, the CGEs exhibit a low activation energy of 0.068 eV, ensuring efficient ion transport, while demonstrating dendrite-free lithium deposition even after prolonged testing periods exceeding 1800 h. These CGEs exhibit excellent rate performance (reversible capacity up to 101 mAh g-1 at a current density of 3C, 1C = 170 mAh g-1) in Li-LiFePO4 coin cells and reversible cycling under extreme conditions (reversible capacity up to 158 mAh g-1 under folding state at 0.1C) in pouch cells. Importantly, our novel methodology extends beyond lithium-ion systems, as it can also be applied to the synthesis of CGEs utilizing potassium, magnesium, zinc, sodium, and calcium ions.

High-speed polarization tracking using thin film lithium niobate integrated dynamic polarization controller.

Dynamic polarization controllers (DPCs) are essential devices in various optical applications. We develop a thin film lithium niobate (TFLN) integrated DPC driven by the real-time implemented Jacobian control algorithm for fast polarization tracking. Experimental results demonstrate a high polarization tracking speed of 100 krad/s when targeting a specific linear state of polarization, with a low control loop delay of 420 ns, half-wave control voltages of 2.75 V, and a fast polarization restoring time of 1.6 us. Compared to previously reported integrated DPCs, the TFLN-based DPC achieves significantly higher tracking speed and lower loop delay. The results highlight the effectiveness of the Jacobian method and the outstanding performance of TFLN-based DPCs. The study opens up possibilities for further advancements in DPC solutions using TFLN technology.

Hydrothermal Synthesis of Highly Crystalline Zwitterionic Vinylene-Linked Covalent Organic Frameworks with Exceptional Photocatalytic Properties.

Ionic covalent organic frameworks (COFs) featuring both crystallinity and ionic characteristics have attracted tremendous attention in recent years. Compared with single anion- or cation-containing ionic COFs, zwitterionic COFs possess unique functionalities beyond single ionic COFs such as tunable charge density and superhydrophilic and highly ion-conductive characteristics, endowing them with huge potential in various applications. However, it remains a considerable challenge to directly synthesize robust, highly crystalline zwitterionic COFs from the original building blocks. Herein, we report a green hydrothermal synthesis strategy to prepare highly crystalline zwitterionic vinylene-linked COFs (ZVCOFs) from the predesigned zwitterionic building block by utilizing 4-dimethylaminopyridine (DMAP) as the high-efficiency catalyst for the first time. Detailed theoretical calculations and experiments revealed that both the high catalytic activity of DMAP and the unique role of water contributed to the formation of highly crystalline ZVCOFs. It was found that the participation of water could not only remarkably reduce the activation energy barrier and thus enhance the reaction reversibility but also enable the hydration of zwitterionic sites and facilitate ordered layered arrangement, which are favorable for the ZVCOF crystallization. Benefiting from the highly π-conjugated structure and hydrophilic characteristic, the obtained ZVCOFs achieved an ultrahigh sacrificial photocatalytic hydrogen evolution rate of 2052 µmol h-1 under visible light irradiation with an apparent quantum yield up to 47.1% at 420 nm, superior to nearly all COF-based photocatalysts ever reported. Moreover, the ZVCOFs could be deposited on a support as a photocatalytic film device, which demonstrated a remarkable photocatalytic performance of 402.1 mmol h-1 m-2 for hydrogen evolution.

Covalent Organic Frameworks in Aqueous Zinc-Ion Batteries.

The development and utilization of green renewable energy are imperative with the aggravation of environmental pollution and energy crisis. In recent years, the exploration of electrochemical energy storage systems has gradually become a research hotspot in energy. Among them, aqueous zinc-ion batteries (ZIBs) have progressively developed into highly competitive and efficient energy storage devices owing to their inherent safety, natural abundance, and higher theoretical capacity. However, the practical application of ZIBs suffers from the limitation of challenges such as the absence of proper cathode materials and the unavoidable zinc dendrites and side reactions of Zn anode. Covalent organic frameworks (COFs) are an attractive class of electrode materials due to their inherent advantages, like structural designability, high stability, and ordered-open channels, bestowing them with great potential to overcome the problems of ZIBs. In this review, we concentrate on the discussion of designed strategies of COFs applied to ZIBs. Furthermore, the methods of using COFs to solve the challenging problems of cathode development, anode modification, and electrolyte optimization for ZIBs are summarized. Finally, the existing difficulties, solution measures, and prospects of COFs for ZIBs applications are discussed. Our commentary hopes to serve as a valuable reference for developing COFs-based ZIBs.

In vitro antibiofilm and bacteriostatic activity of diacerein against Enterococcus faecalis.

Enterococcus faecalis is one of the main pathogens that causes hospital-acquired infections because it is intrinsically resistant to some antibiotics and often is capable of biofilm formation, which plays a critical role in resisting the external environment. Therefore, attacking biofilms is a potential therapeutic strategy for infections caused by E. faecalis. Current research indicates that diacerein used in the treatment of osteoarthritis showed antimicrobial activity on strains of gram-positive cocci in vitro. In this study, we tested the MICs of diacerein using the broth microdilution method, and successive susceptibility testing verified that E. faecalis is unlikely to develop resistance to diacerein. In addition, we obtained a strain of E. faecalis HE01 with strong biofilm-forming ability from an eye hospital environment and demonstrated that diacerein affected the biofilm development of HE01 in a dose-dependent manner. Then, we explored the mechanism by which diacerein inhibits biofilm formation through qRT-PCR, extracellular protein assays, hydrophobicity assays and transcriptomic analysis. The results showed that biofilm formation was inhibited at the initial adhesion stage by inhibition of the expression of the esp gene, synthesis of bacterial surface proteins and reduction in cell hydrophobicity. In addition, transcriptome analysis showed that diacerein not only inhibited bacterial growth by affecting the oxidative phosphorylation process and substance transport but also inhibited biofilm formation by affecting secondary metabolism, biosynthesis, the ribosome pathway and luxS expression. Thus, our findings provide compelling evidence for the substantial therapeutic potential of diacerein against E. faecalis biofilms.

Identification of new aptamer BC-3 targeting RPS7 from rapid screening for bladder carcinoma.

Aptamers, short single DNA or RNA oligonucleotides, have shown immense application potential as molecular probes for the early diagnosis and therapy of cancer. However, conventional cell-SELEX technologies for aptamer discovery are time-consuming and laborious. Here we discovered a new aptamer BC-3 by using an improved rapid X-Aptamer selection process for human bladder carcinoma, for which there is no specific molecular probe yet. We show that BC-3 exhibited excellent affinity in bladder cancer cells but not normal cells. We demonstrate that BC-3 displayed high selectivity for tumor cells over their normal counterparts in vitro, in mice, and in patient tumor tissue specimens. Further endocytosis pathway analysis revealed that BC-3 internalized into bladder cancer cells via clathrin-mediated endocytosis. Importantly, we identified ribosomal protein S7 (RPS7) as the binding target of BC-3 via an integrated methodology (mass spectrometry, colocalization assay, and immunoblotting). Together, we report that a novel aptamer BC-3 is discovered for bladder cancer and its properties in the disease are unearthed. Our findings will facilitate the discovery of novel diagnostic and therapeutic strategies for bladder cancer.

A Non-G-Quadruplex DNA Aptamer Targeting NCL for Diagnosis and Therapy in Bladder Cancer.

Bladder cancer (BC) is a highly aggressive malignant tumor affecting the urinary system, characterized by metastasis and a poor prognosis that often leads to limited therapeutic success. This study aims to develop a novel DNA aptamer for the diagnosis and treatment of BC using a tissue-based systematic evolution of ligands by an exponential enrichment (SELEX) process. By using SELEX, this work successfully generates a new aptamer named TB-5, which demonstrates a remarkable and specific affinity for nucleolin (NCL) in BC tissues and displays marked biocompatibility both in vitro and in vivo. Additionally, this work shows that NCL is a reliable tissue-specific biomarker in BC. Moreover, according to circular dichroism spectroscopy, TB-5 forms a non-G-quadruplex structure, distinguishing it from the current NCL-targeting aptamer AS1411, and exhibits a distinct binding region on NCL compared to AS1411. Notably, this study further reveals that TB-5 activates NCL function by promoting autophagy and suppressing the migration and invasion of BC cells, which occurs by disrupting mRNA transcription processes. These findings highlight the critical role of NCL in the pathological examination of BC and warrant more comprehensive investigations on anti-NCL aptamers in BC imaging and treatment.

Green and Scalable Synthesis of Atomic-Thin Crystalline Two-Dimensional Triazine Polymers with Ultrahigh Photocatalytic Properties.

Scalable and eco-friendly synthesis of crystalline two-dimensional (2D) polymers with proper band gap and single-layer thickness is highly desired for the fundamental research and practical applications of 2D polymers; however, it remains a considerable and unresolved challenge. Herein, we report a convenient and robust method to synthesize a series of crystalline covalent triazine framework nanosheets (CTF NSs) with a thickness of ∼80 nm via a new solvent-free salt-catalyzed nitrile cyclotrimerization process, which enables the cost-effective large-scale preparation of crystalline CTF NSs at the hundred-gram level. Theoretical calculations and detailed experiments revealed for the first time that the conventional salts such as KCl can not only act as physical templates as traditionally believed but also more importantly can efficiently catalyze the cyclotrimerization reaction of carbonitrile monomers as a new kind of green solid catalysts to achieve crystalline CTF NSs. Upon simple liquid-phase sonication, these CTF NSs can be easily further exfoliated into abundant single-layer crystalline 2D triazine polymers (2D-TPs) in high yields. The obtained atomically thin crystalline 2D-TPs with a band gap of 2.36 eV and rich triazine active groups exhibited a remarkable photocatalytic hydrogen evolution rate of 1321 µmol h-1 under visible light irradiation with an apparent quantum yield up to 29.5% at 420 nm and excellent photocatalytic overall water splitting activity with a solar-to-hydrogen efficiency up to 0.35%, which exceed all molecular framework materials and are among the best metal-free photocatalysts ever reported. Moreover, the processable 2D-TPs could be readily assembled on a support as a photocatalytic film device, which demonstrated superior photocatalytic performance (135.2 mmol h-1 m-2 for hydrogen evolution).

Three-dimensional graphene/metal-organic framework composites for electrochemical energy storage and conversion.

Three-dimensional graphene (3DG)/metal-organic framework (MOF)-based composites have attracted more and more attention in the field of energy due to their unique hierarchical porous structure and properties. The combination of graphene with MOFs can not only effectively overcome the limitations of poor electrical conductivity and low stability of MOFs, but also prevent the aggregation and reaccumulation between graphene sheets. Moreover, 3DG/MOF composites can also be used as multifunctional precursors with adjustable structures and composition of derivatives, thus expanding their applications in the field of electrochemistry. This feature article elaborates the latest synthesis methods of 3DG/MOF composites and their derivatives, along with their applications in batteries, supercapacitors (SCs) and electrocatalysis. In addition, the current challenges and future prospects of 3DG/MOF-based composites are discussed.

Aqueous Processable Two-Dimensional Triazine Polymers with Superior Photocatalytic Properties.

Efficient and scalable production of high-quality and processable two-dimensional (2D) polymers are highly desired but have not yet been reported. Herein, we demonstrate a convenient noncovalent functionalization strategy for producing highly uniform, aqueous processable and semiconducting 2D triazine polymers. Experimental and theoretical analysis reveal that the aromatic amphiphilic 1-pyrenebutyrate can adsorb and intercalate into the interlayer of bulk crystalline covalent triazine framework (CTF) through noncovalent π-π stacking interaction between the pyrene moiety and the porous basal plane of 2D triazine polymer layer, which greatly facilitate the exfoliation of CTF in water in large scale. The as-prepared highly water-dispersible single-layer/few-layer 2D triazine polymer nanosheets can be easily processed into ultralight aerogels with a density of 5-15 mg cm-3 , which can be further shaped into mechanically strong films upon simple compression. This noncovalent functionalization not only improve the dispersibility and processability of 2D triazine polymer, but also optimize its band structure and promote the photogenerated carrier separation via an interesting surface molecule doping effect, thus resulting in a remarkable photocatalytic hydrogen evolution rate of 1249 µmol h-1 (24980 µmol g-1 h-1 ) and apparent quantum efficiency up to 27.2 % at 420 nm for the 2D triazine polymer, outperforming most metal-free photocatalysts ever reported.

Antimony Oxides-Based Anode Materials for Alkali Metal-Ion Storage.

With the increasing demand for renewable energy, alkali metal-ion (lithium/sodium/potassium-ion) batteries play more and more important roles in the field of static storage and electrical vehicle industry. Novel anode materials with high reversible capacity, safety and long-term cycling stability are desiderated to meet the ever-growing demand for alkali metal-ion batteries with high electrochemical performance. Antimony oxides (Sbx Oy ) show electrochemical reaction activity with all of lithium, sodium and potassium, and are expected to be promising anode materials for alkali metal-ion storage due to their high theoretical capacities, appropriate operating potential and excellent safety properties. This review is devoted to overview the research progress on reaction mechanism and improvements in electrochemical performance of antimony oxides for alkali metal-ion storage, and look forward to their further prospects.

Influence of Ambivalent Sexism on Intimate Partner Violence Tolerance and Mental Violence in a Chinese Female Sample: Relationship Causality Orientation as a Moderator.

The current study examined how the general tolerance of women's intimate partner violence and mental violence perpetration are affected by women's ambivalent sexism and relationship causality orientation. One hundred and forty-nine of 221 Chinese female participants recruited on an online platform were included in the final data analysis. The results showed that causality orientation plays a moderating role. Specifically, as controlled orientation increased, the relationship between hostile sexism and intimate partner violence tolerance became stronger. As the autonomous orientation increased, the relationship between benevolent sexism and intimate partner violence tolerance became weaker. Hostile sexism and controlled orientation positively predict women's mental violence perpetration.