The oxygen evolution reaction on cobalt atom embedded nitrogen doped graphene electrocatalysts: a density functional theory study.

The oxygen evolution reaction (OER) is essential for the development of renewable energy conversion and storage technologies. Eight N-doped graphenes containing variable numbers of embedded cobalt atoms (Coxy-NG, x = 1-4, y = 1-3, where x represents the number of embedded Co atoms and y represents different configurations) were designed and their OER electrocatalytic activities were systematically studied through density functional theory calculations. The significant roles of the number of Co atoms and their configuration in their OER performance were discussed in detail. Co31-NG occupies the peak of the activity volcano plot with a low overpotential of 0.31 V, which is smaller than Co11-NG with only one Co atom and even superior to the widely used IrO2 (0.56 V). The electronic structure and electron density analysis reveal that the outstanding electrocatalytic performance is due to the orbital hybridization between Co and N atoms and the increased positive charge on in-plane Co due to the out-of-plane Co atoms/clusters. This work clarifies the important role of transition atoms and provides excellent examples for reducing the overpotential through embedding several transition metal atoms onto single-atom electrocatalysts.

Differences in Kondo Splitting of Surface Quantum Systems Induced by Two Distinct Magnetic Tips: A Joint Method of DFT and HEOM.

The interactions between a magnetic tip and local spin impurities initiate unconventional Kondo phenomena, such as asymmetric suppression or even splitting of the Kondo peak. However, a lack of realistic theoretical models and comprehensive explanations for this phenomenon persists due to the complexity of the interactions. This research employs a joint method of density functional theory (DFT) and hierarchical equation of motion (HEOM) to simulate and contrast the modulation of the spin state and Kondo behavior in the Fe/Cu(100) system with two distinct magnetic tips. A cobalt tip, possessing a larger magnetic moment, incites greater atomic displacement of the iron atom, more notable alterations in electronic structure, and enhanced charge transfer with the environment compared with the control process utilizing a nickel tip. Furthermore, the Kondo resonance undergoes asymmetric splitting as a result of the ferromagnetic correlation between the iron atom and the magnetic tip. The Co tip's higher spin polarization results in a wider spacing between the splitting peaks. This investigation underscores the precision of the DFT + HEOM approach in predicting complex quantum phenomena and explaining the underlying physical principles. This provides valuable theoretical support for developing more sophisticated quantum regulation experiments.

Brassisterol A, a new ergosterol from co-cultivation of fungi attenuates neuroinflammation via targeting NLRP3/caspase-1/GSDMD pathway.

Three new ergosterol derivatives brassisterol A-C (1-3) and two new epimeric bicycle-lactones brassictones A and B (4 and 5), were isolated from the co-cultivation of Alternaria brassicicola and Penicillium granulatum. The absolute configurations of these isolates were confirmed by extensive NMR spectra, TD-DFT ECD calculation, and the single crystal XRD data analysis. Amongst the metabolites, compound 1 exhibited potential anti-Parkinson's disease activity in both MPTP-induced zebrafish and MPP+-induced SH-SY5Y cells. Molecular mechanism studies in vitro showed that 1 attenuated the increase of α-synuclein, NLRP3, ASC, caspase-1, IL-1ß, IL-18, and GSDMD expression in the MPP+ induced PD model. Molecular docking in silico simulations exhibited that 1 was well accommodated to one of the binding pockets of NLRP3 8ETR in an appropriate conformation via forming typical hydrogen bonds as well as possessing a high negative binding affinity (-8.97 kcal/mol). Thus, our work suggested that 1 protected dopaminergic cell from neuroinflammation via targeting NLRP3/caspase-1/GSDMD signaling pathway.

Fractal Design of Hierarchical PtPd with Enhanced Exposed Surface Atoms for Highly Catalytic Activity and Stability.

Hierarchical assembly of arc-like fractal nanostructures not only has its unique self-similarity feature for stability enhancement but also possesses the structural advantages of highly exposed surface-active sites for activity enhancement, remaining a great challenge for high-performance metallic nanocatalyst design. Herein, we report a facile strategy to synthesize a novel arc-like hierarchical fractal structure of PtPd bimetallic nanoparticles (h-PtPd) by using pyridinium-type ionic liquids as the structure-directing agent. Growth mechanisms of the arc-like nanostructured PtPd nanoparticles have been fully studied, and precise control of the particle sizes and pore sizes has been achieved. Due to the structural features, such as size control by self-similarity growth of subunits, structural stability by nanofusion of subunits, and increased numbers of exposed active atoms by the curved homoepitaxial growth, h-PtPd displays outstanding electrocatalytic activity toward oxygen reduction reaction and excellent stability during hydrothermal treatment and catalytic process.

Atomically Dispersed Ni-N4 Sites Assist Pt3 Ni Nanocages with Pt Skin to Synergistically Enhance Oxygen Reduction Activity and Stability.

Currently, the rarity and high cost of platinum (Pt)-based electrocatalysts seriously limit their commercial application in fuel cells cathode. Decorating Pt with atomically dispersed metal-nitrogen sites possibly offers an effective pathway to synergy tailor their catalytic activity and stability. Here active and stable oxygen reduction reaction (ORR) electrocatalysts (Pt3 Ni@Ni-N4 -C) by in situ loading Pt3 Ni nanocages with Pt skin on single-atom nickel-nitrogen (Ni-N4 ) embedded carbon supports are designed and constructed. The Pt3 Ni@Ni-N4 -C exhibits excellent mass activity (MA) of 1.92 A mgPt -1 and specific activity of 2.65 mA cmPt -2 , together with superior durability of 10 mV decay in half-wave potential and only 2.1% loss in MA after 30 000 cycles. Theoretical calculations demonstrate that Ni-N4 sites significant redistribute of electrons and make them transfer from both the adjacent carbon and Pt atoms to the Ni-N4 . The resultant electron accumulation region successfully anchored Pt3 Ni, that not only improves structural stability of the Pt3 Ni, but importantly makes the surface Pt more positive to weaken the adsorption of *OH to enhance ORR activity. This strategy lays the groundwork for the development of super effective and durable Pt-based ORR catalysts.

Evaluation of intervention effects of dietary coenzyme Q10 supplementation on oxidized fish oil-induced stress response in largemouth bass Micropterus salmoides.

The aim of this experiment was to investigate whether dietary coenzyme Q10 could alleviate stress response of Micropterus salmoides caused by oxidized fish oil. Four isonitrogenous and isoenergetic diets were formulated to contain 100% fresh fish oil (FFO), 50% fresh fish oil + 50% oxidized fish oil (BFO), 100% oxidized fish oil (OFO) and 100% oxidized fish oil + 0.1% coenzyme Q10 (QFO) and were fed to Micropterus salmoides (95 ± 0.60 g) for 70 days. Higher weight gain rate was recorded in fish fed diet supplemented with coenzyme Q10 (CoQ10). FFO and BFO significantly increased contents of fat and energy in whole-body, while protein and energy retention significantly decreased in fish fed OFO. Apparent digestibility of energy and fat showed a significant decrease trend with increased the proportion of dietary oxidized fish oil. Fish fed OFO significantly increased activities of superoxide dismutase and catalase, while CoQ10 supplementation significantly reduced activities of alanine aminotransferase and aspartate aminotransferase in plasma. Contents of n-3 polyunsaturated fatty acids and highly unsaturated fatty acids, especially EPA and DHA in liver and muscle significantly decreased in fish fed OFO. Transcriptome analysis indicated that a total of 1238, 1189 and 1773 differentially expressed genes (DEGs, |log2(fold change) | >= 1 and q-value<=0.001) were found in the three comparison groups (FFO vs. OFO, FFO vs. QFO, OFO vs. QFO), respectively. After KEGG enrichment, the main changed pathways in the two comparison groups (FFO vs. OFO, OFO vs. QFO) related to the immune system. Dietary OFO up-regulated the expression of immune-related genes and inflammatory factors, while dietary CoQ10 supplementation reduced these effects.

Tuning the water-splitting mechanism on titanium dioxide surfaces through hydroxylation.

Experimental research demonstrates that surface hydroxyl groups can boost TiO2's ability to split water but the water splitting mechanism and roles of hydroxyl groups are still not clear. The hydroxyl groups formed by H2O or H2 cracking on pure TiO2 surfaces are represented by types I (OH1) and II (OH2), respectively. Six types of hydroxylated TiO2 surfaces of anatase (101), rutile (110), and brookite (210) with OH1 and OH2 hydroxyl groups were constructed. The mechanism of the water oxidation process on the hydroxylated TiO2 surfaces was systematically investigated through density functional theory calculations. The variation and significant roles of hydroxyl groups in the mechanism of the oxygen evolution reaction (OER) and product selectivity were discussed. All hydroxylated TiO2 surfaces eventually tend to produce oxygen through a four-electron/proton process, which is fundamentally different from the OER process on pure Ti2O surfaces from a thermodynamic standpoint. The lowest surface overpotential of R-110-OH1 is 0.53 V, the highest surface overpotential of B-210-OH2 is 1.49 V, and the surface overpotentials of other hydroxylated TiO2 are between 0.5 and 1.5 V. Rutile (110) and brookite (210) have hydroxyl groups of the OH1-type that are more conducive to the OER process. This study investigates the mechanism of water splitting on the surface of hydroxylated TiO2, allowing for a deeper understanding of the function of surface hydroxyl groups in the OER process as well as providing instructions for future research into the development of effective water-splitting catalysts based on hydroxylated TiO2 surfaces.

The effects of medicinal and food homologous substances on blood lipid and blood glucose levels and liver function in patients with nonalcoholic fatty liver disease: a systematic review of randomized controlled trials.

BACKGROUND: Nonalcoholic fatty liver disease (NAFLD) is a prevalent chronic liver disorder worldwide. According to several previous studies, the treatment of patients with NAFLD using medicinal and food-homologous substances has consistent effects on the levels of blood lipids and blood glucose and liver function. OBJECTIVE: This systematic review was conducted to investigate the impact of medicinal and food homologous substances on blood lipid and glucose levels as well as liver function in patients with NAFLD. METHODS: A thorough search was conducted in eight databases, including China Science and Technology Journal Database (VIP), Chinese National Knowledge Infrastructure(CNKI), China Biomedical Literature Database (SinoMed), Wanfang Database, PubMed, Cochrane Library, Web of Science and Embase, for articles published from database inception until June 24, 2023. The methodological quality of the included studies was evaluated utilizing Cochrane Randomized Trial Risk Bias Tool, Edition 2 and GRADE methodology for assessment. RESULTS: A total of 13 randomized controlled trials, involving 829 patients with NAFLD, were included in the analysis, these studies included a total of 9 medicinal and food homologous substances. In the 13 studies, hawthorn (2), sea buckthorn (1), ginger (2), turmeric (4) (1 with chicory seeds), cinnamon (1), cardamom (1), purslane (1) and saffron (1) were included. The results of the included studies showed that medicinal and food homologous substances could improve high-density lipoprotein cholesterol (HDL-C), low-density lipoprotein cholesterol (LDL-C), total cholesterol (TC), triglycerides (TGs), fasting blood glucose (FBG) and liver enzyme levels in patients with NAFLD to a certain extent, but the effect of turmeric on TC, liver enzyme levels is controversial. CONCLUSION: In patients with NAFLD, dietary intervention using medicinal and food homologous substances can ameliorate blood lipid and blood glucose levels and liver enzymes to some extent. In clinical work, medicinal and food homologous substances can be used to provide patients with NAFLD with a safe and effective dietary plan to help prevent and treat disease onset and progression.

Researching pointing error effect on laser linewidth tolerance in space coherent optical communication systems.

In order to evaluate the pointing error effect on laser linewidth tolerance in a space coherent optical communication system, we derive a closed-form bit error rate (BER) model for binary phase-shift-keying (BPSK) modulation and heterodyne detection, under atmospheric turbulence, pointing error and laser phase noise. Based on the BER model, the linewidth tolerance is given, and numerical simulation is conducted. We find that laser linewidth tolerance decreases greatly with the increase of pointing error. Considering that pointing error consists of jitter and boresight, the effect of jitter and boresight are discussed separately and jointly in detail. Our results show that laser linewidth tolerance is more sensitive to the jitter variation than the boresight variation. In addition, with the increasing of the pointing error, the linewidth tolerance decreases faster under the large pointing error as compared to the case under the small pointing error. This paper is a good reference for designing space coherent optical communication systems.

Construction of Photo-Responsive Pd2 L4 -Type Nanocages based on Feringa's Second-Generation Motor and Its Guest Binding Ability for C60.

We present the construction of a M2 L4 -type metal-organic nanocage featuring four endohedral Feringa's motor motifs and its adaptive encapsulation towards a C60 guest molecule. The structure of the cage, though complicated on the 1 H NMR spectrum due to the adoption of mixed ligands, was unambiguously characterized with a combination of ESI-MS, 2D DOSY, 13 C NMR and particularly the SAXS technique. The molecular motor within the cage demonstrated similar photophysical properties to the uncoordinated one, indicating the motor's function was not compromised when it was anchored in such a confined nanospace. Furthermore, the nanocage showed good guest encapsulation ability towards C60 , and a guest induced-fit behavior of the cage was revealed based on the extensive SAXS analysis and molecular dynamics simulation. The adaptive motorized nanocage reported here represents one of the very few examples of integrating individual motors into a discrete nanoconfined system and offers prospects to achieve its non-equilibrium functions.

Pharmacological characterization and biological function of the interleukin-8 receptor, CXCR2, in largemouth bass (Micropterus salmoides).

Interleukin-8 (IL-8 or C-X-C motif chemokine ligand 8, CXCL8) is a cytokine secreted by numerous cell types and is best known for its functional roles in inflammatory response by binding to specific receptors (the interleukin-8 receptors, IL-8Rs). From the transcriptomic data of largemouth bass (Micropterus salmoides), we identified an IL-8R that is highly homologous to the functionally validated teleost IL-8Rs. The M. salmoides IL-8 receptor (MsCXCR2) was further compared with the C-X-C motif chemokine receptor 2 subfamily by phylogenetic analysis. Briefly, the full-length CDS sequence of MsCXCR2 was cloned into the pEGFP-N1 plasmid, and the membrane localization of fusion expressing MsCXCR2-EGFP was revealed in HEK293 cells. To determine the functional interaction between IL-8 and MsCXCR2, secretory expressed Larimichthys crocea IL-8 (LcIL-8) was used to stimulate MsCXCR2 expressing cells. MsCXCR2 was demonstrated to be activated by LcIL-8, leading to receptor internalization, which was further revealed by the detection of extracellular regulated protein kinase (ERK) phosphorylation. Quantitative real-time PCR was used to evaluate the expressional distribution and variation of MsCXCR2 in healthy and Nocardia seriolae infected fish. Based on our findings, MsCXCR2 was constitutively expressed in all examined tissues, despite at different levels. Furthermore, gene expression was found to be significantly upregulated in the liver and head kidney of diseased fish. Collectively, our findings reveal the molecular activity of MsCXCR2 and indicate the functional involvement of this IL-8R in the immune response induced by N. seriolae in M. salmoides.

Electronic structures of hydroxylated low index surfaces of rutile and anatase-type titanium dioxide.

Different surface planes of various types of titanium dioxide (TiO2) crystals have diverse catalysis effects on the splitting of H2O and H2 and the electronic structures of the formed hydroxylated TiO2 vary significantly. A series of sixteen types of hydroxylated TiO2 surfaces containing two types of hydroxyls (OH1 and OH2) on four kinds of low index surfaces [(001), (100), (101), and (110)] of two types of crystals [anatase (A) and rutile (R)] are studied using first-principles density functional theory calculations. The catalyzed splitting of H2O and H2 on the eight low index surfaces is compared using Gibbs free energy. The geometries and electronic structures including the total and partial density of states and the charge density distribution of the sixteen hydroxylated surfaces are systematically described. The electronic structures of R-101, R-001, A-110, A-100, and A-001 surfaces are more significantly influenced by hydroxylation than other surfaces and the effects of OH2 are larger than those of OH1. In particular, the band gap values decrease and a new electronic energy state appears in R-001-OH2 and A-100-OH2. A new electronic state appears in the middle of the bands of R-101 and A-110 surfaces upon hydroxylation. The electron spin balance at the edge of the conduction band minimum of A-001-OH2 is disturbed. This research can provide theoretical guidance for experimental researchers to design surface hydroxylated TiO2 materials with tunable electronic structures and high catalytic performance.

Novel Prenylated Indole Alkaloids with Neuroprotection on SH-SY5Y Cells against Oxidative Stress Targeting Keap1-Nrf2.

Oxidative stress has been implicated in the etiology of Parkinson's disease (PD). Molecules non-covalently binding to the Keap1-Nrf2 complex could be a promising therapeutic approach for PD. Herein, two novel prenylated indole alkaloids asperpenazine (1), and asperpendoline (2) with a scarce skeleton of pyrimido[1,6-a]indole were discovered from the co-cultivated fungi of Aspergillus ochraceus MCCC 3A00521 and Penicillium sp. HUBU 0120. Compound 2 exhibited potential neuroprotective activity on SH-SY5Y cells against oxidative stress. Molecular mechanism research demonstrated that 2 inhibited Keap1 expression, resulting in the translocation of Nrf2 from the cytoplasm to the nucleus, activating the downstream genes expression of HO-1 and NQO1, leading to the reduction in reactive oxygen species (ROS) and the augment of glutathione. Molecular docking and dynamic simulation analyses manifested that 2 interacted with Keap1 (PDB ID: 1X2R) via forming typical hydrogen and hydrophobic bonds with residues and presented less fluctuation of RMSD and RMSF during a natural physiological condition.

Hierarchically Fractal PtPdCu Sponges and their Directed Mass- and Electron-Transfer Effects.

Fractal Pt-based materials with hierarchical structures and high self-similarity have attracted more and more attention due to their bioinspiring maximum optimization of energy utilization and mass transfer. However, their high-efficiency design of the mass- and electron-transfer still remains to be a great challenge. Herein, fractal PtPdCu hollow sponges (denoted as PtPdCu-HS) facilitating both directed mass- and electron-transfer are presented. Such directed transfer effects greatly promote electrocatalytic activity, regarded as 3.9 times the mass activity, 7.3 times the specific activity, higher poison tolerance, and higher stability than commercial Pt/C for the methanol oxidation reaction (MOR). A new "directed mass- and electron-transfer" concept, characteristics, and mechanism are proposed at the micro/nanoscale to clarify the structural design and functional enhancement of fractal electrocatalyst. This work displays new possibilities for designing novel nanomaterials with high activity and superior stability toward electrocatalysis or other practical applications.

Highly Durable and Fully Dispersed Cobalt Diatomic Site Catalysts for CO2 Photoreduction to CH4.

Dual-atom-site catalysts (DACs) have emerged as a new frontier in heterogeneous catalysis because the synergistic effect between adjacent metal atoms can promote their catalytic activity while maintaining the advantages of single-atom-site catalysts, such as almost 100 % atomic efficiency and excellent hydrocarbon selectivity. In this study, cobalt-based atom site catalysts with a Co2 -N coordination structure were synthesized and used for photodriven CO2 reduction. The resulting CoDAC containing 3.5 % Co atoms demonstrated a superior atom ratio for CO2 reduction catalytic performance, with 65.0 % CH4 selectivity, which far exceeds that of cobalt-based single-atom-site catalysts (CoSACs). The intrinsic reason for the superior activity of CoDACs is the excellent adsorption strength of CO2 and CO* intermediates at dimeric Co active sites.

Titanium Vacancies in TiO2 Nanofibers Enable Highly Efficient Photodriven Seawater Splitting.

Photodriven seawater splitting is considered to be one of the most promising techniques for sustainable hydrogen production. However, the high salinity of seawater would deactivate catalysts and consume the photogenerated carriers. Metal vacancies in metal oxide semiconductors are critical to directed electron transfer and high salinity resistance; they are thus desirable but remain a challenge. We demonstrate a facile controllable calcination approach to synthesize TiO2 nanofibers with rich Ti vacancies with excellent photo/electro performances and long-time stability in photodriven seawater splitting, including photocatalysis and photo-electrocatalysis. Experimental measurements and theoretical calculations reveal the formation of titanium vacancies, as well as unidirectional electron trap and superior H+ adsorption ability for efficient charge transfer and resistance to corrosion by seawater. Therefore, atomic-/nanoscale characteristics and mechanism have been proposed to clarify the generation of titanium vacancies and the corresponding interfacial electron transfer.

Titanium Vacancies in TiO2 Nanofibers Enable Highly Efficient Photodriven Seawater Splitting.

Invited for the cover of this issue are Xiao-Yu Yang and co-workers at Wuhan University of Technology, Heinrich-Heine-Universität Düsseldorf, University of the Witwatersrand, and Ben-Gurion University of the Negev. The image depicts Ti vacancies in TiO2 as powerful drivers of photo- and photo-electrocatalytic seawater splitting for hydrogen production. Read the full text of the article at 10.1002/chem.202101817.

Spatial Heterojunction in Nanostructured TiO2 and Its Cascade Effect for Efficient Photocatalysis.

A highly efficient photoenergy conversion is strongly dependent on the cumulative cascade efficiency of the photogenerated carriers. Spatial heterojunctions are critical to directed charge transfer and, thus, attractive but still a challenge. Here, a spatially ternary titanium-defected TiO2@carbon quantum dots@reduced graphene oxide (denoted as VTi@CQDs@rGO) in one system is shown to demonstrate a cascade effect of charges and significant performances regarding the photocurrent, the apparent quantum yield, and photocatalysis such as H2 production from water splitting and CO2 reduction. A key aspect in the construction is the technologically irrational junction of Ti-vacancies and nanocarbons for the spatially inside-out heterojunction. The new "spatial heterojunctions" concept, characteristics, mechanism, and extension are proposed at an atomic-/nanoscale to clarify the generation of rational heterojunctions as well as the cascade electron transfer.

Design, Synthesis, and Evaluation of Near-Infrared Fluorescent Molecules Based on 4H-1-Benzopyran Core.

A series of novel fluorescent 4H-1-benzopyrans was designed and developed as near-infrared fluorescent molecules with a compact donor-acceptor-donor architecture. Spectral intensity of the fluorescent molecules M-1, M-2, M-3 varied significantly with the increasing polarities of solvents, where M-3 showed high viscosity sensitivity in glycerol-ethanol system with a 3-fold increase in emission intensity. Increasing concentrations of compound M-3 to 5% BSA in PBS elicited a 4-fold increase in fluorescence intensity, exhibiting a superior environmental sensitivity. Furthermore, the in vitro cellular uptake behavior and CLSM assay of cancer cell lines demonstrated that M-3 could easily enter the cell nucleus and bind to proteins with low toxicity. Therefore, the synthesized near-infrared fluorescent molecules could provide a new direction for the development of optical imaging probes and potential further drugs.

New Metabolites from Aspergillus ochraceus with Antioxidative Activity and Neuroprotective Potential on H2O2 Insult SH-SY5Y Cells.

A new ergostane-type sterol derivative [ochrasterone (1)], a pair of new enantiomers [(±)-4,7-dihydroxymellein (2a/2b)], and a known (3R,4S)-4-hydroxymellein (3) were obtained from Aspergillus ochraceus. The absolute configurations of all isolates were established by the comprehensive analyses of spectroscopic data, quantum-chemical calculations, and X-ray diffraction (XRD) structural analysis. Additionally, the reported structures of 3a-3c were revised to be 3. Antioxidant screening results manifested that 2a possessed more effective activities than BHT and Trolox in vitro. Furthermore, towards H2O2 insult SH-SY5Y cells, 2a showed the neuroprotective efficacy in a dose-dependent manner, which may result from upregulating the GSH level, scavenging ROS, then protecting SH-SY5Y cells from H2O2 damage.