Controllable Double Difluoromethylene Insertions into S-Cu Bonds: (Arylthio)tetrafluoroethylation of Aryl Iodides with TMSCF2Br.

A new method of constructing "ArSCF2CF2Cu" from ArSCu and TMSCF2Br (TMS=trimethylsilyl) has been developed. The cross-coupling reactions of the obtained "ArSCF2CF2Cu" with diverse aryl iodides (Ar'I) provide an efficient access to Ar'CF2CF2SAr. Mechanistic studies demonstrate that the "ArSCF2CF2Cu" species were generated through controllable double difluoromethylene insertions into ArS-Cu bonds rather than the 1,2-addition of ArSCu to tetrafluoroethylene.

Progress and Perspectives on the Development of Pouch-Type Lithium Metal Batteries.

Lithium (Li) metal batteries (LMBs) are the "holy grail" in the energy storage field due to their high energy density (theoretically >500 Wh kg-1 ). Recently, tremendous efforts have been made to promote the research & development (R&D) of pouch-type LMBs toward practical application. This article aims to provide a comprehensive and in-depth review of recent progress on pouch-type LMBs from full cell aspect, and to offer insights to guide its future development. It will review pouch-type LMBs using both liquid and solid-state electrolytes, and cover topics related to both Li and cathode (including LiNix Coy Mn1-x-y O2 , S and O2 ) as both electrodes impact the battery performance. The key performance criteria of pouch-type LMBs and their relationship in between are introduced first, then the major challenges facing the development of pouch-type LMBs are discussed in detail, especially those severely aggravated in pouch cells compared with coin cells. Subsequently, the recent progress on mechanistic understandings of the degradation of pouch-type LMBs is summarized, followed with the practical strategies that have been utilized to address these issues and to improve the key performance criteria of pouch-type LMBs. In the end, it provides perspectives on advancing the R&Ds of pouch-type LMBs towards their application in practice.

Solid-Solution or Intermetallic Compounds: Phase Dependence of the Li-Alloying Reactions for Li-Metal Batteries.

Electrochemical Li-alloying reactions with Li-rich alloy phases render a much higher theoretical capacity that is critical for high-energy batteries, and the accompanying phase transition determines the alloying/dealloying reversibility and cycling stability. However, the influence of phase-transition characteristics upon the thermodynamic properties and diffusion kinetic mechanisms among the two categories of alloys, solid-solutions and intermetallic compounds, remains incomplete. Here we investigated three representative Li-alloys: Li-Ag alloy of extended solid-solution regions; Li-Zn alloy of an intermetallic compound with a solid-solution phase of a very narrow window in Li atom concentration; and Li-Al alloy of an intermetallic compound. Solid-solution phases undertake a much lower phase-transition energy barrier than the intermetallic compounds, leading to a considerably higher Li-alloying/dealloying reversibility and cycling stability, which is due to the subtle structural change and chemical potential gradient built up inside of the solid-solution phases. These two effects enable the Li atoms to enter the bulk of the Li-Ag alloy to form a homogeneous alloy phase. The pouch cell of the Li-rich Li20Ag alloy pairs with a LiNi0.8Co0.1Mn0.1O2 cathode under an areal capacity of 3.5 mAh cm-2 can retain 87% of its initial capacity after 250 cycles with an enhanced Coulombic efficiency of 99.8 ± 0.1%. While Li-alloying reactions and the alloy phase transitions have always been tightly linked in past studies, our findings provide important guidelines for the intelligent design of components for secondary metal batteries.

Stability Analysis of Anionic-CO2-Soluble Surfactant Di-(2-ethylhexyl) Sodium Sulfosuccinate-Assisted Oily Foam Based on Statistical Analysis of Bubble Dynamic Characteristics.

Currently, oily foam stability in CO2 injection for heavy oil recovery exhibits inadequacies that considerably constrain its extensive application. Some scholars have conducted research demonstrating that CO2-soluble surfactants can assist in inducing heavy oil to form oil-based foams (oily foam). In this study, stability tests for the oily foam were conducted at different surfactant concentrations using a visualized PVT cell. Oily foam stability was assessed by calculating the comprehensive foam index (S) and analyzing the bubble images. The research indicates that AOT can effectively reduce the interfacial tension between oil and gas. At a concentration of 0.1 wt % AOT, the interfacial tension can be effectively reduced from 1.75 to 1.14 mN/m. The concentration of 0.3 wt % AOT represents a turning point, with an S of 16 101.7 mL·min. Beyond this concentration, the increase in S becomes less pronounced. As the concentration of CO2-soluble surfactant is increased from 0.1 to 0.5 wt %, the average bubble radius decreases from 2.74 to 0.43 mm, while the number of bubbles per unit area increases from 5.56 to 81.1 per cm2. With an increasing concentration of the CO2-soluble surfactant, the system generates more and smaller gas bubbles within the oily foam, resulting in a slower bubble coalescence. The findings of this study are poised to play a pivotal role in enhancing heavy oil recovery efficiency.

Efficiencies of Various in situ Polymerizations of Liquid Electrolytes and the Practical Implications for Quasi Solid-state Batteries.

In situ polymerization of liquid electrolytes is currently the most feasible way for constructing solid-state batteries, which, however, is affected by various interfering factors of reactions and so the electrochemical performance of cells. To disclose the effects from polymerization conditions, two types of generally used in situ polymerizing reactions of ring-opening polymerization (ROP) and double bond radical polymerization (DBRP) were investigated on the aspects of monomer conversion and electrochemical properties (Li+ -conductivity and interfacial stability). The ROP generated poly-ester and poly-carbonate show a high monomer conversion of ≈90 %, but suffer a poor Li+ -conductivity of lower than 2×10-5  S cm-1 at room temperature (RT). Additionally, the terminal alkoxy anion derived from the ROP is not resistant to high-voltage cathodes. While, the DBRP produced poly-VEC(vinyl ethylene carbonate) and poly-VC(vinylene carbonate) show lower monomer conversions of 50-80 %, delivering relatively higher Li+ -conductivities of 2×10-4  S cm-1 at RT. Compared two polymerizing reactions and four monomers, the VEC-based F-containing copolymer possesses advantages in Li+ -conductivity and antioxidant capacity, which also shows simultaneous stability towards Li-metal with the help of LiF-based passivating layer, allowing a long-term stable cycling of high-voltage quasi solid-state cells.

Machine Learning Driven Synthesis of Few-Layered WTe2 with Geometrical Control.

Reducing the lateral scale of two-dimensional (2D) materials to one-dimensional (1D) has attracted substantial research interest not only to achieve competitive electronic applications but also for the exploration of fundamental physical properties. Controllable synthesis of high-quality 1D nanoribbons (NRs) is thus highly desirable and essential for further study. Here, we report the implementation of supervised machine learning (ML) for the chemical vapor deposition (CVD) synthesis of high-quality quasi-1D few-layered WTe2 NRs. Feature importance analysis indicates that H2 gas flow rate has a profound influence on the formation of WTe2, and the source ratio governs the sample morphology. Notably, the growth mechanism of 1T' few-layered WTe2 NRs is further proposed, which provides new insights for the growth of intriguing 2D and 1D tellurides and may inspire the growth strategies for other 1D nanostructures. Our findings suggest the effectiveness and capability of ML in guiding the synthesis of 1D nanostructures, opening up new opportunities for intelligent materials development.

Structure Analysis and Study of Biological Activities of Condensed Tannins from Bruguiera gymnorhiza (L.) Lam and Their Effect on Fresh-Cut Lotus Roots.

Bruguiera gymnorhiza (L.) Lam is a mangrove plant that spread in many parts of the world. Though mangrove plant polyphenols have been reported to exhibit many biological activities, little is known about mangrove plant tannins. To explore the application value of tannins from B. gymnorhiza, analyses on the structure and biological activity of condensed tannins (CTs) from Bruguiera gymnorhiza (L.) Lam were carried out. The results from 13C nuclear magnetic resonance (13C-NMR) and reversed-phase, high-performance liquid chromatography (RP-HPLC) showed that the CTs were dominated by procyanidins, with a small quantity of prodelphinidins and propelargonidins; and that the monomeric constituents of B. gymnorhiza tannins were catechin/epicatechin, gallocatechin/epigallocatechin and afzelechin/epiafzelechin. The CTs were reversible and mixed competitive inhibitors of tyrosinase and the 50% inhibiting concentration (IC50) was estimated to be 123.90 ± 0.140 µg/mL. The antioxidant activities of CTs from B. gymnorhiza leaves were evaluated, the IC50 for 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis (3-ethylbenzo-thiazoline-6-sulfonic acid diammonium salt) (ABTS) scavenging activities were 88.81 ± 0.135 and 105.03 ± 0.130 µg/mL, respectively, and the ferric ion reducing antioxidant power (FRAP) value was 1052.27 ± 4.17 mgAAE/g. In addition, the results from fresh-keeping assays on fresh-cut lotus root reveal that CTs from B. gymnorhiza had excellent effects on inhibiting the activities of polyphenol oxidase (PPO) and peroxidase (POD), protecting fresh-cut lotus root from the oxidation of total phenolics and malondialdehyde (MDA) content and slowing the increase in total phenol content (TPC) at 4 °C during the whole storage period. Therefore, CTs showed good effects against the browning of fresh-cut lotus root. Together, these results suggested that B. gymnorhiza CTs are promising antibrowning agents for fresh-cut fruits.

Modification of Transition-Metal Redox by Interstitial Water in Hexacyanometalate Electrodes for Sodium-Ion Batteries.

A sodium-ion battery (SIB) solution is attractive for grid-scale electrical energy storage. Low-cost hexacyanometalate is a promising electrode material for SIBs because of its easy synthesis and open framework. Most hexacyanometalate-based SIBs work with aqueous electrolyte, and interstitial water in the material has been found to strongly affect the electrochemical profile, but the mechanism remains elusive. Here we provide a comparative study of the transition-metal redox in hexacyanometalate electrodes with and without interstitial water based on soft X-ray absorption spectroscopy and theoretical calculations. We found distinct transition-metal redox sequences in hydrated and anhydrated NaxMnFe(CN)6·zH2O. The Fe and Mn redox in hydrated electrodes are separated and are at different potentials, leading to two voltage plateaus. On the contrary, mixed Fe and Mn redox in the same potential range is found in the anhydrated system. This work reveals for the first time how transition-metal redox in batteries is strongly affected by interstitial molecules that are seemingly spectators. The results suggest a fundamental mechanism based on three competing factors that determine the transition-metal redox potentials. Because most hexacyanometalate electrodes contain water, this work directly reveals the mechanism of how interstitial molecules could define the electrochemical profile, especially for electrodes based on transition-metal redox with well-defined spin states.

Invisible own- and other-race faces presented under continuous flash suppression produce affective response biases.

One triumph of the human mind is the ability to place the multitudinous array of people we encounter into in- and out-group members based on racial characteristics. One fundamental question that remains to be answered is whether invisible own- and other-race faces can nevertheless influence subsequent affective judgments. Here, we employed continuous flash suppression (CFS) to render own- and other-race faces unperceivable in an affective priming task. Both on-line and off-line awareness checks were employed to provide more stringent control of partial awareness. Results revealed that relative to own-race faces, imperceptible other-race faces significantly facilitated participants' identification of negative words, suggesting an other-race derogation bias. When faces were presented consciously, we found that not only other-race faces facilitated detection of negative words, but also own-race faces facilitated detection of positive words. These findings together provide novel and strong evidence suggesting that invisible racial faces can bias affective responses.

Removal of interstitial H2O in hexacyanometallates for a superior cathode of a sodium-ion battery.

Sodium is globally available, which makes a sodium-ion rechargeable battery preferable to a lithium-ion battery for large-scale storage of electrical energy, provided a host cathode for Na can be found that provides the necessary capacity, voltage, and cycle life at the prescribed charge/discharge rate. Low-cost hexacyanometallates are promising cathodes because of their ease of synthesis and rigid open framework that enables fast Na(+) insertion and extraction. Here we report an intriguing effect of interstitial H2O on the structure and electrochemical properties of sodium manganese(II) hexacyanoferrates(II) with the nominal composition Na2MnFe(CN)6·zH2O (Na2-δMnHFC). The newly discovered dehydrated Na2-δMnHFC phase exhibits superior electrochemical performance compared to other reported Na-ion cathode materials; it delivers at 3.5 V a reversible capacity of 150 mAh g(-1) in a sodium half cell and 140 mAh g(-1) in a full cell with a hard-carbon anode. At a charge/discharge rate of 20 C, the half-cell capacity is 120 mAh g(-1), and at 0.7 C, the cell exhibits 75% capacity retention after 500 cycles.

Rhombohedral prussian white as cathode for rechargeable sodium-ion batteries.

A novel air-stable sodium iron hexacyanoferrate (R-Na1.92Fe[Fe(CN)6]) with rhombohedral structure is demonstrated to be a scalable, low-cost cathode material for sodium-ion batteries exhibiting high capacity, long cycle life, and good rate capability. The cycling mechanism of the iron redox is clarified and understood through synchrotron-based soft X-ray absorption spectroscopy, which also reveals the correlation between the physical properties and the cell performance of this novel material. More importantly, successful preparation of a dehydrated iron hexacyanoferrate with high sodium-ion concentration enables the fabrication of a discharged sodium-ion battery with a non-sodium metal anode, and the manufacturing feasibility of low cost sodium-ion batteries with existing lithium-ion battery infrastructures has been tested.

Metal-organic-framework-confined quantum dots enhance photocurrent signals: A molecularly imprinted photoelectrochemical cathodic sensor for rapid and sensitive tetracycline detection.

BACKGROUND: Tetracycline (TC), a cost-effective broad-spectrum antibacterial drug, has been excessively utilized in the livestock and poultry industry, leading to a serious overabundance of TC in livestock wastewater. However, conventional analytical methods such as liquid chromatography and gas chromatography face challenges in achieving sensitive detection of trace amounts of TC in complex substrates. Therefore, it is imperative to develop a highly sensitive and anti-interference analytical method for the detection of tetracycline in livestock wastewater. RESULTS: A porphyrin-based MOF (PCN-224)-confined carbon dots (CDs) material (CDs@PCN-224) was synthesized by a "bottle-around-ship" strategy. The reduced carrier migration distance is conducive to the separation of electron-hole pairs and enhanced the photocurrent signal due to the tight coupling of CDs and PCN-224. Further, molecularly imprinted polymer (MIP) was synthesized by rapid in-situ UV-polymerization and employed as a recognition element. The specific recognition of the target by imprinted cavities blocks electron transfer, resulting in a "turn off" response signal, thus realizing the selective detection of TC. Under optimal conditions, the constructed MIP-PEC cathodic sensor detected 1.00 × 10-12 M to 1.00 × 10-7 M of TC sensitively, with a limit of detection of 3.72 × 10-13 M. In addition, the proposed MIP-PEC sensor demonstrated good TC detection performance in actual livestock wastewater. SIGNIFICANCE: The strategy based on MOF pore-confined quantum dots can effectively enhance the photocurrent response of the photosensitive substrate. Simultaneously, the MIP constructed by in-situ rapid UV-polymerization showed excellent anti-interference and reusable properties. This work provides a promising MIP-PEC cathodic sensing method for the rapid and sensitive detection of antibiotics in complex-matrix environmental samples.

Machine learning-guided realization of full-color high-quantum-yield carbon quantum dots.

Carbon quantum dots (CQDs) have versatile applications in luminescence, whereas identifying optimal synthesis conditions has been challenging due to numerous synthesis parameters and multiple desired outcomes, creating an enormous search space. In this study, we present a novel multi-objective optimization strategy utilizing a machine learning (ML) algorithm to intelligently guide the hydrothermal synthesis of CQDs. Our closed-loop approach learns from limited and sparse data, greatly reducing the research cycle and surpassing traditional trial-and-error methods. Moreover, it also reveals the intricate links between synthesis parameters and target properties and unifies the objective function to optimize multiple desired properties like full-color photoluminescence (PL) wavelength and high PL quantum yields (PLQY). With only 63 experiments, we achieve the synthesis of full-color fluorescent CQDs with high PLQY exceeding 60% across all colors. Our study represents a significant advancement in ML-guided CQDs synthesis, setting the stage for developing new materials with multiple desired properties.

Advances in tumor microenvironment and underlying molecular mechanisms of bladder cancer: a systematic review.

Bladder cancer is one of the most frequent malignant tumors of the urinary system. The prevalence of bladder cancer among men and women is roughly 5:2, and both its incidence and death have been rising steadily over the past few years. At the moment, metastasis and recurrence of advanced bladder cancer-which are believed to be connected to the malfunction of multigene and multilevel cell signaling network-remain the leading causes of bladder cancer-related death. The therapeutic treatment of bladder cancer will be greatly aided by the elucidation of these mechanisms. New concepts for the treatment of bladder cancer have been made possible by the advancement of research technologies and a number of new treatment options, including immunotherapy and targeted therapy. In this paper, we will extensively review the development of the tumor microenvironment and the possible molecular mechanisms of bladder cancer.

Na3V2O2(PO4)2F/graphene sandwich structure for high-performance cathode of a sodium-ion battery.

A Na3V2O2(PO4)2F/reduced-graphene-oxide (RGO) sandwich structure has been synthesized by a facile one-step solvothermal method. Cubic Na3V2O2(PO4)2F nanoparticles are homogeneously trapped between conductive RGO sheets during its growth and assembled into a compact sandwich structure, which allows the electrically insulating Na3V2O2(PO4)2F nanoparticles to be wired up to a current collector through the underlying graphene conducting layers. As a sodium-insertion cathode material, the structure exhibits a high reversible capacity of 120 mA h g(-1) at a discharge rate of C/20 with a capacity retention of 100.4 mA h g(-1) at 1 C and an excellent cyclic retention of 91.4% after the 200th cycle at C/10. These results highlight the importance of anchoring Na3V2O2(PO4)2F on a conducting scaffold for maximum utilization of the electrochemically active Na3V2O2(PO4)2F particles in a high-performance sodium-ion battery.

Preparation and Characterization of Multi-Doped Porous Carbon Nanofibers from Carbonization in Different Atmospheres and Their Oxygen Electrocatalytic Properties Research.

Recently, electrocatalysts for oxygen reduction reaction (ORR) as well as oxygen evolution reaction (OER) hinged on electrospun nanofiber composites have attracted wide research attention. Transition metal elements and heteroatomic doping are important methods used to enhance their catalytic performances. Lately, the construction of electrocatalysts based on metal-organic framework (MOF) electrospun nanofibers has become a research hotspot. In this work, nickel-cobalt zeolitic imidazolate frameworks with different molar ratios (NixCoy-ZIFs) were synthesized in an aqueous solution, followed by NixCoy-ZIFs/polyacrylonitrile (PAN) electrospun nanofiber precursors, which were prepared by a simple electrospinning method. Bimetal (Ni-Co) porous carbon nanofiber catalysts doped with nitrogen, oxygen, and sulfur elements were obtained at high-temperature carbonization treatment in different atmospheres (argon (Ar), Air, and hydrogen sulfide (H2S)), respectively. The morphological properties, structures, and composition were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Moreover, the specific surface area of materials and their pore size distribution was characterized by Brunauer-Emmett-Teller (BET). Linear sweep voltammetry curves investigated catalyst performances towards oxygen reduction and evolution reactions. Importantly, Ni1Co2-ZIFs/PAN-Ar yielded the best ORR activity, whereas Ni1Co1-ZIFs/PAN-Air exhibited the best OER performance. This work provides significant guidance for the preparation and characterization of multi-doped porous carbon nanofibers carbonized in different atmospheres.

Highly Stable 4.6 V LiCoO2 Cathodes for Rechargeable Li Batteries by Rubidium-Based Surface Modifications.

Among extensively studied Li-ion cathode materials, LiCoO2 (LCO) remains dominant for portable electronic applications. Although its theoretical capacity (274 mAh g-1 ) cannot be achieved in Li cells, high capacity (≤240 mAh g-1 ) can be obtained by raising the charging voltage up to 4.6 V. Unfortunately, charging Li-LCO cells to high potentials induces surface and structural instabilities that result in rapid degradation of cells containing LCO cathodes. Yet, significant stabilization is achieved by surface coatings that promote formation of robust passivation films and prevent parasitic interactions between the electrolyte solutions and the cathodes particles. In the search for effective coatings, the authors propose RbAlF4 modified LCO particles. The coated LCO cathodes demonstrate enhanced capacity (>220 mAh g-1 ) and impressive retention of >80/77% after 500/300 cycles at 30/45 °C. A plausible mechanism that leads to the superior stability is proposed. Finally the authors demonstrate that the main reason for the degradation of 4.6 V cells is the instability of the anode side rather than the failure of the coated cathodes.

Aqueous cathode for next-generation alkali-ion batteries.

The lithium-ion batteries that ushered in the wireless revolution rely on electrode strategies that are being stretched to power electric vehicles. Low-cost, safe electrical-energy storage that enables better use of alternative energy sources (e.g., wind, solar, and nuclear) requires an alternative strategy. We report a demonstration of the feasibility of a battery having a thin, solid alkali-ion electrolyte separating a water-soluble redox couple as the cathode and lithium or sodium in a nonaqueous electrolyte as the anode. The cell operates without a catalyst and has high storage efficiency. The possibility of a flow-through mode for the cathode allows flexibility of the cell design for safe, large-capacity electrical-energy storage at an acceptable cost.

Simultaneous leaching of multiple heavy metals from a soil column by extracellular polymeric substances of Aspergillus tubingensis F12.

The use of the biological agents for leaching heavy metals from contaminated soils is a very promising method that is both efficient and eco-friendly. In this study, a fungus Aspergillus tubingensis F12 was reported to possess a strong adsorption capacity for various heavy metal ions and shown to adsorb 90.8% Pb, 68.4% Zn, 64.5% Cr, 13.1% Cu, 12.9% Ni, and 6.9% Cd in aqueous solution. As extracellular polymeric substance (EPS) was found to play a leading role in the adsorption of metal ions, we applied EPS as a leaching agent to simultaneously remove six metals from soil in a column leaching experiment. The flow rate, initial solution pH, initial EPS concentration, and ionic strength were investigated using response surface methodology. The minimum and maximum metal leaching capacities were determined to be 0.089 mg/g and 3.703 mg/g, respectively. Verified by Fourier transform infrared spectroscopy, scanning electron microscope energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy, we made the preliminary deductions that ion exchange determines the leaching capacity limit and that biosorption plays a large role in reaching that limit. Additionally, the redox behaviour of Cu produced more carboxyl groups, which increased the adsorption of heavy metals. The ecological impact of this method was also examined; we found that the influences of leaching with EPS on soil properties and microbial community structure were slight. Therefore, the reported leaching process might have application prospects for metal removal from soil.