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ZnO thin films were deposited on semi-insulating (0 0 1) GaAs substrates at different growth conditions by metal-organic chemical vapour deposition. The effect of growth temperature and ambient oxygen partial pressure on the properties of the ZnO films was studied. It was found that these two important parameters affected the structure, crystallinity, surface morphology, and optical and electrical characteristics of the ZnO films. At the present growth conditions, the full width at half maximum of a ZnO (0 0 2) diffraction peak decreased to 0.185° at 610 °C under an oxygen partial pressure of 45 Pa. By increasing the oxygen partial pressure from 45 to 68 Pa, the surface of the ZnO films became smoother and the grain size smaller and more homogeneous. In addition, the near-band-edge emission and the deep-level emission in the photoluminescence spectra and the electrical properties of the ZnO thin films strongly depended on the ambient oxygen content. [ABSTRACT FROM AUTHOR]

In the quest for efficient supercapacitor materials, manganese-based layered oxide cathodes stand out for their cost-effectiveness and high theoretical capacity. However, their progress is hindered by the Jahn-Teller (J-T) distortion due to the unavoidable Mn 4+ to Mn 3+ reduction during ion storage processes. Our study addresses this challenge by stabilizing the K 0.5 MnO 2 cathode through strategic Mg 2+ substitution. This substitution leads to an altered Mn 3+ electronic configuration, effectively mitigating the strong J-T distortion during ion storage processes. We provide a comprehensive analysis combining experimental evidence and theoretical insights, highlighting the emergence of the weak and negative J-T effects with reduced structural deformation during electrochemical cycling. Our findings reveal that the K 0.5 Mn 0.85 Mg 0.15 O 2 cathode exhibits remarkable durability, retaining 96.0% of initial capacitance after 8000 cycles. This improvement is attributed to the specific electronic configurations of Mn 3+ ions, which play a crucial role in minimizing volumetric changes and counteracting structural deformation typically induced by the strong J-T distortion. Our study not only advances the understanding of managing J-T distortion in manganese-based cathodes but also opens new avenues for designing high-stability supercapacitors and other energy storage devices by tailoring electrode materials based on their electronic configurations.

Transition metal oxides (TMOs) are promising cathode materials for aqueous zinc ion batteries (ZIBs), however, their performance is hindered by a substantial Hubbard gap, which limits electron transfer and battery cyclability. Addressing this, we introduce a heteroatom coordination approach, using triethanolamine to induce axial N coordination on Mn centers in MnO 2 , yielding N-coordinated MnO 2 (TEAMO). This approach leverages the change of electronegativity disparity between Mn and ligands (O and N) to disrupt spin symmetry and augment spin polarization. This enhancement leads to the closure of the Hubbard gap, primarily driven by the intensified occupancy of the Mn e g orbitals. The resultant TEAMO exhibit a significant increase in storage capacity, reaching 351 mAh g -1 at 0.1 A g -1 . Our findings suggest a viable strategy for optimizing the electronic structure of TMO cathodes, enhancing the potential of ZIBs in energy storage technology., (© 2024 Wiley-VCH GmbH.)

Three pairs of enantiomers and one achiral molecule that are new ethylated derivatives of sulfur and nitrogen-containing compounds named mantidisamides E-H ( 1 - 4 ), along with twenty known ones ( 5 - 24 ), were derived from the ethanol extract of Tenodera sinensis Saussure. The structures of these new compounds and their absolute configurations were assigned on the basis of spectroscopic analyses and computational methods. The assessment of activities in NRK-52e cells induced by TGF-β1 demonstrated that the previously undescribed compounds 1 and 2 exhibited a significant capacity to inhibit the expression of proteins (fibronectin, collagen I, and α -SMA). Moreover, the biological activity of these compounds was found to increase with rising concentrations. Notably, compounds 1 - 4 should be artifacts; however, undescribed compounds 1 and 2, which possessed obvious biological activity, might be attractive for chemists and biologists due to the potential for more detailed exploration of their properties. It is worth mentioning that compounds 1 and 2 remain novel structures even in the absence of the ethoxy group.

Selenium (Se), a component of selenoproteins and selenocompounds in the human body, is crucial for the development of male reproductive organs, DNA synthesis, thyroid hormone, metabolism, and defence against infections and oxidative damage. In the testis, it must exceed a desirable level since either a shortage or an overabundance causes aberrant growth. The antioxidant properties of selenium are essential for preserving human reproductive health. Selenoproteins, which have important structural and enzymatic properties, control the biological activities of Se primarily. These proteins specifically have a role in metabolism and a variety of cellular processes, such as the control of selenium transport, thyroid hormone metabolism, immunity, and redox balance. Selenium nanoparticles (SeNPs) are less hazardous than selenium-based inorganic and organic materials. Upon being functionalized with active targeting ligands, they are both biocompatible and capable of efficiently delivering combinations of payloads to particular cells. In this review, we discuss briefly the chemistry, structure and functions of selenium and milestones of selenium and selenoproteins. Next we discuss the various factors influences male infertility, biological functions of selenium and selenoproteins, and role of selenium and selenoproteins in spermatogenesis and male fertility. Furthermore, we discuss the molecular mechanism of selenium transport and protective effects of selenium on oxidative stress, apoptosis and inflammation. We also highlight critical contribution of selenium nanoparticles on male fertility and spermatogenesis. Finally ends with conclusion and future perspectives., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors. Published by Elsevier Ltd.)

The electrocatalytic conversion of formate in alkaline solutions is of paramount significance in the realm of fuel cell applications. Nonetheless, the adsorptive affinity of adsorbed hydrogen (H ad ) on the catalyst surface has traditionally impeded the catalytic efficiency of formate in such alkaline environments. To circumvent this challenge, our approach introduces an interfacial push-pull effect on the catalyst surface. This mechanism involves two primary actions: First, the anchoring of palladium (Pd) nanoparticles on a phosphorus-doped TiO 2 substrate (Pd/TiO 2 -P) promotes the formation of electron-rich Pd with a downshifted d band center, thereby "pushing" the desorption of H ad from the Pd active sites. Second, the TiO 2 -P support diminishes the energy barrier for H ad transfer from the Pd sites to the support itself, "pulling" H ad to effectively relocate from the Pd active sites to the support. The resultant Pd/TiO 2 -P catalyst showcases a remarkable mass activity of 4.38 A mg Pd -1 and outperforms the Pd/TiO 2 catalyst (2.39 A mg Pd -1 ) by a factor of 1.83. This advancement not only surmounts a critical barrier in catalysis but also delineates a scalable pathway to bolster the efficacy of Pd-based catalysts in alkaline media.

Manganese-based oxides (MnO x ) suffer from sluggish charge diffusion kinetics and poor cycling stability in sodium ion storage. Herein, an interfacial electric field (IEF) in CeO 2 /MnO x is constructed to obtain high electronic/ionic conductivity and structural stability of MnO x . The as-designed CeO 2 /MnO x exhibits a remarkable capacity of 397 F g -1 and favorable cyclic stability with 92.13% capacity retention after 10,000 cycles. Soft X-ray absorption spectroscopy and partial density of states results reveal that the electrons are substantially injected into the Mn t 2g orbitals driven by the formed IEF. Correspondingly, the MnO 6 units in MnO x are effectively activated, endowing the CeO 2 /MnO x with fast charge transfer kinetics and high sodium ion storage capacity. Moreover, In situRaman verifies a remarkably increased structural stability of CeO 2 /MnO x , which is attributed to the enhanced Mn─O bond strength and efficiently stabilized MnO 6 units. Mechanism studies show that the downshift of Mn 3d-band center dramatically increases the Mn 3d-O 2p orbitals overlap, thus inhibiting the Jahn-Teller (J-T) distortion of MnO x during sodium ion insertion/extraction. This work develops an advanced strategy to achieve both fast and sustainable sodium ion storage in metal oxides-based energy materials., (© 2024 Wiley‐VCH GmbH.)

The electrochemical nitrogen oxidation reaction (NOR) holds significant potential to revolutionize the traditional nitrate synthesis processes. However, the progression in NOR has been notably stymied due to the sluggish kinetics of initial N 2 adsorption and activation processes. Herein, the research embarks on the development of a CeO 2 -Co 3 O 4 heterostructure, strategically engineered to facilitate the electron transfer from CeO 2 to Co 3 O 4 . This orchestrated transfer operates to amplify the d-band center of the Co active sites, thereby enhancing N 2 adsorption and activation dynamics by strengthening the Co─N bond and diminishing the resilience of the N≡N bond. The synthesized CeO 2 -Co 3 O 4 manifests promising prospects, showcasing a significant HNO 3 yield of 37.96 µg h -1 mg cat -1 and an elevated Faradaic efficiency (FE) of 29.30% in a 0.1 m Na 2 SO 4 solution at 1.81 V versus RHE. Further substantiating these findings, an array of in situ methodologies coupled with DFT calculations vividly illustrate the augmented adsorption and activation of N 2 on the surface of CeO 2 -Co 3 O 4 heterostructure, resulting in a substantial reduction in the energy barrier pertinent to the rate-determining step within the NOR pathway. This research carves a promising pathway to amplify N 2 adsorption throughout the electrochemical NOR operations and delineates a blueprint for crafting highly efficient NOR electrocatalysts., (© 2024 Wiley‐VCH GmbH.)

Transition metal oxides (TMOs) are key in electrochemical energy storage, offering cost-effectiveness and a broad potential window. However, their full potential is limited by poor understanding of their slow reaction kinetics and stability issues. This study diverges from conventional complex nano-structuring, concentrating instead on spin-related charge transfer and orbital interactions to enhance the reaction dynamics and stability of TMOs during energy storage processes. We successfully reconfigured the orbital degeneracy and spin-dependent electronic occupancy by disrupting the symmetry of magnetic cobalt (Co) sites through straightforward strain stimuli. The key to this approach lies in the unfilled Co 3d shell, which serves as a spin-dependent regulator for carrier transfer and orbital interactions within the reaction. We observed that the opening of these 'spin gates' occurs during a transition from a symmetric low-spin state to an asymmetric high-spin state, resulting in enhanced reaction kinetics and maintained structural stability. Specifically, the spin-rearranged Al-Co 3 O 4 exhibited a specific capacitance of 1371 F g -1 , which is 38 % higher than that of unaltered Co 3 O 4 . These results not only shed light on the spin effects in magnetic TMOs but also establish a new paradigm for designing electrochemical energy storage materials with improved efficiency., (© 2024 Wiley-VCH GmbH.)

Falonolide A (1) and B (2), two novel polyyne hybrid phthalides resulting from unprecedented carbon skeleton polymerized by Z-ligustilide and falcarindiol, along with six new related phthalides (3-8), were isolated from Ligusticum chuanxiong Hort. Their structures were elucidated by spectroscopic analysis, computer-assisted structure elucidation (CASE) analysis, DP4+ probability analysis and electronic circular dichroism (ECD) calculations. A plausible biosynthetic pathway for 1-8 was proposed, and the production mechanism of 2 was revealed by density functional theory (DFT) method. Compounds 4 and 6 exhibited significant vasodilatory activity with EC 50 of 8.00 ± 0.86 and 6.92 ± 1.02 μM, respectively. Compound 4 also displayed significant inhibitory effect of NO production with EC 50 value of 8.82 ± 0.30 μM. Based on the established compounds library, structure-activity relationship analysis of phthalides was explored to provide insights into the drug development of vasodilators and anti-flammatory., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Ustiloxins I-M (1-5), five undescribed cyclopeptides bearing a 15-membered macrocyclic skeleton, were isolated from Cordyceps militaris. The structures of 1 and 5 were identified by spectroscopic and crystallographic methods, whereas the structures of 2-4 were assigned by spectroscopic and computational approaches. Biological evaluation of all the compounds toward human triple-negative breast cancer cells revealed that compounds 4 and 5 are toxic with IC 50 values of 64.29 μM and 28.89 μM, respectively., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The NAD + -dependent deacetylase SIRT7 is a pivotal regulator of DNA damage response (DDR) and a promising drug target for developing cancer therapeutics. However, limited progress has been made in SIRT7 modulator discovery. Here, we applied peptide-based deacetylase platforms for SIRT7 enzymatic evaluation and successfully identified a potent SIRT7 inhibitor YZL-51N . We initially isolated bioactive YZL-51N from cockroach ( Periplaneta americana ) extracts and then developed the de novo synthesis of this compound . Further investigation revealed that YZL-51N impaired SIRT7 enzymatic activities through occupation of the NAD + binding pocket. YZL-51N attenuated DNA damage repair induced by ionizing radiation (IR) in colorectal cancer cells and exhibited a synergistic anticancer effect when used in combination with etoposide. Overall, our study not only identified YZL-51N as a selective SIRT7 inhibitor from insect resources, but also confirmed its potential use in combined chemo-radiotherapy by interfering in the DNA damage repair process., Competing Interests: The authors declare no competing interests., (© 2024 The Authors.)

Highly active nonprecious-metal single-atom catalysts (SACs) toward catalytic transfer hydrogenation (CTH) of α,β-unsaturated aldehydes are of great significance but still are deficient. Herein, we report that Zn-N-C SACs containing Zn-N 3 moieties can catalyze the conversion of cinnamaldehyde to cinnamyl alcohol with a conversion of 95.5% and selectivity of 95.4% under a mild temperature and atmospheric pressure, which is the first case of Zn-species-based heterogeneous catalysts for the CTH reaction. Isotopic labeling, in situ FT-IR spectroscopy, and DFT calculations indicate that reactants, coabsorbed at the Zn sites, proceed CTH via a "Meerwein-Ponndorf-Verley" mechanism. DFT calculations also reveal that the high activity over Zn-N 3 moieties stems from the suitable adsorption energy and favorable reaction energy of the rate-determining step at the Zn active sites. Our findings demonstrate that Zn-N-C SACs hold extraordinary activity toward CTH reactions and thus provide a promising approach to explore the advanced SACs for high-value-added chemicals.

In the quest for proficient electrocatalysts for ammonia's electrocatalytic nitrogen reduction, cobalt oxides, endowed with a rich d-electron reservoir, have emerged as frontrunners. Despite the previously evidenced prowess of CoO in this realm, its ammonia yield witnesses a pronounced decline as the reaction unfolds, a phenomenon linked to the electron attrition from its Co 2+ active sites during electrocatalytic nitrogen reduction reaction (ENRR). To counteract this vulnerability, we harnessed electron-laden phosphorus (P) elements as dopants, aiming to recalibrate the electronic equilibrium of the pivotal Co active site, thereby bolstering both its catalytic performance and stability. Our empirical endeavors showcased the doped P-CoO's superior credentials: it delivered an impressive ammonia yield of 49.6 and, notably, a Faradaic efficiency (FE) of 9.6% at -0.2 V versus RHE, markedly eclipsing its undoped counterpart. Probing deeper, a suite of ex-situ techniques, complemented by rigorous theoretical evaluations, was deployed. This dual-pronged analysis unequivocally revealed CoO's propensity for an electron-driven valence metamorphosis to Co 3+ post-ENRR. In stark contrast, P-CoO, fortified by P doping, exhibits a discernibly augmented ammonia yield. Crucially, P's intrinsic ability to staunch electron leakage from the active locus during ENRR ensures the preservation of the valence state, culminating in enhanced catalytic dynamism and fortitude. This investigation not only illuminates the intricacies of active site electronic modulation in ENRR but also charts a navigational beacon for further enhancements in this domain.

Twelve new alkaloids, scolopenolines A-L ( 1 - 7 , 9 - 11 , 13 , 14 ), along with six known analogues, were isolated from Scolopendra subspinipes mutilans , identified by analysis of spectroscopic data and quantum chemical and computational methods. Scolopenoline A ( 1 ), a unique guanidyl-containing C 14 quinoline alkaloid, features a 6/6/5 ring backbone. Scolopenoline B ( 2 ) is a novel sulfonyl-containing heterodimer comprising quinoline and tyramine moieties. Scolopenoline G ( 7 ) presents a rare C 12 quinoline skeleton with a 6/6/5 ring system. Alkaloids 1 , 8 , 10 , and 15 - 18 display anti-inflammatory activity, while 10 and 16 - 18 also exhibit anti-renal-fibrosis activity. Drug affinity responsive target stability and RNA-interference assays show that Lamp2 might be a potentially important target protein of 16 for anti-renal-fibrosis activity.

Background and Purpose: The mammalian target of rapamycin (mTOR) pathway plays critical roles in intrinsic chemoresistance by regulating Fanconi anaemia complementation group D2 (FANCD2) expression. However, the mechanisms by which mTOR regulates FANCD2 expression and related inhibitors are not clearly elucidated. Extracts of Centipeda minima (C. minima) showed promising chemosensitizing effects by inhibiting FANCD2 activity. Here, we have aimed to identify the bioactive chemosensitizer in C. minima extracts and elucidate its underlying mechanism., Experimental Approach: The chemosensitizing effects of arnicolide C (ArC), a bioactive compound in C. minima, on non-small cell lung cancer (NSCLC) were investigated using immunoblotting, immunofluorescence, flow cytometry, the comet assay, small interfering RNA (siRNA) transfection and animal models. The online SynergyFinder software was used to determine the synergistic effects of ArC and chemotherapeutic drugs on NSCLC cells., Key Results: ArC had synergistic cytotoxic effects with DNA cross-linking drugs such as cisplatin and mitomycin C in NSCLC cells. ArC treatment markedly decreased FANCD2 expression in NSCLC cells, thus attenuating cisplatin-induced FANCD2 nuclear foci formation, leading to DNA damage and apoptosis. ArC inhibited the mTOR pathway and attenuated mTOR-mediated expression of E2F1, a critical transcription factor of FANCD2. Co-administration of ArC and cisplatin exerted synergistic anticancer effects in the A549 xenograft mouse model by suppressing mTOR/FANCD2 signalling in tumour tissues., Conclusion and Implications: ArC suppressed DNA cross-linking drug-induced DNA damage response by inhibiting the mTOR/E2F1/FANCD2 signalling axis, serving as a chemosensitizing agent. This provides insight into the anticancer mechanisms of ArC and offers a potential combinatorial anticancer therapeutic strategy., (© 2023 British Pharmacological Society.)

This study addresses the critical challenge in alkaline direct formate fuel cells (DFFCs) of slow formate oxidation reaction (FOR) kinetics as a result of strong hydrogen intermediate (H ad ) adsorption on Pd catalysts. We developed WO 3 -supported Pd nanoparticles (EG-Pd/WO 3 ) via an organic reduction method using ethylene glycol (EG), aiming to modulate the d-band center of Pd and alter H ad adsorption dynamics. Cyclic voltammetry demonstrated significantly improved H ad desorption kinetics in EG-Pd/WO 3 catalysts. Density functional theory (DFT) calculations revealed that the presence of EG reduces the d-band center of Pd, leading to weaker Pd-H bonds and enhanced H ad desorption during the FOR. This research provides a new approach to optimize catalyst efficiency in DFFCs, highlighting the potential for more effective and sustainable energy solutions through advanced material engineering.

Background: The prevalence of metabolic dysfunction-associated fatty liver disease (MAFLD) is rapidly increasing, currently affecting approximately 25% of the global population. Liver fibrosis represents a crucial stage in the development of MAFLD, with advanced liver fibrosis elevating the risks of cirrhosis and hepatocellular carcinoma. Simple serum markers are less effective in diagnosing liver fibrosis compared to more complex markers. However, imaging techniques like transient elastography face limitations in clinical application due to equipment and technical constraints. Consequently, it is imperative to identify a straightforward yet effective method for assessing MAFLD-associated liver fibrosis., Aim: To investigate the predictive value of angiopoietin-like protein 8 (ANGPTL8) in MAFLD and its progression., Methods: We analyzed 160 patients who underwent abdominal ultrasonography in the Endocrinology Department, Xiaogan Central Hospital affiliated to Wuhan University of Science and Technology, during September 2021-July 2022. Using abdominal ultrasonography and MAFLD diagnostic criteria, among the 160 patients, 80 patients (50%) were diagnosed with MAFLD. The MAFLD group was divided into the liver fibrosis group ( n = 23) and non-liver fibrosis group ( n = 57) by using a cut-off fibrosis-4 index ≥ 1.45. Logistical regression was used to analyze the risk of MAFLD and the risk factors for its progression. Receiver operating characteristic curves were used to evaluate the predictive value of serum ANGPTL8 in MAFLD and its progression., Results: Compared with non-MAFLD patients, MAFLD patients had higher serum ANGPTL8 and triglyceride-glucose (TyG) index (both P < 0.05). Serum ANGPTL8 ( r = 0.576, P < 0.001) and TyG index ( r = 0.473, P < 0.001) were positively correlated with MAFLD. Serum ANGPTL8 was a risk factor for MAFLD [odds ratio (OR): 1.123, 95% confidence interval (CI): 1.066-1.184, P < 0.001). Serum ANGPTL8 and ANGPTL8 + TyG index predicted MAFLD [area under the curve (AUC): 0.832 and 0.886, respectively; both P < 0.05]. Compared with MAFLD patients without fibrosis, those with fibrosis had higher serum ANGPTL8 and TyG index (both P < 0.05), and both parameters were positively correlated with MAFLD-associated fibrosis. Elevated serum ANGPTL8 (OR: 1.093, 95%CI: 1.044-1.144, P < 0.001) and TyG index (OR: 2.383, 95%CI: 1.199-4.736, P < 0.013) were risk factors for MAFLD-associated fibrosis. Serum ANGPTL8 and ANGPTL8 + TyG index predicted MAFLD-associated fibrosis (AUC: 0.812 and 0.835, respectively; both P < 0.05)., Conclusion: The serum levels of ANGPTL8 are elevated and positively correlated with MAFLD. They can serve as predictors for the risk of MAFLD and liver fibrosis, with the ANGPTL8 + TyG index potentially exhibiting even higher predictive value., Competing Interests: Conflict-of-interest statement: The authors have no conflicts of interest to declare., (©The Author(s) 2024. Published by Baishideng Publishing Group Inc. All rights reserved.)

Two previously undescribed chain diarylheptanoid derivatives (2-3), five previously undescribed dimeric diarylheptanoids (4-8), together with one known cyclic diarylheptanoid (1) were isolated from Zingiber officinale. Their structures were elucidated by extensive spectroscopic analyses (HR-ESI-MS, IR, UV, 1D and 2D NMR) and ECD calculations. Biological evaluation of compounds 1-8 revealed that compounds 2, 3 and 4 could inhibit nitrite oxide and IL-6 production in lipopolysaccharide induced RAW264.7 cells in a dose-dependent manner., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Four undescribed compounds including one aromatic glucoside derivative, cordyceglycoside A (1), one new isoleucine derivative inner salt, cordycepisosalt A (2), a rare four-membered lactam, cinerealactam B (3), and one sesquiterpene derivative, cordycepsetp A (4), together with six known compounds were isolated from Cordyceps militaris. The structures including absolute configurations of these new compounds, were unambiguously elucidated by spectroscopic data analysis and single crystal X-ray diffraction. Biological evaluation of compounds 1-4 showed that 3 displays anti-renal fibrotic activities in TGF-β1 induced NRK-52e cells. Furthermore, DARTS coupled with LC-MS/MS analysis was used to identify candidate target proteins for 3. Subsequently, C1qbp knockdown using siRNA allowed us to validate the target protein of 3., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Aspongopyrimidine A ( 1 ), a hexa-1,3-diene-histidine-hexanoic acid adduct featuring a 4,5-dihydro-2 H -10λ 4 -imidazo[5,1- f ]pyrrolo[2,1- b ]pyrimidine motif, was isolated from the insect Aspongopus chinensis . The structure was clarified by spectroscopic and computational methods and X-ray diffraction. Peralkylation of N -atoms in histidine by two C6 units makes 1 an inner salt with a 5/6/5 tricyclic system. Biological evaluation found that 1 exerts activity against Alzheimer's disease targeting MAPRE3 through a chemical proteomics approach. This study revealed unusual modifications of amino acids as the fundamental units of protein.

Mantidisflavin A ( 1 ) was isolated from the egg cases of the Tenodera sinensis Saussure. It exhibits an unprecedented 6/6/6/5/5 skeleton, accompanied by the formation of two additional fused heterocycles through a novel C-C bond and an oxygen bridge on riboflavin backbone. The structure of 1 was identified by spectroscopic and computational methods. To assess the inhibitory effect against renal fibrosis, compound 1 was evaluated in TGF-β1-induced rat kidney epithelial cells, and the results were compared to those of its precursor, riboflavin.

Direct formate fuel cells have gained traction due to their eco-friendly credentials and inherent safety. However, their potential is hampered by the kinetic challenges of the formate oxidation reaction (FOR) on Pd-based catalysts, chiefly due to the unfavorable adsorption of hydrogen species (H ad ). These species clog the active sites, hindering efficient catalysis. Here, we introduce a straightforward strategy to remedy this bottleneck by incorporating Pd with Cu to expedite the removal of Pd-H ad in alkaline media. Notably, Cu plays a pivotal role in bolstering the concentration of hydroxyl adsorbates (OH ad ) on the surface of catalyst. These OH ad species can react with H ad , effectively unblocking the active sites for FOR. The as-synthesized catalyst of PdCu/C exhibits a superior FOR performance, boasting a remarkable mass activity of 3.62 A mg -1 . Through CO-stripping voltammetry, we discern that the presence of Cu in Pd markedly speeds up the formation of adsorbed hydroxyl species (OH ad ) at diminished potentials. This, in turn, aids the oxidative removal of Pd-H ad , leveraging a synergistic mechanism during FOR. Density functional theory computations further reveal intensified interactions between adsorbed oxygen species and intermediates, underscoring that the Cu-Pd interface exhibits greater oxyphilicity compared to pristine Pd. In this study, we present both experimental and theoretical corroborations, unequivocally highlighting that the integrated copper species markedly amplify the generation of OH ad , ensuring efficient removal of H ad . This work paves the way, shedding light on the strategic design of high-performing FOR catalysts.

Background: Gastric cancer (GC) is a prevalent malignant tumor of the gastrointestinal system. ZNF710 is a transcription factor (TF), and zinc finger protein 710 (ZNF710)-AS1-201 is an immune-related long noncoding RNA (lncRNA) that is upregulated in GC cells., Aim: To assess the correlation between ZNF710-AS1-201 and immune microenvironment features and to investigate the roles of ZNF710-AS1-201 in the invasion and metastasis processes of GC cells., Methods: We obtained data from The Cancer Genome Atlas and Wujin Hospital. We assessed cell growth, migration, invasion, and programmed cell death using cell counting kit-8, EdU, scratch, Transwell, and flow cytometry assays. Quantitative real-time polymerase chain reaction (qRT-PCR) was used to identify the potential downstream targets of ZNF710-AS1-201., Results: In GC tissues with low ZNF710-AS1-201 expression, immunoassays detected significant infiltration of various antitumor immune cells, such as memory CD8 T cells and activated CD4 T cells. In the low-expression group, the half-maximal inhibitory concentrations (IC 50 s) of 5-fluorouracil, cisplatin, gemcitabine, and trametinib were lower, whereas the IC 50 s of dasatinib and vorinostat were higher. The malignant degree of GC was higher and the stage was later in the high-expression group. Additionally, patients with high expression of ZNF710-AS1-201 had lower overall survival and disease-free survival rates. In vitro, the overexpression of ZNF710-AS1-201 greatly enhanced growth, metastasis, and infiltration while suppressing cell death in HGC-27 cells. In contrast, the reduced expression of ZNF710-AS1-201 greatly hindered cell growth, enhanced apoptosis, and suppressed the metastasis and invasion of MKN-45 cells. The expression changes in ZNF710 were significant, but the corresponding changes in isocitrate dehydrogenase-2, Semaphorin 4B, ARHGAP10, RGMB, hsa-miR-93-5p, and ZNF710-AS1-202 were not consistent or statistically significant after overexpression or knockdown of ZNF710-AS1-201, as determined by qRT-PCR., Conclusion: Immune-related lncRNA ZNF710-AS1-201 facilitates the metastasis and invasion of GC cells. It appears that ZNF710-AS1-201 and ZNF710 have potential as effective targets for therapeutic intervention in GC. Nevertheless, it is still necessary to determine the specific targets of the ZNF710 TF., Competing Interests: Conflict-of-interest statement: All other authors have nothing to disclose., (©The Author(s) 2024. Published by Baishideng Publishing Group Inc. All rights reserved.)

Eight previously undescribed compounds comprising pyrrole-2-carboxaldehyde derivatives, namely periplanpyrroles A-D (1-4), spirooxindole derivatives perispirooxindoles A (5) and B (6), and the phenolic compounds periplanetols G (7) and H (8), along with eight known compounds were isolated from the 70% ethanol extract of the whole bodies of Periplaneta americana. Their structures including absolute configurations were unambiguously identified by comprehensive spectroscopic analyses and computational methods. In addition, all compounds were evaluated for their activities against triple negative breast cancer in vitro. The wound healing assay revealed that 7, 9, and 11 significantly inhibit the migration of BT549 and MDA-MB-231 cells. Further observations made in Western blotting experiments showed that 7 could dose-dependently decrease the protein level of vimentin and N-cadherin in MDA-MB-231 and BT549 cells., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Aspongamide F ( 1 ), a novel N -acetyldopamine (NADA) dimer possessing a 6/6/6 ring system, and (±)-aspongamides G ( 2 ) and H ( 3 ), rare NADA derivatives with fragmented benzene rings, were isolated from Aspongopus chinensis . (±)-Cicadamides C ( 4 ) and D ( 5 ), the first 1,4-Benzodioxane NADA dimers featuring a seco-benzene system, and (±)-cicadamides E ( 6 ) and F ( 7 ), the NADA dimers derivatives, were isolated from Periostracum cicadae . The structures of all compounds were elucidated by spectroscopic analyses and computational methods. A plausible biosynthetic pathway for compounds 1 - 5 was proposed. The biological assay revealed that (+)- 4 and (-)- 4 exhibit renal protection in a dose-dependent manner.

Transition-metal oxides (TMOs) often struggle with challenges related to low electronic conductivity and unsatisfactory cyclic stability toward cationic intercalation. In this work, we tackle these issues by exploring an innovative strategy: leveraging heightened π-donation to activate the t 2g orbital, thereby enhancing both electron/ion conductivity and structural stability of TMOs. We engineered Ni-doped layered manganese dioxide (Ni-MnO 2 ), which is characterized by a distinctive Ni-O-Mn bridging configuration. Remarkably, Ni-MnO 2 presents an impressive capacitance of 317 F g -1 and exhibits a robust cyclic stability, maintaining 81.58% of its original capacity even after 20,000 cycles. Mechanism investigations reveal that the incorporation of Ni-O-Mn configurations stimulates a heightened π-donation effect, which is beneficial to the π-type orbital hybridization involving the O 2p and the t 2g orbital of Mn, thereby accelerating charge-transfer kinetics and activating the redox capacity of the t 2g orbital. Additionally, the charge redistribution from Ni to the t 2g orbital of Mn effectively elevates the low-energy orbital level of Mn, thus mitigating the undesirable Jahn-Teller distortion. This results in a subsequent decrease in the electron occupancy of the π*-antibonding orbital, which promotes an overall enhancement in structural stability. Our findings pave the way for an innovative paradigm in the development of fast and stable electrode materials for intercalation energy storage by activating the low orbitals of the TM center from a molecular orbital perspective.

Blapspirooxindoles A-C (1-3), three novel spirooxindole alkaloids with a unique spiro[chromane-4,3'-indoline]-2,2'-dione motif, blapcumaranons A and B (4 and 5), two new 2-cumaranon derivatives, blapoxindoles A-J (6-15), ten new oxindole alkaloid derivatives, along with one known compound (16), were isolated from the whole bodies of Blaps japanensis. Their structures including absolute configurations were determined by using spectroscopic, X-ray crystallographic, and computational methods. Compounds 1-11 and 13 exist as racemic mixtures in nature, and their (-)- and (+)-antipodes were separated by chiral HPLC. Biological evaluations of these compounds were determined with multiple assays including anti-tumor, anti-inflammatory, and renal protection activities in vitro. Several compounds displayed effective activity in one or more assays., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Background: Benign paroxysmal positional vertigo (BPPV) is the most prevalent form of peripheral vertigo, with vascular lesions being one of its suspected causes. The older adults are particularly vulnerable to BPPV. Cerebral small vessel disease (CSVD), on the other hand, is a clinical condition that results from damage of cerebral small vessels. Vascular involvement resulting from age-related risk factors and proinflammatory state may act as the underlying factor linking both BPPV and CSVD., Aim: The objective of this study is to explore the potential correlation between BPPV and CSVD by examining whether individuals aged 50 and older with BPPV exhibit a greater burden of CSVD., Materials and Methods: This retrospective study included patients aged 50 years and older who had been diagnosed with BPPV. A control group consisting of patients diagnosed with idiopathic facial neuritis (IFN) during the same time period was also included. The burden of cerebral white matter hyperintensities (WMHs) was evaluated using the Fazekas scale. An ordinal regression analysis was conducted to investigate the potential correlation between BPPV and WMHs., Results: The study included a total of 101 patients diagnosed with BPPV and 116 patients with IFN. Patients with BPPV were found to be significantly more likely (OR = 2.37, 95% CI 1.40-4.03, p = 0.001) to have a higher Fazekas score compared to the control group. Brain infarctions, hypertension, and age were all identified as significant predictors of white matter hyperplasia on MRI, with OR of 9.9 (95% CI 4.21-24.84, P<0.001), 2.86 (95% CI 1.67-5.0, P<0.001), and 1.18 (95% CI 1.13-1.22, P<0.001) respectively., Conclusion: Our findings suggest that vascular impairment caused by age-related risk factors and proinflammatory status may be contributing factors to the development of BPPV in individuals aged 50 and above, as we observed a correlation between the suffering of BPPV and the severity of WMHs., Competing Interests: Declaration of Competing Interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023. Published by Elsevier Inc.)

An unprecedented dimeric abietane, succipenoid A (1), and two previously undescribed nor-abietane diterpenoids featuring a rarely occurring naphthalene ring or with a large conjugated system, succipenoids B and C (2 and 3), along with seven known diterpenoids (4-10) were isolated from the CH 2 Cl 2 extract of succinum. The structures of these compounds, including their absolute configurations, were elucidated using spectroscopic and computational techniques. Notably, compounds 1-4 and 6-10 were isolated from succinum for the first time. In order to evaluate their anti-inflammatory potential, in vitro tests were conducted. The results demonstrated that compounds 1, 2, 4, and 6-10 exhibite dose-dependent inhibition of iNOS expression in lipopolysaccharide-induced RAW 264.7 cells., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

As a widely consumed spice and Traditional Chinese Medicine, Alpinae oxyphylla has been used to treat conditions such as diarrhea, ulcers, dementia, and enuresis. Fruits of A. oxyphylla were phytochemically studied and the bioactive constituents against renal fibrosis were identified. Eight previously undescribed acetylated flavonol glucuronides named oxyphyllvonides A-H (1-7 and 10), two known acetylated flavonol glucuronides (8 and 9), together with seven known flavone glycosides (11-17) were isolated from the fruits of A. oxyphylla. Among them, flavonol glucuronides were discovered in Zingiberaceae for the first time. The planar structures of 1-7 and 10 were determined using HRESIMS and extensive spectroscopic techniques (UV, IR, 1D-NMR, and 2D-NMR). The absolute configurations of the sugar moiety in these compounds were determined by using LC-MS analysis of acid-hydrolyzed derivatized monosaccharides. Biological evaluation showed that 7-10, 13, 14, 16 and 17 inhibit renal fibrosis in TGF-β1-induced kidney proximal tubular cells. In addition, 7, 8 and 14 were superior to nootkatone in inhibiting Fibronectin expression. The finding has significant relevance to our ongoing research on the anti-renal fibrosis activity of A. oxyphylla., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

As a widely consumed spice and traditional Chinese medicine, Zingiber officinale Roscoe (ginger) has been used in the treatment of nausea, coughs, and colds. In this article, 18 new glycosides ( 1 - 18 ) and six known analogues ( 19 - 24 ) were isolated from the peel of ginger. The planar structures of these compounds were determined by using HR-ESI-MS and extensive spectroscopic techniques (UV, IR, 1D-NMR, and 2D-NMR). Their relative and absolute configurations of the stereogenic centers in the new natural products were determined by analysis of NMR data, using a quantum mechanical NMR approach and time-dependent density functional theory based electronic circular dichroism calculations. The renal fibrosis activities of the isolated natural products together with those of 6-gingerol (6-Gi), 8-gingerol (8-Gi), and 10-gingerol (10-Gi) were evaluated in TGF-β1 induced NRK-52E cells. Compounds 9 , 10 , 15 , 22 - 24 , 6-Gi, 8-Gi, and 10-Gi were found to be active toward extracellular matrix, indicating that they have potential renal fibrosis activities.

Co 3 O 4 is a highly selective catalyst for the electrochemical conversion of N 2 to NH 3 . However, the large work function (WF) of Co 3 O 4 leads to unsatisfactory activity. To address this issue, a strong built-in electric field (BIEF) was constructed in Co 3 O 4 by doping C atoms (C-Co 3 O 4 ) to reduce the WF for improving the electrocatalytic performance. C-Co 3 O 4 exhibited a remarkable NH 3 yield of 38.5 μg h -1 mg cat -1 and a promoted FE of 15.1% at -0.3 V vs RHE, which were 2.2 and 1.9 times higher than those of pure Co 3 O 4 , respectively. Kelvin probe force microscopy (KPFM), zeta potential, and ultraviolet photoelectron spectrometry (UPS) confirmed the formation of strong BIEF and WF reduction in C-Co 3 O 4 . Additionally, in situ Raman measurements and density functional theory (DFT) calculations revealed the relationship between BIEF and WF and provided insights into the reaction mechanism. Our work offers valuable guidance for the design and development of more efficient nitrogen reduction catalysts.

Nine pairs of undescribed enantiomers, (±)-styraxoids A-I (1-9), were isolated from the resin of Styrax tonkinensis, and their structures were assigned by spectroscopic and computational methods. Compounds (±)-1 are a pair of degraded lignans, and the remaining compounds (±)-(2-9) are phenylpropanoid skeletons. Compounds (±)-8 and (±)-9 feature a 1,3-dioxolane moiety. The biological evaluation showed that both enantiomers of 1 could inhibit LPS-induced INOS and COX-2 in RAW264.7 cells in a dose-dependent manner., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Internal electric field (IEF) construction is an innovative strategy to regulate the electronic structure of electrode materials to promote charge transfer processes. Despite the wide use of IEF in various applications, the underlying mechanism of its formation in an asymmetric TM-O-TM unit still remains poorly understood. Herein, the essential principles for the IEF construction at electron occupancy state level and explore its effect on hybrid capacitive deionization (HCDI) performance is systematically investigated. By triggering a charge separation in Ni-MnO 2 via superexchange interactions in a coordination structure unit of Mn 4+ -O 2- -Ni 2+ , the formation of an IEF that can enhance charge transfer during the HCDI process is demonstrated. Experimental and theoretical results confirm the electrons transfer from O 2p orbital to TM (Ni 2+ and Mn 4+ ) e g orbital via superexchange interactions in the basic Mn 4+ -O 2- -Ni 2+ coordination unit. As a result of the charge redistribution, the IEF endows Ni-MnO 2 with superior electron and ion transfer property. This work presents a unique material design strategy that activates the electrochemical performance, and provides insights into the formation mechanism of IEF in an asymmetric TM-O-TM unit, which has potential applications in the construction of other innovative materials., (© 2023 Wiley-VCH GmbH.)

Three new compounds, arneatas A-C ( 1 - 3 ), together with three known compounds ( 4 - 6 ) were isolated from the roots of Arnebia guttata Bunge. The structures were established on the basis of extensive spectroscopic data including NMR and HRESIMS. All the new compounds ( 1 - 3 ) were tested for their cytotoxic activity against two glioma cell lines (U118-MG and U373-MG) in vitro after treatment for 48 h. Compound 1 exhibited moderate cytotoxic activity against U118-MG and U373-MG glioma cell lines, with IC 50 values of 10.4 and 17.5 µM, respectively.

Efficient conversion of carbon dioxide (CO 2 ) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions and close the anthropogenic carbon loop. Recently, there has been intense interest in Cu 2 O-based catalysts for the CO 2 reduction reaction (CO 2 RR), owing to their capabilities in enhancing C-C coupling. However, the electrochemical instability of Cu + in Cu 2 O leads to its inevitable reduction to Cu 0 , resulting in poor selectivity for C 2+ products. Herein, we propose an unconventional and feasible strategy for stabilizing Cu + through the construction of a Ce 4+ 4f-O 2p-Cu + 3d network structure in Ce-Cu 2 O. Experimental results and theoretical calculations confirm that the unconventional orbital hybridization near E f based on the high-order Ce 4+ 4f and 2p can more effectively inhibit the leaching of lattice oxygen, thereby stabilizing Cu + in Ce-Cu 2 O, compared with traditional d-p hybridization. Compared to pure Cu 2 O, the Ce-Cu 2 O catalyst increased the ratio of C 2 H 4 /CO by 1.69-fold during the CO 2 RR at -1.3 V. Furthermore, in situ and ex situ spectroscopic techniques were utilized to track the oxidation valency of copper under CO 2 RR conditions with time resolution, identifying the well-maintained Cu + species in the Ce-Cu 2 O catalyst. This work not only presents an avenue to CO 2 RR catalyst design involving the high-order 4f and 2p orbital hybridization but also provides deep insights into the metal-oxidation-state-dependent selectivity of catalysts.

Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, the protonation of intermediates is the rate-determining step (RDS). Enhancing the adsorption of intermediates is crucial to increase the protonation of intermediates, which can lead to improved catalytic performance. Herein, we constructed a strong interfacial electric field in WS 2 -WO 3 to elevate the d-band center of W, thereby strengthening the adsorption of intermediates. Experimental results demonstrated that this approach led to a significantly improved ENRR performance. Specifically, WS 2 -WO 3 exhibited a high NH 3 yield of 62.38 μg h -1  mg cat -1 and a promoted faraday efficiency (FE) of 24.24 %. Furthermore, in situ characterizations and theoretical calculations showed that the strong interfacial electric field in WS 2 -WO 3 upshifted the d-band center of W towards the Fermi level, leading to enhanced adsorption of -NH 2 and -NH intermediates on the catalyst surface. This resulted in a significantly promoted reaction rate of the RDS. Overall, our study offers new insights into the relationship between interfacial electric field and d-band center and provides a promising strategy to enhance the intermediates adsorption during the ENRR process., (© 2023 Wiley-VCH GmbH.)

Background: Systemic sclerosis (scleroderma; SSc), a rare and heterogeneous connective tissue disease, remains unclear in terms of its underlying causative genes and effective therapeutic approaches. The purpose of the present study was to identify hub genes, diagnostic markers and explore potential small-molecule drugs of SSc. Methods: The cohorts of data used in this study were downloaded from the Gene Expression Complex (GEO) database. Integrated bioinformatic tools were utilized for exploration, including Weighted Gene Co-Expression Network Analysis (WGCNA), least absolute shrinkage and selection operator (LASSO) regression, gene set enrichment analysis (GSEA), Connectivity Map (CMap) analysis, molecular docking, and pharmacokinetic/toxicity properties exploration. Results: Seven hub genes (THY1, SULF1, PRSS23, COL5A2, NNMT, SLCO2B1, and TIMP1) were obtained in the merged gene expression profiles of GSE45485 and GSE76885. GSEA results have shown that they are associated with autoimmune diseases, microorganism infections, inflammatory related pathways, immune responses, and fibrosis process. Among them, THY1 and SULF1 were identified as diagnostic markers and validated in skin samples from GSE32413, GSE95065, GSE58095 and GSE125362. Finally, ten small-molecule drugs with potential therapeutic effects were identified, mainly including phosphodiesterase (PDE) inhibitors (BRL-50481, dipyridamole), TGF-β receptor inhibitor (SB-525334), and so on. Conclusion: This study provides new sights into a deeper understanding the molecular mechanisms in the pathogenesis of SSc. More importantly, the results may offer promising clues for further experimental studies and novel treatment strategies., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Yan, Jin, Li, Wu, Wang, Hu, Shen and Yin.)

Investigation on the chemical components of Valeriana jatamansi Jones (Caprifoliaceae), a new lignan with pyran-ring, dipsalignan G ( 1 ), along with eight known compounds ( 2 - 9 ) were isolated. Their structures were elucidated by extensive analysis of 1D, 2D NMR and HR-ESI-MS spectroscopic data. Additionally, possible biosynthetic pathway of 1 was proposed. Finally, biological evaluation results showed that 8 had significant scavenging ability to ABTS and DPPH free radicals, with IC 50 values of 1.35 ± 0.01 and 2.94 ± 0.01 μg/ml, respectively.

The rational design of electrocatalysts for formate oxidation reaction (FOR) in alkaline media is crucial to promote the practical applications of direct formate fuel cells (DFFCs). The FOR kinetic on palladium (Pd) based electrocatalysts is strongly hindered by unfavorably adsorbed hydrogen (H ad ) as the major intermediate species blocking the active sites. Herein, we report a strategy of modulating the interfacial water network of dual-site Pd/FeO x /C catalyst to significantly enhance the desorption kinetics of H ad during FOR. Aberration-corrected electron microscopy and synchrotron characterizations revealed the successful construction of Pd/FeO x interfaces on carbon support as a dual-site electrocatalyst for FOR. Electrochemical tests and in situ Raman spectroscopy results showed that H ad could be effectively removed from the active sites of the as-designed Pd/FeO x /C catalyst. CO-stripping voltammetry and density functional theory calculations (DFT) demonstrated that the introduced FeO x could effectively accelerate the dissociative adsorption of water molecules on active sites, which accordingly generates adsorbed hydroxyl species (OH ad ) to facilitate the removal of H ad during FOR. This work provides a novel route to develop advanced FOR catalysts for fuel cell applications.

Six new compounds, including a tetralone 1 , two xanthones 2 and 3 , a flavan derivative 4 , and two nor-diterpenoids 7 and 8 , accompanied by two known flavan derivatives 5 and 6 and a known olefine acid ( 9 ) were isolated from whole bodies of Kronopolites svenhedini (Verhoeff). The structures of the new compounds were determined by 1D and 2D nuclear magnetic resonance (NMR) and other spectroscopic methods, as well as computational methods. Selected compounds were evaluated for their biological properties against a mouse pancreatic cancer cell line and inhibitory effects on iNOS and COX-2 in RAW264.7 cells., (Copyright © 2023, Yuan et al.)

Transition metal oxides suffer from slow salt removal rate (SRR) due to inferior ions diffusion ability in hybrid capacitive deionization (HCDI). Local electric field (LEF) can efficiently improve the ions diffusion kinetics in thin electrodes for electrochemical energy storage. Nevertheless, it is still a challenge to facilitate the ions diffusion in bulk electrodes with high loading mass for HCDI. Herein, this work delicately constructs a LEF via engineering atomic-level donor (O vacancies)-acceptor (Mn atoms) couples, which significantly facilitates the ions diffusion and then enables a high-performance HCDI. The LEF boosts an extended accelerated ions diffusion channel at the particle surface and interparticle space, resulting in both remarkably enhanced SRR and salt removal capacity. Convincingly, the theoretical calculations demonstrate that electron-enriched Mn atoms center coupled with an electron-depleted O vacancies center is formed due to the electron back-donation from O vacancies to adjacent Mn centers. The resulted LEF efficiently reduce the ions diffusion energy barrier. This work sheds light on the effect of atomic-level LEF on improving ions diffusion kinetics at high loading mass application and paves the way for the design of transition metal oxides toward high-performance HCDI applications., (© 2023 Wiley-VCH GmbH.)

We report on the synthesis of a cage-type calix[4]pyrrole ( 1 ) bearing an additional basic pyridinebisthiazolamine group on the strap. The receptor in its protonated form shows strong affinity and selectivity for sulfate over a wide range of inorganic anions. With receptor 1 as a liquid-liquid extractant, H + /SO 4 2- in the form of H 2 SO 4 is almost quantitatively extracted from an aqueous solution containing HNO 3 at a high concentration to CH 2 Cl 2 in a recyclable manner.

Direct formate fuel cells (DFFCs) have drawn tremendous attention because they are environmentally benign and have good safety. However, the lack of advanced catalysts for formate electrooxidation hinders the development and applications of DFFCs. Herein, we report a strategy of regulating the metal-substrate work function difference to effectively promote the transfer of adsorbed hydrogen (H ad ), thus enhancing formate electrooxidation in alkaline solutions. By introducing rich oxygen vacancies, the obtained catalysts of Pd/WO 3- x -R show outstanding formate electrooxidation activity, exhibiting an extremely high peak current of 15.50 mA cm -2 with a lower peak potential of 0.63 V. In situ electrochemical Fourier transform infrared and in situ Raman measurements verify an enhanced in situ phase transition from WO 3- x to H x WO 3- x during the formate oxidation reaction process over the Pd/WO 3- x -R catalyst. The results of experimental and density functional theory (DFT) calculations confirm that the work function difference (ΔΦ) between the metal (Pd) and substrate (WO 3- x ) would be regulated by inducing oxygen vacancies in the substrate, resulting in improved hydrogen spillover at the interface of the catalyst, which is essentially responsible for the observed high performance of formate oxidation. Our findings provide a novel strategy of rationally designing efficient formate electrooxidation catalysts.