Constructing Hollow Microcubes SnS2 as Negative Electrode for Sodium-ion and Potassium-ion Batteries.

Sodium/potassium-ion batteries (NIBs and KIBs) are considered the most promising candidates for lithium-ion batteries in energy storage fields. Tin sulfide (SnS2) is regarded as an attractive negative candidate for NIBs and KIBs thanks to its superior power density, high-rate performance and natural richness. Nevertheless, the slow dynamics, the enormous volume change and the decomposition of polysulfide intermediates limit its practical application. Herein, microcubes SnS2 were prepared through sacrificial MnCO3 template-assisted and a facile solvothermal reaction strategy and their performance was investigated in Na and K-based cells. The unique hollow cubic structure and well-confined SnS2 nanosheets play an important role in Na+/K+ rapid kinetic and alleviating volume change. The effect of the carbon additives (Super P/C65) on the electrochemical properties were investigated thoroughly. The in operando and ex-situ characterization provide a piece of direct evidence to clarify the storage mechanism of such conversion-alloying type negative electrode materials.

Exploring the Key Amino Acid Residues Surrounding the Active Center of Lactate Dehydrogenase A for the Development of Ideal Inhibitors.

Lactate dehydrogenase A (LDHA) primarily catalyzes the conversion between lactic acid and pyruvate, serving as a key enzyme in the aerobic glycolysis pathway of sugar in tumor cells. LDHA plays a crucial role in the occurrence, development, progression, invasion, metastasis, angiogenesis, and immune escape of tumors. Consequently, LDHA not only serves as a biomarker for tumor diagnosis and prognosis but also represents an ideal target for tumor therapy. Although LDHA inhibitors show great therapeutic potential, their development has proven to be challenging. In the development of LDHA inhibitors, the key active sites of LDHA are emphasized. Nevertheless, there is a relative lack of research on the amino acid residues around the active center of LDHA. Therefore, in this study, we investigated the amino acid residues around the active center of LDHA. Through structure comparison analysis, five key amino acid residues (Ala30, Met41, Lys131, Gln233, and Ala259) were identified. Subsequently, the effects of these five residues on the enzymatic properties of LDHA were investigated using site-directed mutagenesis. The results revealed that the catalytic activities of the five mutants varied to different degrees in both the reaction from lactic acid to pyruvate and pyruvate to lactic acid. Notably, the catalytic activities of LDHAM41G and LDHAK131I were improved, particularly in the case of LDHAK131I. The results of the molecular dynamics analysis of LDHAK131I explained the reasons for this phenomenon. Additionally, the optimum temperature of LDHAM41G and LDHAQ233M increased from 35 °C to 40 °C, whereas in the reverse reaction, the optimum temperature of LDHAM41G and LDHAK131I decreased from 70 °C to 60 °C. These findings indicate that Ala30, Met41, Lys131, Gln233, and Ala259 exert diverse effects on the catalytic activity and optimum temperature of LHDA. Therefore, these amino acid residues, in addition to the key catalytic site of the active center, play a crucial role. Considering these residues in the design and screening of LDHA inhibitors may lead to the development of more effective inhibitors.

Polydentate Ligand Reinforced Chelating to Stabilize Buried Interface toward High-Performance Perovskite Solar Cells.

The instability of the buried interface poses a serious challenge for commercializing perovskite photovoltaic technology. Herein, we report a polydentate ligand reinforced chelating strategy to strengthen the stability of buried interface by managing interfacial defects and stress. The bis(2,2,2-trifluoroethyl) (methoxycarbonylmethyl)phosphonate (BTP) is employed to manipulate the buried interface. The C=O, P=O and two -CF3 functional groups in BTP synergistically passivate the defects from the surface of SnO2 and the bottom surface of the perovskite layer. Moreover, The BTP modification contributes to mitigated interfacial residual tensile stress, promoted perovskite crystallization, and reduced interfacial energy barrier. The multidentate ligand modulation strategy is appropriate for different perovskite compositions. Due to much reduced nonradiative recombination and heightened interface contact, the device with BTP yields a promising power conversion efficiency (PCE) of 24.63 %, which is one of the highest efficiencies ever reported for devices fabricated in the air environment. The unencapsulated BTP-modified devices degrade to 98.6 % and 84.2 % of their initial PCE values after over 3000 h of aging in the ambient environment and after 1728 h of thermal stress, respectively. This work provides insights into strengthening the stability of the buried interface by engineering multidentate chelating ligand molecules.

Single-Molecule Tracking of Reagent Diffusion during Chemical Reactions.

Recent experiments have shown that the diffusion of reagent molecules is inconsistent with what the Stokes-Einstein equation predicts during a chemical reaction. Here, we used single-molecule tracking to observe the diffusion of reactive reagent molecules during click and Diels-Alder (DA) reactions. We found that the diffusion coefficient of the reagents remained unchanged within the experimental uncertainty upon the DA reaction. Yet, diffusion of reagent molecules is faster than predicted during the click reaction when the reagent concentration and catalyst concentration exceed a threshold. A stepwise analysis suggested that the fast diffusion scenario is due to the reaction but not the involvement of the tracer with the reaction itself. The present results provide experimental evidence on the faster-than-expected reagent diffusion during a CuAAC reaction in specific conditions and propose new insights into understanding this unexpected behavior.

Multispectral camouflage nanostructure design based on a particle swarm optimization algorithm for color camouflage, infrared camouflage, laser stealth, and heat dissipation.

With the development of camouflage technology, single camouflage technology can no longer adapt to existing environments, and multispectral camouflage has attracted much research focus. However, achieving camouflage compatibility across different bands remains challenging. This study proposes a multispectral camouflage metamaterial structure using a particle swarm optimization algorithm, which exhibits multifunctional compatibility in the visible and infrared bands. In the visible band, the light absorption rate of the metamaterial structure exceeds 90%. In addition, color camouflage can be achieved by modifying the top cylindrical nanostructure to display different colors. In the infrared band, the metamaterial structure can achieve three functions: dual-band infrared camouflage (3-5 µm and 8-14 µm), laser stealth (1.06, 1.55, and 10.6 µm), and heat dissipation (5-8 µm). This structure exhibits lower emissivity in both the 3-5-µm (ɛ=0.18) and 8-14-µm (ɛ=0.27) bands, effectively reducing the emissivity in the atmospheric window band. The structure has an absorption rate of 99.7%, 95.5%, and 95% for 1.06, 1.55, and 10.6 µm laser wavelengths, respectively. Owing to its high absorptivity, laser stealth is achieved. Simultaneously, considering the heat dissipation requirements of metamaterial structures, the structural emissivity is 0.7 in the non-atmospheric window (5-8 µm), and the heat can be dissipated through air convection. Therefore, the designed metamaterial structure can be used in military camouflage and industrial applications.

Impact of H2O on the Microscopic Oxidation Mechanism of Lollingite: Experimental and Theoretical Analyses.

Lollingite (FeAs2) is considered an arsenic-bearing mineral that is oxidized faster than arsenopyrite. The geometric configuration, chemical valence bond, and microscopic reaction of the oxidation on the surface of lollingite were systematically studied, which are of great significance for understanding the mechanism of oxidative dissolution. X-ray photoelectron spectroscopy (XPS) measurements and density functional theory (DFT) calculations were carried out to characterize the (101) surface oxidation process of lollingite under the O2/O2 + H2O conditions. XPS results confirmed that the participation of water molecules can promote the formation of abundant OH structures on the surface of lollingite, while the relative concentration of O, As(III), and Fe(III) increased. Moreover, the DFT results demonstrated that the (101) As-terminal plane of FeAs2 was the most stable surface with the lowest surface energy. H2O molecules were physically adsorbed onto the Fe atoms of the lollingite surface, while oxygen molecules can readily be adsorbed on the Fe-As2 site by chemical adsorption processes. The oxidation process of the lollingite surface with water includes the following mechanisms: adsorption, dissociation, formation of the hydrogen bond, and desorption. The dissociation of the H2O molecule into OH and H led to the hydroxylation of both Fe and As atoms and the formation of hydrogen bonding. The participation of H2O molecules can also reduce the reaction energy barrier and accelerate the oxidation reaction of the lollingite surface, especially as far as the water dissociation and formation of hydrogen bonds are concerned. According to PDOS data, there is considerable hybridization between the d orbitals of bonded Fe atoms and the p orbitals of O atoms, as well as between the p orbitals of bonded As atoms and the p orbitals of O atoms. Due to a strong propensity for orbital hybridization and bonding between the s orbitals of the H atoms in H2O molecules and the p orbitals of the O atoms on the (101) surface, water molecules have the ability to speed up the oxidation on the surface.

Manipulating the Water Dissociation Electrocatalytic Sites of Bimetallic Nickel-Based Alloys for Highly Efficient Alkaline Hydrogen Evolution.

Transition-metal alloys are currently drawing increasing attention as promising electrocatalysts for the alkaline hydrogen evolution reaction (HER). However, traditional density-functional-theory-derived d-band theory fails to describe the hydrogen adsorption energy (ΔGH ) on hollow sites. Herein, by studying the ΔGH for a series of Ni-M (M=Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Mo, W) bimetallic alloys, an improved d-band center was provided and a potential NiCu electrocatalyst with a near-optimal ΔGH was discovered. Moreover, oxygen atoms were introduced into Ni-M (O-NiM) to balance the adsorption/desorption of hydroxyl species. The tailored electrocatalytic sites for water dissociation can synergistically accelerate the multi-step alkaline HER. The prepared O-NiCu shows the optimum HER activity with a low overpotential of 23 mV at 10 mA cm-2 . This work not only broadens the applicability of d-band theory, but also provides crucial understanding for designing efficient HER electrocatalysts.

Red mud-metakaolin based cementitious material for remediation of arsenic pollution: Stabilization mechanism and leaching behavior of arsenic in lollingite.

The proper treatment of lollingite is of great significance due to its rapid oxidation leading to release of arsenic into the environment. Herein, a green multi-solid waste geopolymer, consisting of red mud, metakaolin, blast furnace slag, and flue gas desulfurization gypsum, was developed. The obtained red mud-metakaolin-based (RMM) geopolymer demonstrated good arsenic retention capability. The results showed that the replacement of SO42- in ettringite with AsO42- via ion exchange, formation of Ca-As and Fe-As precipitates, and physical encapsulation with aluminosilicate gel were the main mechanisms that prevented the release of arsenic. Further dissolution of ettringite in RMM was alleviated by adding a suitable amount of Ca(OH)2 and controlling the pH of the leachate. TCLP results verified that RMM materials possessed an outstanding ability to stabilize arsenic, with a leaching rate below the permitted value of 5 mg/L for safe disposal. The low leachability of the RMM geopolymers (<0.50 mg/L) is potentially related to the pH buffering capacity of the hydration products at a pH range of 2-5. RMM geopolymers showed a high compressive strength (>15 MPa) and low arsenic leaching concentration (<2.66 mg/L) after 28 days of curing. These results demonstrate the potential of RMM geopolymers to be utilized as an environmentally friendly backfilling cementitious material for sustainable remediation of arsenic pollution.

Effects of embolic agents with different particle sizes on interventional treatment of uterine fibroids.

OBJECTIVE: To compare the effects of embolic agents with different particle sizes on interventional treatment of uterine fibroids (UFs). METHODS: One-hundred and thirty patients with UFs were divided into a treatment group and a control group (n=65) by random draw. All patients were treated by uterine artery embolization, with the treatment group using 200 µm polyvinyl alcohol (PVA) particles and the control group using 500 µm PVA particles. RESULTS: The success rate of embolization was 100%. After intervention, the treatment group was significantly less prone to complications such as lower abdominal pain, fever, nausea, vomiting and bleeding than the control group (P<0.05). The follicle-stimulating hormone levels of both groups were similar before and after intervention, and there were also no significant inter-group differences. The uterine and UF volumes of both groups significantly decreased six months after intervention (P<0.05), and those of the treatment group were significantly lower (P<0.05). The two groups had similar physical function, role-physical, bodily pain and general health scores before intervention, but the treatment group scored significantly higher than the control group did six months after intervention (P<0.05). CONCLUSION: Interventional embolization can well treat UFs, without apparently affecting ovarian functions. Small-sized PVA particles can improve the quality of life by shrinking the uterus and UFs as well as by reducing the risks of complications.

[Roles of epidermal growth factor receptor signaling pathway in silicon dioxide-induced epithelial-mesenchymal transition in human pulmonary epithelial cells].

OBJECTIVE: To investigate the effect of silicon dioxide (SiO2) on the expression of E-cadherin, α-smooth muscle actin (α-SMA), and transforming growth factor ß1(TGF-ß1) in human pulmonary epithelial cells (A549) with epithelial-mesenchymal transition (EMT), and to study the roles of epidermal growth factor receptor (EGFR) signaling pathway in SiO2-induced EMT in A549 cells in vitro. METHODS: Alveolar macrophages (AMs) were stimulated with 50 µg/ml SiO2for 3, 6, 12, 18, 24, or 36 h, and the supernatants were collected to measure the expression of TGF-ß1protein by ELISA. The AM supernatant in which TGF-ß1reached the highest expression (T=18 h) was used as AM-conditioned supernatant. A549 cells were cultured in AM-conditioned supernatant and stimulated with indicated doses of SiO2(0, 50, 100, and 200 µg/ml) for 48 h. The cell morphological changes were observed using an inverted microscope. The cells were collected at different times, and the mRNA and protein expression levels of E-cadherin, α-SMA, and EGFR were measured by RT-PCR and immunocytofluorescence, respectively. RESULTS: After stimulation by SiO2, the expression level of TGF-ß1protein at each time point was significantly higher in the presence of AM supernatants than in the absence of AM supernatants (P<0.05). With the action time, the expression level of TGF-ß1protein increased at first and then decreased, and the highest level was reached at 18 h. After exposure to SiO2, A549 cells exhibited mesenchymal characteristics, such as a spindle shape, pseudopodia change, and fibroblast-like morphology, as observed by inverted microscope, especially in the 200 µg/ml group. With increased concentration of SiO2, the mRNA and protein expression of E-cadherin was down-regulated gradually, especially in the 200 µg/ml group, whereas the mRNA and protein expression of α-SMA and EGFR was up-regulated gradually, especially in the 200 µg/m1 group. There were significant differences between the SiO2-treated groups (50, 100, and 200 µg/ml SiO2) and the control group (P<0.05). CONCLUSION: After being stimulated by SiO2in vitro, AMs have significantly increased expression level of TGF-ß1protein. The AM supernatant together with SiO2can induce the transition of pulmonary epithelial cells to mesenchymal cells, and its mechanism may be related to the EGFR signaling pathway.