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The electrochemical splitting of water for hydrogen production faces a major challenge due to its anodic oxygen evolution reaction (OER), necessitating research on the rational design and facile synthesis of OER catalysts to enhance catalytic activity and stability. This study proposes a ligand-induced MOF-on-MOF approach to fabricate various trimetallic MnFeCo-based Prussian blue analog (PBA) nanostructures. The addition of [Fe(CN)6]3- transforms them from cuboids with protruding corners (MnFeCoPBA-I) to core-shell configurations (MnFeCoPBA-II), and finally to hollow structures (MnFeCoPBA-III). After pyrolysis at 800 °C, they are converted into corresponding PBA-derived carbon nanomaterials, featuring uniformly dispersed Mn2Co2C nanoparticles. A comparative analysis demonstrates that the Fe addition enhances catalytic activity, while Mn-doped materials exhibit excellent stability. Specifically, the optimized MnFeCoNC-I-800 demonstrates outstanding OER performance in 1.0 m KOH solution, with an overpotential of 318 mV at 10 mA cm-2, maintaining stability for up to 150 h. Theoretical calculations elucidate synergistic interactions between Fe dopants and the Mn2Co2C matrix, reducing barriers for oxygen intermediates and improving intrinsic OER activity. These findings offer valuable insights into the structure-morphology relationships of MOF precursors, advancing the development of highly active and stable MOF-derived OER catalysts for practical applications.

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Hydrogen peroxide (H2O2) electrosynthesis via the two-electron oxygen reduction reaction (2e- ORR) represents a green alternative to the energy-intensive anthraquinone process. However, the practical application of this method is limited by the lack of cost-effective and high-performance electrocatalysts. Reported here is a hybrid catalyst composed of nickel (Ni) clusters immobilized onto the surface of two-dimensional siloxene nanosheets (Ni/siloxene), which exhibits excellent efficiency and selectivity in electrocatalytic oxygen reduction to H2O2 in an alkaline medium, demonstrating a standard 2e- pathway with >95% H2O2 selectivity across a wide potential range. Experimental results disclose that the high performance of Ni/siloxene can be traced to a synergy of the Ni clusters and the oxygen-rich surface of siloxene. Density functional theory (DFT) calculations further reveal a weakened interaction between Ni/siloxene and *OOH and the consequently reduced energy barrier for the *OOH protonation toward H2O2 desorption, thus leading to a high 2e- ORR reactivity and selectivity. This work provides a valuable and practical guidance for designing high-performance 2e- ORR electrocatalysts based on the rational engineering of the metal-support interaction.

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Conventional enzyme-based glucose biosensors have limited extensive applications in daily life because glucose oxidase is easily inactivated and is expensive. In this paper, we propose a strategy to prepare a new type of cost-effective, efficient, and robust nonenzymatic Ni-CNT-O for electrochemical glucose sensing. It is first followed by the pyrolysis of Ni-ABDC nanostrips using melamine to grow carbon nanotubes (CNTs) to give an intermediate product of Ni-CNT, which is further accompanied by partial oxidation to enable the facile formation of hierarchical carbon nanomaterials with improved hydrophilicity. A series of physicochemical characterizations have fully proved that Ni-CNT-O is a carbon-coated heterostructure of Ni and NiO nanoparticles embedded into coordination polymer-derived porous carbons. The obtained Ni-CNT-O exhibits a better electrocatalytic activity for glucose oxidation stemming from the synergistic effect of a metal element and a metal oxide than unoxidized Ni-CNT, which also shows high performance with a wide linear range from 1 to 3000 µM. It also offers a high sensitivity of 79.4 µA mM-1 cm-2, a low detection limit of 500 nM (S/N = 3), and a satisfactory long-term durability. Finally, this glucose sensor exhibits good reproducibility, high selectivity, as well as satisfactory results by comparing the current response of simulated serum within egg albumen.

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The complex oxygen evolution reaction (OER) is recognized as the most studied and explored electrochemical conversion, which plays a crucial role in energy-related applications. In this work, a series of metal-organic framework (MOF)-derived FeNi oxides from a barrel-shaped Ni-based BMM-10 precursor are conveniently obtained to show an excellent OER performance. Under mild Fe(III) etching, a type of core-shell Fe0.5-BMM-10 can be well preserved and the coordination bond of the middle frame structure is decomposed. Furthermore, the Fex-BMM-10-T series is successfully synthesized with a well-preserved morphology compared to precursors after direct oxidation. Finally, followed by initial electrochemical activation, the decomposition of FeNi oxides generates active Fe-doped nickel oxyhydroxides for efficient water oxidation. The improved OER performance stems from the high specific surface area and abundant exposed active centers, as well as the significant synergistic effect between iron and nickel, which is further verified by the theoretical calculation. This approach can be extended to precisely adjust the morphology of MOFs and their derivatives that can result in superior electrocatalytic properties in terms of energy conversion and storage applications.

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The relative contributions of decreased upstream sediment loads and local estuarine engineering activities to the estuarine channel geometry are poorly understood. In this study, we analyze the hydrological changes and identify the location, duration and intensity of the estuarine engineering activities based on the channel morphologic changes from 1965 to 2017 at the five stations in the Pearl River Estuary. Thereafter, the Mann-Kendall (M-K) statistical test, empirical orthogonal function (EOF) tests, and channel geometry reconstruction based on the hydrological coefficient were performed to quantitatively estimate the relative contributions from upstream dam construction and estuarine engineering activities. The results show that the geometric changes in the five transects over the last 50 years could be divided into three stages. Stage I extends over approximately 23-33 years at the different channel transects, during which the channel geometries were mainly influenced by natural factors, with a balance between erosion and deposition. Stage II occurred during the next 11-20 years and the changes in the cumulated water depth in comparison to the values in the previous adjacent years at this stage are approximately 5-25 times the values in stage I. The human activities (e.g., sand excavation) contribute to >70-90% of the extreme geometric changes. Stage III lasted for <3-11 years in the different transects with a slight depositional trend, and policies regulating sand excavation were implemented during this stage. The rapid increase in the channel area and water depth caused by sand excavation can cause the downcutting of the riverbed, a decrease in the water level, and redistribution of the water and sediment discharge. Therefore, the monitoring, simulation and analysis of the variation in the typical channel geometry over the long term provide important means to understand the human activities occurring and insights for future sustainable estuarine management.

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Simultaneous sampling and observation were conducted at 16 stations in the Pearl River Estuary, and the temporal and spatial characteristics of the contents of six heavy metals (Cr, Cu, Zn, Pb, As, and Cd) were analyzed. The influencing factors of suspended particulate matter (SPM) were explored through the combined results of our statistical analyses. With the influence of discharge, temperature and particle size, the content of heavy metals in the dry season is higher than that in flood season. Regarding the estuary filter, the content of heavy metals in the estuary segment was lower than that in the far mouth segment, which was principally caused by the difference in salinity and sediment concentration between the two segments during the dry season. Both the sediment quality standard and enrichment factor methods were used to evaluate heavy metals. The results showed that the threat of heavy metals in the dry season was stronger than that in the flood season. As and Zn were more harmful to the ecological risk, while Cd, As, and Zn were the more abundant pollutants in the Pearl River Estuary. Heavy metal pollution was more severe in the far mouth segment. The degree of pollution for Cu, Zn, As, and Cd- which are classified as heavy pollution, severe to extremely heavy pollution, severe heavy pollution, and extremely heavy pollution, respectively-in the Beijiang River were higher compared to the Xijiang River and Dongjiang River. The pollution level of the six heavy metals in the four eastern outlets and four western outlets were similar, and the most serious pollution in Humen may be related to local industrial development. The source of heavy metals in SPM of the Pearl River Estuary is related to geological background, industry, and the mining area.

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Recent studies have revealed that circular RNAs (circRNAs) play important roles in the tumorigenesis of human cancer, including hepatocellular carcinoma (HCC). In present study, we screen the circular RNA expression profiles in HCC tissue and investigate the molecular roles on HCC tumorigenesis. Human circRNA microarray analysis showed there were total 1,245 differently expressed circular RNAs, including 756 up-regulated circRNAs and 489 down-regulated circRNAs, in three pairs of HCC tissue and adjacent normal tissue. Hsa_circ_0016788 was identified to be up-regulated in both HCC tissue and cell lines. Loss-of-functional experiments in vivo and vitro revealed that hsa_circ_0016788 silencing inhibited the proliferation, invasion and promoted the apoptosis in vitro, and inhibited the tumor growth in vivo. Bioinformatics tools and luciferase reporter assay validated that miR-486 targeted hsa_circ_0016788 and CDK4 accompanying with negatively correlated expression, suggesting the hsa_circ_0016788/miR-486/CDK4 pathway. Receiver operating characteristic (ROC) curve showed that hsa_circ_0016788 had high diagnostic value (AUC = 0.851). In summary, results reveal the role of hsa_circ_0016788/miR-486/CDK4 in HCC tumorigenesis, providing a novel therapeutic target for HCC.

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Generally accepted, inflammation and neuron apoptosis are two characterized pathological features of cerebral ischemia-reperfusion (IR) injury. Ginsenoside Rg1 was reported showing distinct neuroprotective effect in cerebral IR injury but the underlying mechanisms are still unclear. PPARγ/Heme oxygenase-1 (HO-1) signaling was proved effective in suppressing both apoptosis and inflammation. This study was aimed to investigate whether PPARγ/HO-1 signaling was involved in cerebral IR injury and ginsenoside Rg1's neuroprotective effect in cerebral IR injury. Cerebral IR injury was induced by middle cerebral artery occlusion in rats. The PPARγ agonist rosiglitazone (ROZ) and the HO-1 inhibitor zinc protoporphyrin-IX (ZnPP) and ginsenoside Rg1 at various concentrations were used to treat the modeled rats. Neurological deficits, apoptosis and inflammation in hippocampus were evaluated. Furthermore, HO-1 enzymatic activity, expression levels of apoptosis-related and inflammation-related proteins, concentrations of inflammatory cytokines were also determined. The results showed that PPARγ activation by ROZ significantly attenuated neurological deficits, apoptosis and inflammation in hippocampus in cerebral IR rats. However, the neuroprotective effect of ROZ was then impaired by HO-1 inhibitor ZnPP. This effect was evidenced by changes of expression levels of PPARγ, bcl-2, cleaved caspase-3, cleaved caspase-9, IL-1ß, TNF-α, HMGB1, and RAGE in hippocampus of modeled animals. Ginsenoside Rg1 showed similar effect to ROZ in activating PPARγ/HO-1 in protecting against apoptosis and inflammation but also impaired by ZnPP administration. In conclusion, PPARγ/HO-1 signaling was critical in mediating apoptosis and inflammation, which was also the therapeutic target of ginsenoside Rg1 in cerebral IR injury.

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