Stabilizing the oxidation state of catalysts for effective electrochemical carbon dioxide conversion.

In the electrocatalytic CO2 reduction reaction (CO2RR), metal catalysts with an oxidation state generally demonstrate more favorable catalytic activity and selectivity than their corresponding metallic counterparts. However, the persistence of oxidative metal sites under reductive potentials is challenging since the transition to metallic states inevitably leads to catalytic degradation. Herein, a thorough review of research on oxidation-state stabilization in the CO2RR is presented, starting from fundamental concepts and highlighting the importance of oxidation state stabilization while revealing the relevance of dynamic oxidation states in product distribution. Subsequently, the functional mechanisms of various oxidation-state protection strategies are explained in detail, and in situ detection techniques are discussed. Finally, the prevailing and prospective challenges associated with oxidation-state protection research are discussed, identifying innovative opportunities for mechanistic insights, technology upgrades, and industrial platforms to enable the commercialization of the CO2RR.

Integrated analysis reveals the regulatory mechanism of the neddylation inhibitor MLN4924 on the metabolic dysregulation in rabbit granulosa cells.

BACKGROUND: Neddylation, an important post-translational modification (PTM) of proteins, plays a crucial role in follicular development. MLN4924 is a small-molecule inhibitor of the neddylation-activating enzyme (NAE) that regulates various biological processes. However, the regulatory mechanisms of neddylation in rabbit ovarian cells have not been emphasized. Here, the transcriptome and metabolome profiles in granulosa cells (GCs) treated with MLN4924 were utilized to identify differentially expressed genes, followed by pathway analysis to precisely define the altered metabolisms. RESULTS: The results showed that 563 upregulated and 910 downregulated differentially expressed genes (DEGs) were mainly enriched in pathways related to cancer, cell cycle, PI3K-AKT, progesterone-mediated oocyte maturation, and PPAR signaling pathway. Furthermore, we characterized that MLN4924 inhibits PPAR-mediated lipid metabolism, and disrupts the cell cycle by promoting the apoptosis and proliferation of GCs. Importantly, we found the reduction of several metabolites in the MLN4924 treated GCs, including glycerophosphocholine, arachidic acid, and palmitic acid, which was consistent with the deregulation of PPAR signaling pathways. Furthermore, the increased metabolites included 6-Deoxy-6-sulfo-D-glucono-1,5-lactone and N-Acetyl-D-glucosaminyldiphosphodolichol. Combined with transcriptome data analyses, we identified genes that strongly correlate with metabolic dysregulation, particularly those related to glucose and lipid metabolism. Therefore, neddylation inhibition may disrupt the energy metabolism of GCs. CONCLUSIONS: These results provide a foundation for in-depth research into the role and molecular mechanism of neddylation in ovary development.

Conformation-Driven Responsive 1D and 2D Lanthanide-Metal-Organic Framework Heterostructures for High-Security Photonic Barcodes.

Development of luminescent segmented heterostructures featuring multiple spatial-responsive blocks is important to achieve miniaturized photonic barcodes toward anti-counterfeit applications. Unfortunately, dynamic manipulation of the spatial color at micro/nanoscale still remains a formidable challenge. Here, a straightforward strategy is proposed to construct spatially varied heterostructures through amplifying the conformation-driven response in flexible lanthanide-metal-organic frameworks (Ln-MOFs), where the thermally induced minor conformational changes in organic donors dramatically modulate the photoluminescence of Ln acceptors. Notably, compositionally and structurally distinct heterostructures (1D and 2D) are further constructed through epitaxial growth of multiple responsive MOF blocks benefiting from the isomorphous Ln-MOF structures. The thermally controlled emissive colors with distinguishable spectra carry the fingerprint information of a specific heterostructure, thus allowing for the effective construction of smart photonic barcodes with spatially responsive characteristics. The results will deepen the understanding of the conformation-driven responsive mechanism and also provide guidance to fabricate complex stimuli-responsive hierarchical microstructures for advanced optical recording and high-security labels.

AMPK/PGC-1α and p53 modulate VDAC1 expression mediated by reduced ATP level and metabolic oxidative stress in neuronal cells.

Voltage-dependent anion channel 1 (VDAC1) is a pore protein located in the outer mitochondrial membrane. Its channel gating mediates mitochondrial respiration and cell metabolism, and it has been identified as a critical modulator of mitochondria-mediated apoptosis. In many diseases characterized by mitochondrial dysfunction, such as cancer and neurodegenerative diseases, VDAC1 is considered a promising potential therapeutic target. However, there is limited research on the regulatory factors involved in VDAC1 protein expression in both normal and pathological states. In this study, we find that VDAC1 protein expression is up-regulated in various neuronal cell lines in response to intracellular metabolic and oxidative stress. We further demonstrate that VDAC1 expression is modulated by intracellular ATP level. Through the use of pharmacological agonists and inhibitors and small interfering RNA (siRNA), we reveal that the AMPK/PGC-1α signaling pathway is involved in regulating VDAC1 expression. Additionally, based on bioinformatics predictions and biochemical verification, we identify p53 as a potential transcription factor that regulates VDAC1 promoter activity during metabolic oxidative stress. Our findings suggest that VDAC1 expression is regulated by the AMPK/PGC-1α and p53 pathways, which contributes to the maintenance of stress adaptation and apoptotic homeostasis in neuronal cells.

Ultrathin Nitrogen-Doped Carbon Encapsulated Ni Nanoparticles for Highly Efficient Electrochemical CO2 Reduction and Aqueous Zn-CO2 Batteries.

Electrochemical CO2 reduction reaction (CO2 RR), powered by renewable electricity, has attracted great attention for producing high value-added fuels and chemicals, as well as feasibly mitigating CO2 emission problem. Here, this work reports a facile hard template strategy to prepare the Ni@N-C catalyst with core-shell structure, where nickel nanoparticles (Ni NPs) are encapsulated by thin nitrogen-doped carbon shells (N-C shells). The Ni@N-C catalyst has demonstrated a promising industrial current density of 236.7 mA cm-2 with the superb FECO of 97% at -1.1 V versus RHE. Moreover, Ni@N-C can drive the reversible Zn-CO2 battery with the largest power density of 1.64 mW cm-2 , and endure a tough cycling durability. These excellent performances are ascribed to the synergistic effect of Ni@N-C that Ni NPs can regulate the electronic microenvironment of N-doped carbon shells, which favor to enhance the CO2 adsorption capacity and the electron transfer capacity. Density functional theory calculations prove that the binding configuration of N-C located on the top of Ni slabs (Top-Ni@N-C) is the most thermodynamically stable and possess a lowest thermodynamic barrier for the formation of COOH* and the desorption of CO. This work may pioneer a new method on seeking high-efficiency and worthwhile electrocatalysts for CO2 RR and Zn-CO2 battery.

Impact of coprophagy prevention on the growth performance, serum biochemistry, and intestinal microbiome of rabbits.

BACKGROUND: Coprophagy plays a vital role in maintaining growth and development in many small herbivores. Here, we constructed a coprophagy model by dividing rabbits into three groups, namely, control group (CON), sham-coprophagy prevention group (SCP), and coprophagy prevention group (CP), to explore the effects of coprophagy prevention on growth performance and cecal microecology in rabbits. RESULTS: Results showed that CP treatment decreased the feed utilization and growth performance of rabbits. Serum total cholesterol and total triglyceride in the CP group were remarkably lower than those in the other two groups. Furthermore, CP treatment destroyed cecum villi and reduced the content of short-chain fatty acids (SCFAs) in cecum contents. Gut microbiota profiling showed significant differences in the phylum and genus composition of cecal microorganisms among the three groups. At the genus level, the abundance of Oscillospira and Ruminococcus decreased significantly in the CP group. Enrichment analysis of metabolic pathways showed a significantly up-regulated differential metabolic pathway (PWY-7315, dTDP-N-acetylthomosamine biosynthesis) in the CP group compared with that in the CON group. Correlation analysis showed that the serum biochemical parameters were positively correlated with the abundance of Oscillospira, Sutterella, and Butyricimonas but negatively correlated with the abundance of Oxalobacte and Desulfovibrio. Meanwhile, the abundance of Butyricimonas and Parabacteroidesde was positively correlated with the concentration of butyric acid in the cecum. CONCLUSIONS: In summary, coprophagy prevention had negative effects on serum biochemistry and gut microbiota, ultimately decreasing the growth performance of rabbits. The findings provide evidence for further revealing the biological significance of coprophagy in small herbivorous mammals.

Dehydration-rehydration mechanism of vegetables at the cell-wall and cell-membrane levels and future research challenges.

The quality of dehydrated vegetables is affected by the degree to which they are returned to their original state during rehydration (restorability). At present, whether this mechanism occurs at the cell-wall or cell-membrane level is unclear. This paper reviews the important factors affecting the mechanism of dehydration-rehydration, focusing on the analysis of the composition and structure of the cell wall and cell membrane, and summarizes the related detection and analytical techniques that can be used to explore the mechanisms of dehydration-rehydration at the cell-wall and cell-membrane levels. The integrity and permeability of the cell membrane affect water transport during the dehydration-rehydration process. The cell wall and cell membrane are supporting materials for tissue morphology. The arabinan side chains of the primary structure and fibers are important for water retention. Water transport may be classified as symplastic and apoplastic. Cell membrane disruption occurs with symbiotic transport but increases the drying rate. An in-depth analysis of the dehydration-rehydration mechanism of vegetables will help develop and improve their processing methods and inspire new applications.

Clostridium butyricum Ameliorates the Effect of Coprophagy Prevention on Hepatic Lipid Synthesis in Rabbits via the Gut-Liver Axis.

Coprophagy prevention (CP) affects the growth performance, hepatic lipid synthesis, and gut microbiota in rabbits. Supplementation with Clostridium butyricum (C. butyricum, Strain number: CCTCC M 2019962) has been found to improve growth performance in rabbits. However, it remains unknown whether C. butyricum can ameliorate the effects of CP on hepatic lipid synthesis and the underlying mechanisms are yet to be elucidated. Therefore, this study aimed to investigate the impact of CP on hepatic lipid synthesis and the underlying mechanism based on the gut-liver axis. The findings revealed that supplementation with C. butyricum could reverse CP-related growth performance, lipid accumulation, bile acid synthesis, and inflammation. Furthermore, C. butyricum exerted protective effects on the gut by preserving intestinal barrier integrity and modulating gut microbiota composition; these factors may represent potential mechanisms through which C. butyricum improves CP-related outcomes. Specifically, C. butyricum reshaped the microbiota by increasing butyric acid levels, thereby maintaining secondary bile acid (deoxycholic acid, chenodeoxycholic acid) balance and attenuating the inhibitory effects of the FXR/SHP pathway on lipid synthesis (SREBP1c/ApoA1). Moreover, the activation of butyrate/GPR43pathway by C. butyricum reduced damage to the intestinal barrier (ZO-1/Occludin/Claudin1) and restored the gut immune microenvironment in CP rabbits. In summary, supplementation with C. butyricum can alleviate the adverse effects of CP on growth performance and hepatic lipid synthesis by modulating the gut-liver axis.

Advanced Platinum-Based Oxygen Reduction Electrocatalysts for Fuel Cells.

ConspectusFuel cells are among the cutting-edge energy technologies. Their commercial development is still hindered by noble platinum (Pt) catalysts for the oxygen reduction reaction (ORR) at the cathode, which not only determine the energy conversion efficiency and service life but also are closely related to the cost and broad application of fuel cells. Given the bright and enormous future of fuel cells, ORR catalysts should possess highly efficient performance yet meet the acceptable Pt costs for large-scale application. Extensive efforts are concentrated on the optimization of Pt-based nanostructures and upgradation of functional carriers to achieve the low-cost and high-activity Pt-based catalysts. By improving the Pt utilization and accessible surface, reducing Pt consumption and catalyst costs, accelerating mass exchange and electron transfer, alleviating the corrosion and agglomeration of carriers and Pt, accompanying with the assistance of robust yet effective functional supports, the service level and life of Pt-based electrocatalysts would be significantly improved and fuel cells could get into commercial market covering broader applications.In this Account, we focus on the recent development of Pt-based catalysts to figure out the problems associated with ORR catalysts in fuel cells. Recent development of Pt-based catalysts is discussed in different stages: (1) multiscale development of Pt-based nanostructures; (2) multielement regulation over Pt-based alloy composition; (3) upgradation of carbon and noncarbon support architectures; (4) development of integrated Pt-based catalysts for fuel cells. Finally, we propose some future issues (such as reaction mechanism, dynamic evolutions, and structure-activity relationship) for Pt-based catalysts, which mainly involve the preparation strategy of Pt-integrated catalysts (combination of Pt nanostructures with nanocarbons), performance evaluation (standard measurement protocols, laboratory-level rotating disk electrode (RDE) measurements, application-level membrane electrode assembly (MEA) service test), advanced interpretation techniques (spectroscopy, electron microscopy, and in situ monitoring), and cutting-edge simulation/calculations and artificial intelligence (simulation, calculations, machine learning, big data screening). This Account calls for the comprehensive development of multiscale, multicomponent, and high-entropy Pt-based alloy nanostructures, and novel and stable carriers, which provide more available options for rational design of low-cost and high-performance Pt-integrated ORR catalysts. More importantly, it will give an in-depth understanding of the reaction mechanism, dynamic development, and structure-performance relationship for Pt-based catalysts in fuel cells and related energy technologies.

Carbon-Confined Indium Oxides for Efficient Carbon Dioxide Reduction in a Solid-State Electrolyte Flow Cell.

Developing robust electrocatalysts and advanced devices is important for electrochemical carbon dioxide (CO2 ) reduction toward the generation of valuable chemicals. We present herein a carbon-confined indium oxide electrocatalyst for stable and efficient CO2 reduction. The reductive corrosion of oxidative indium to the metallic state during electrolysis could be prevented by carbon protection, and the applied carbon layer also optimizes the reaction intermediate adsorption, which enables both high selectivity and activity for CO2 reduction. In a liquid-phase flow cell, the formate selectivity exceeds 90 % in a wide potential window from -0.8 V to -1.3 V vs. RHE. The continuous production of ca. 0.12 M pure formic acid solution is further demonstrated at a current density of 30 mA cm-2 in a solid-state electrolyte mediated reactor. This work provides significant concepts in the parallel development of electrocatalysts and devices for carbon-neutral technologies.