Photoexcited Ru single-atomic sites for efficient biomimetic redox catalysis.

The unsatisfactory catalytic activity of nanozymes owing to their inefficient electron transfer (ET) is the major challenge in biomimetic catalysis-related biomedical applications. Inspired by the photoelectron transfers in natural photoenzymes, we herein report a photonanozyme of single-atom Ru anchored on metal-organic frameworks (UiO-67-Ru) for achieving photoenhanced peroxidase (POD)-like activity. We demonstrate that the atomically dispersed Ru sites can realize high photoelectric conversion efficiency, superior POD-like activity (7.0-fold photoactivity enhancement relative to that of UiO-67), and good catalytic specificity. Both in situ experiments and theoretical calculations reveal that photoelectrons follow the cofactor-mediated ET process of enzymes to promote the production of active intermediates and the release of products, demonstrating more favorable thermodynamics and kinetics in H2O2 reduction. Taking advantage of the unique interaction of the Zr-O-P bond, we establish a UiO-67-Ru-based immunoassay platform for the photoenhanced detection of organophosphorus pesticides.

Strong d-π Orbital Coupling of Co-C4 Atomic Sites on Graphdiyne Boosts Potassium-Sulfur Battery Electrocatalysis.

Potassium-sulfur (K-S) batteries are severely limited by the sluggish kinetics of the solid-phase conversion of K2S3/K2S2 to K2S, the rate-determining and performance-governing step, which urgently requires a cathode with facilitated sulfur accommodation and improved catalytic efficiency. To this end, we leverage the orbital-coupling approach and herein report a strong d-π coupling catalytic configuration of single-atom Co anchored between two alkynyls of graphdiyne (Co-GDY). The d-π orbital coupling of the Co-C4 moiety fully redistributes electrons two-dimensionally across the GDY, and as a result, drastically accelerates the solid-phase K2S3/K2S2 to K2S conversion and enhances the adsorption of sulfur species. Applied as the cathode, the S/Co-GDY delivered a record-high rate performance of 496.0 mAh g-1 at 5 A g-1 in K-S batteries. In situ and ex situ characterizations coupling density functional theory (DFT) calculations rationalize how the strong d-π orbital coupling of Co-C4 configuration promotes the reversible solid-state transformation kinetics of potassium polysulfide for high-performance K-S batteries.

Integrated Catalyst-Substrate Electrodes for Electrochemical Water Splitting: A Review on Dimensional Engineering Strategy.

Water splitting (or, water electrolysis) is considered as a promising approach to produce green hydrogen and relieve the ever-increasing energy consumption as well as the accompanied environmental impact. Development of high-efficiency, low-cost practical water-splitting systems demands elegant design and fabrication of catalyst-loaded electrodes with both high activity and long-life time. To this end, dimensional engineering strategies, which effectively tune the microstructure and activity of electrodes as well as the electrochemical kinetics, play an important role and have been extensively reported over the past years. Here, a type of most investigated electrode configurations is reviewed, combining particulate catalysts with 3D porous substrates (aerogels, metal foams, hydrogels, etc.), which offer special advantages in the field of water splitting. It is analyzed the design principles, structural and interfacial characteristics, and performance of particle-3D substrate electrode systems including overpotential, cycle life, and the underlying mechanism toward improved catalytic properties. In particular, it is also categorized the catalysts as different dimensional particles, and show the importance of building hybrid composite electrodes by dimensional control and engineering. Finally, present challenges and possible research directions toward low-cost high-efficiency water splitting and hydrogen production is discussed.

Strategies for the Construction of Benzobicyclo[3.2.1]octane in Natural Product Synthesis.

Benzobicyclo[3.2.1]octane is a cage-like unique motif containing a bicyclo[3.2.1]octane structure fused with at least one benzene ring. It is found in various natural products that exhibit structural complexities and important biological activities. The total synthesis of natural products possessing this challenging structure has received considerable attention, and great advances have been made in this field during the past 15 years. This review summarizes thus far achieved chemical syntheses and synthetic studies of natural compounds featuring the benzobicyclo[3.2.1]octane core. It focuses on strategic approaches constructing the bridged structure, aiming to provide a useful reference for inspiring further advancements in strategies and total syntheses of natural products with such a framework.

Harmonizing Enzyme-like Cofactors to Boost Nanozyme Catalysis.

Engineering isolated metal sites resembling the primary coordination sphere of metallocofactors enables atomically dispersed materials as promising nanozymes. However, most existing nanozymes primarily focus on replicating specific metallocofactors while neglecting other supporting cofactors within active pockets, leading to reduced electron transfer (ET) efficiency and thus inferior catalytic performances. Herein, we report a metal-organic framework UiO-67 nanozyme with atomically dispersed iron sites, which involves multiple tailored enzyme-like nanocofactors that synergistically drive the ET process for enhanced peroxidase-like catalysis. Among them, the linker-coupled atomic iron site plays a critical role in substrate activation, while bare linkers and zirconia nodes facilitate the ET efficiency of intermediates. The synergy of three nanocofactors results in a 4.29-fold enhancement compared with the single effort of isolated metal site-based nanocofactor, holding promise in immunoassay for sensitive detection of chlorpyrifos. This finding opens a new way for designing high-performance nanozymes by harmonizing various nanocofactors at the atomic and molecular scale.

Fluorination of Covalent Organic Framework Reinforcing the Confinement of Pd Nanoclusters Enhances Hydrogen Peroxide Photosynthesis.

Metal-isolated clusters (MICs) physically confined on photoactive materials are of great interest in the field of photosynthesis of hydrogen peroxide (H2O2). Despite recent important endeavors, weak confinement of MICs in the reported photocatalytic systems leads to their low catalytic activity and stability. Herein, we report a new strategy of fluorinated covalent organic frameworks (COFs) to strongly confine Pd ICs for greatly boosting the photocatalytic activity and stability of H2O2 photosynthesis. Both experimental and theoretical results reveal that strong electronegative fluorine can increase the metal-support interaction and optimize the d-band center of Pd ICs, thus significantly enhancing the stability and activity of photocatalytic H2O2. An optimal TAPT-TFPA COFs@Pd ICs photocatalyst delivers a stable H2O2 yield rate of 2143 µmol h-1 g-1. Most importantly, the as-made TAPT-TFPA COFs@Pd ICs exhibit high catalytic stability over 100 h, which is the best among the reported materials.

Single-Atom Cr-N4 Sites with High Oxophilicity Interfaced with Pt Atomic Clusters for Practical Alkaline Hydrogen Evolution Catalysis.

Although dispersing Pt atomic clusters (ACs) on a conducting support is a promising way to minimize the Pt amount required in hydrogen evolution reaction (HER), the catalytic mass activity and durability of Pt ACs are often unsatisfactory for alkaline HER due to their unfavorable water dissociation and challenges in stabilizing them against agglomeration and detachment. Herein, we report a class of single-atom Cr-N4 sites with high oxophilicity interfaced with Pt ACs on mesoporous carbon for achieving a highly active and stable alkaline HER in an anion-exchange-membrane water electrolyzer (AEMWE). The as-made catalyst achieves the highest reported Pt mass activity (37.6 times higher than commercial Pt/C) and outstanding operational stability. Experimental and theoretical studies elucidate that the formation of a unique Pt-Cr quasi-covalent bonding interaction at the interface of Cr-N4 sites and Pt ACs effectively suppresses the migration and thermal vibration of Pt atoms to stabilize Pt ACs and contributes to the greatly enhanced catalytic stability. Moreover, oxophilic Cr-N4 sites adjacent to Pt ACs with favorable adsorption of hydroxyl species facilitate nearly barrierless water dissociation and thus enhance the HER activity. An AEMWE using this catalyst (with only 50 µgPt cm-2) can operate stably at an industrial-level current density of 500 mA cm-2 at 1.8 V for >100 h with a small degradation rate of 90 µV h-1.

Comparative phosphoproteomic analysis reveals that phosphorylation of sucrose synthase GhSUS2 by Ca2+-dependent protein kinases GhCPK84/93 affects cotton fiber development.

Cotton fiber elongation is a critical growth phase that affects final fiber length. Morphological analysis indicated an asynchronous fiber elongation pattern between two cotton varieties, J7-1 and J14-1. Through phosphoproteomic analysis, a total of 89 differentially-phosphorylated proteins (DPPs) were identified in elongating fibers between J7-1 and J14-1. Gene ontology (GO) analysis showed that these DPPs were mainly enriched in sucrose synthase activity, transferase activity, and UDP-glycosyltransferase activity. In J14-1, the phosphorylation level of GhSUS2, a key sucrose synthase in the sucrose metabolism pathway, was significantly higher than that in J7-1. We further revealed that GhSUS2 positively regulates fiber elongation, and GhSUS2-silenced transgenic cotton displayed the phenotype of 'short fibers' compared with the controls. During fiber development, the residue Ser11 in the GhSUS2 protein is phosphorylated by the Ca2+-dependent protein kinases GhCPK84 and GhCPK93. Phosphorylated GhSUS2 is localized in the cytoplasm, whereas unphosphorylated GhSUS2 is localized in the plasma membrane. Moreover, abscisic acid (ABA) could promote the transcription and translation of GhCPK84 and GhCPK93, thereby enhancing the phosphorylation of GhSUS2 to impede fiber elongation. Thus, our data demonstrates that GhSUS2 plays a positive role in fiber development, but its phosphorylation by GhCPK84 and GhCPK93 hinders fiber elongation of cotton.

Converting industrial waste into a value-added cement material through ambient pressure carbonation.

Converting industrial wastes into value-added building products in an environmental management strategy is a challenging yet vital component of the industrial process. Steel slag (SS), an industrial waste by-product from the steel-making process, is typically disposed of in landfill which consumes land resources and pollutes the environment. This paper explores the possibility of a closed-loop system to convert steel slag into a cement material through carbonation activation, thereby significantly reducing the amount of steel slag waste sent to landfills across Canada. The production of this cementing material can occur next to the steel mill, utilizing steel slag and carbon dioxide collected on-site to fabricate carbon-negative products. To save energy and allow production to be feasible on an industrial scale, ambient pressure (AP) carbonation is developed to reduce carbon emissions while improving their performance. High pressure (HP) carbonation curing and normal hydration (NH) references were also implemented at the same time to justify the application of AP carbonation in reducing CO2 emission. The results of this study found AP carbonation-activated SS compacts have comparable CO2 uptake (about 7.5 tons CO2/100 tons slag) and mechanically compressive strength values as those subjected to HP carbonation, suggesting that AP could be used to replace HP in carbonation curing to ensure a lower energy input. Additionally, AP seemed to possess as effective carbonation as HP. The studies investigated by multiple techniques including X-ray diffractometer (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopic analysis, and scanning electron microscopy (SEM) aim to identify the microstructure development of carbonated SS paste to assess carbonation results. Developed with life cycle assessment (LCA), environmental impact evaluation shows that AP presents a smaller global warming potential (GWP) value than HP. The comparable CO2 sequestration, satisfactory engineering properties, enhanced microstructure and lesser environmental impact in AP carbonation confirm the feasibility of replacing high pressure with extremely low pressure to cure concrete products. The use of AP carbonation for cement material created using steel slag reduces carbon emissions, energy usage, and natural resource consumption.

Three-Step Synthesis of the Antiepileptic Drug Candidate Pynegabine.

Pynegabine, an antiepileptic drug candidate in phase I clinical trials, is a structural analog of the marketed drug retigabine with improved chemical stability, strong efficacy, and a better safety margin. The reported shortest synthetic route for pynegabine contains six steps and involves the manipulation of highly toxic methyl chloroformate and dangerous hydrogen gas. To improve the feasibility of drug production, we developed a concise, three-step process using unconventional methoxycarbonylation and highly efficient Buchwald-Hartwig cross coupling. The new synthetic route generated pynegabine at the decagram scale without column chromatographic purification and avoided the dangerous manipulation of hazardous reagents.

Asymmetric Total Synthesis of Naphthospironone A.

Naphthospironone A, a polyhydroxy cagelike bioactive natural product, was synthesised for the first time in this study. The spiro[bicyclo[3.2.1]octane-pyran] core was constructed by an acid-promoted epoxide-opening lactonisation and a base-induced intramolecular aldol-type cyclisation.

Structure Engineering of Vanadium Tetrasulfides for High-Capacity and High-Rate Sodium Storage.

Structure engineering of electrode materials can significantly improve the life cycle and rate capability of the sodium-ion battery (SIB), yet remains a challenging task due to the lack of an effective synthetic strategy. Herein, the microstructure of VS4 hollow spheres is successfully engineered through a facile hydrothermal method. The hollow VS4 microspheres possess rich porosity and are covered with 2D ultrathin nanosheets on the surface. The finite element simulation (FES) reveals that such heterostructures can effectively relieve the stress induced by the sodiation and thereby enhance the structural integrity. The SIB with the hollow VS4 microspheres as anode displays impressively high specific capacity, excellent stability upon ultra-long cycling, and extraordinary rate capacity, e.g., a reversible capacity of ≈378 mA h g-1 at ultra-high 10 A g-1 , while retaining 73.2% capacity after 1000 cycles. The Na storage mechanism is also elucidated through in situ/ex situ characterizations. Moreover, the hollow VS4 microspheres demonstrate reliable rate performance at a low temperature of -40 °C (e.g., the capacity is ≈163 mA h g-1 at 2 A g-1 ). This work provides novel insights toward high-performance SIBs.

Elevated levels of Metrnl in rheumatoid arthritis: Association with disease activity.

BACKGROUND: Meteorin-like (Metrnl) is a novel adipokine that is highly expressed in white adipose tissues. Whether Metrnl plays a role in rheumatoid arthritis (RA) remains unclear. In this study, sera from 159 RA patients, 28 osteoarthritis (OA) patients, and 50 healthy individuals were included. The serum levels of Metrnl were measured using an enzyme-linked immunosorbent assay. Clinical parameters, including disease activity score 28 (DAS28), C-reactive protein (CRP), erythrocyte sedimentation rate (ESR), rheumatoid factor (RF), antibodies to cyclic citrulline peptide (anti-CCP), inflammatory cytokines, and blood biochemical indices were collected. RESULTS: Metrnl levels were higher in RA patients compared to OA patients and controls. In the RA group, serum Metrnl levels were positively correlated with DAS28, RF, and CRP levels. However, in the RA group, serum Metrnl levels were not correlated with ESR, anti-CCP, immunoglobulins, and blood biochemical indices. CONCLUSION: This study showed that Metrnl is involved in the pathogenesis of RA. Increase in serum Metrnl levels is closely related to RA activity.

Anthropogenic Aerosols Modulated 20th-Century Sahel Rainfall Variability Via Their Impacts on North Atlantic Sea Surface Temperature.

The Sahel rainfall has a close teleconnection with North Atlantic sea surface temperature (NASST) variability, which has separately been shown to be affected by aerosols. Therefore, changes in regional aerosols emission could potentially drive multidecadal Sahel rainfall variability. Here we combine ensembles of state-of-the-art global climate models (the CESM and CanESM large ensemble simulations and CMIP6 models) with observational data sets to demonstrate that anthropogenic aerosols have significantly impacted 20th-century detrended Sahel rainfall multidecadal variability through modifying NASST. We show that aerosol-induced multidecadal variations of downward solar radiative fluxes over the North Atlantic cause NASST variability during the 20th century, altering the ITCZ position and dynamically linking aerosol effects to Sahel rainfall variability. This process chain is caused by aerosol-induced changes in radiative surface fluxes rather than changes in ocean circulations. CMIP6 models further suggest that aerosol-cloud interactions modulate the inter-model uncertainty of simulated NASST and potentially the Sahel rainfall variability.

Association between air pollution and the prevalence of allergic rhinitis in Chinese children: A systematic review and meta-analysis.

Background: Allergic rhinitis (AR) is a common chronic inflammatory disease with bothersome symptoms. However, the effect of air pollution on the prevalence of AR in children is controversial. Objective: This study aimed to investigate the association between air pollution and the prevalence of AR in Chinese children. Methods: This study, in China, included 160,356 students ages 0-18 years who completed a questionnaire about the accuracy of the International Study of Asthma and Allergies in Childhood (ISAAC). The effect of different air pollutants on the prevalence rate were evaluated by meta-analysis. Also, it evaluated the effect of different air pollutants on the prevalence rate. Results: The differences in the effects of sulfur dioxide (SO2) exposure (combined odds ratio [ORcombined] 1.03 [95% confidence interval {CI}, 1.01-1.05]; p = 0.010) and nitrogen dioxide (NO2) exposure (ORcombined 1.11 [95% CI, 1.05-1.18]; p = 0.0006) on the risk of childhood AR was statistically significant. The effect of particulate matter with aerodynamic diameter of <10 µm (PM10) exposure on the risk of childhood AR was statistically significant (ORcombined 1.02 [95% CI, 1.01-1.03]; p < 0.001), the effect of particulate matter with aerodynamic diameter of <2.5 µm (PM2.5) exposure on the risk of childhood AR was statistically significant (ORcombined 1.15 [95% CI, 1.03-1.29]; p = 0.02), and the effect of ozone exposure on the risk of childhood AR was not statistically significant (ORcombined 0.98 [95% CI, 0.67-1.41]; p = 0.13). Conclusion: NO2, SO2, PM2.5, and PM10 were associated with the prevalence of AR in Chinese children. PM2.5 had the highest correlation with AR prevalence.

Antidiarrheal effect of the ethanol extract from Scutellaria barbata and its effect on the contraction of jejunum smooth muscles.

Scutellaria barbata (S. barbata), a traditional herbal medicine used in southern China, possesses anti-inflammatory, antitumor, spasmolytic and expectorant effects. However, there are not many recent studies on its gastrointestinal effects. This study aimed to evaluate the antidiarrheal effect of the ethanol extract of S. barbata (SBE) and its effect on the isolated jejunum smooth muscle. METHODS: The antidiarrheal effect of SBE (doses: 125, 250 and 500 mg/kg) on castor oil-induced diarrhea was investigated in vivo. The effect of SBE (0.01-10 mg/mL) on spontaneous or acetylcholine chloride (ACh, 10µM)/KCl (60mM)-induced contraction of isolated rabbit jejunum smooth muscle was examined in vitro. The possible spasmolytic mechanism of SBE (1 and 3mg/mL) was analyzed by accumulating CaCl2 in a Ca2+-free high-K+ (60mM) solution. RESULTS: SBE (125, 250 and 500mg/kg) could delay the initial semi-solid onset time of mice and also reduce the diarrhea index in vivo. Furthermore, SBE (0.01-10mg/mL) could alleviate the spontaneous or ACh/KCl-induced contraction in vitro. SBE (1 and 3mg/mL) also inhibited the contraction induced by CaCl2, and the concentration-response curves of CaCl2 moved downward and to the right, similar to those of verapamil (0.01 and 0.1µM). CONCLUSIONS: SBE exerts antidiarrheal and spasmolytic effects, which provides a pharmacological basis for its use in functional gastrointestinal disorders.

Vanadium-Based Materials: Next Generation Electrodes Powering the Battery Revolution?

ConspectusAs the world transitions away from fossil fuels, energy storage, especially rechargeable batteries, could have a big role to play. Though rechargeable batteries have dramatically changed the energy landscape, their performance metrics still need to be further enhanced to keep pace with the changing consumer preferences along with the increasing demands from the market. For the most part, advances in battery technology rely on the continuing development of materials science, where the development of high-performance electrode materials helps to expand the world of battery innovation by pushing the limits of performance of existing batteries. This is where vanadium-based compounds (V-compounds) with intriguing properties can fit in to fill the gap of the current battery technologies.The history of experimenting with V-compounds (i.e., vanadium oxides, vanadates, vanadium-based NASICON) in various battery systems, ranging from monovalent-ion to multivalent-ion batteries, stretches back decades. They are fascinating materials that display rich redox chemistry arising from multiple valency and coordination geometries. Over the years, researchers have made use of the inherent ability of vanadium that undergoes metamorphosis between different coordination polyhedra accompanied by transitions in the oxidation state for reversible intercalation/insertion of more than one guest ions without breaking the structure apart. Such infinitely variable properties endow them with a wide range of electronic and crystallographic structures. The former attribute varies from insulators to metallic conductors while the latter feature gives rise to layered structures or 3D open tunnel frameworks that allow facile movement of a wide range of metal cations and guest species along the gallery. Accompanied by a growing stringent requirements for energy storage applications, most V-compounds face difficulty in resolving the problems of their own lack competitiveness mostly due to their intrinsically low ionic/electronic conductivity. The key to producing vanadium-based electrodes with the desired performance characteristics is the ability to fabricate and optimize them consistently to realize certain specifications through effective engineering strategies for property modulation.In this Account, we aim to provide a comprehensive article that correlates the fundamental of charge storage mechanism to crystallographic forms and design principle for V-compounds. More importantly, the essential roles played by engineering strategies in the property modulation of V-compounds are pinpointed to further explain the rationale behind their anomalous behavior. Apart from that, we further summarize the key theoretical and experimental results of some representative examples for tuning of properties. On the other hand, advances in characterization techniques are now sufficiently mature that they can be relied upon to understand the reaction mechanism of V-compounds by tracing real-time transformation and structural changes at the atomic scale during their working state. The mechanistic insights covered in this Account could be used as a fundamental guidance for several key strategies in electrode materials design in terms of dimension, morphology, composition, and architecture that govern the rate and degree of chemical reaction.

Microbiome Links Cigarette Smoke-Induced Chronic Obstructive Pulmonary Disease and Dietary Fiber via the Gut-Lung Axis: A Narrative Review.

Existing comprehensive management strategies for COPD effectively relieve the symptoms of patients, delay the deterioration of lung function, and prevent the progression of COPD through various means and multidisciplinary interventions. However, there has been limited progress in therapies that address the underlying causes of COPD pathogenesis. Recent studies have identified specific changes in the gut and pulmonary microbiota in response to exposure to smoke that can cause or exacerbate CS-COPD by regulating the inflammatory immune response in the lungs through the gut-lung axis. As a convenient and controllable intervention, modifying the diet to include more dietary fiber can effectively improve the prognosis of CS-COPD. Gut microbiota ferment dietary fiber to produce short-chain fatty acids, which connect the microbial communities in the lung and gut mucosa across the gut-lung axis, playing an anti-inflammatory and immunosuppressive role in the lungs. Given that the effect of dietary fiber on gut microbiota was highly similar to that of quitting smoking on gut microbiota, we assume that microbiota might be a potential therapeutic target for dietary fiber to alleviate and prevent CS-COPD. This study examines the similarities between pulmonary and gut microbiota changes in the presence of smoking and dietary fiber. It also highlights the mechanism by which SCFAs link pulmonary and gut microbiota in CS-COPD and analyzes the anti-inflammatory and immunomodulatory effects of short-chain fatty acids on CS-COPD via the gut-lung axis.

Toward the total synthesis of grayanane diterpene mollanol A by a Prins [3 + 2] strategy.

Toward the total synthesis of a novel grayanoid, mollanol A, we developed a concise convergent strategy based on a formal [3 + 2] cyclization initiated by the Prins reaction. In this key intermolecular reaction between an unprotected hydroxyaldehyde and activating-group-free olefins, two chiral carbons and one densely substituted tetrahydrofuran ring were constructed stereoselectively.

Source apportionment and health risk assessment of air pollution particles in eastern district of Chengdu.

This paper systematically studied the mass concentration levels of PM2.5 and PM10 and obtained the morphological characteristics and components of the particles through scanning electron microscopy (SEM-EDX) and discussed the sources of the particles. Meanwhile, the health risk was evaluated according to the mass concentration of particulate matter. The results showed that the average annual PM2.5 and PM10 in the eastern part of Chengdu were 101.99 µg/m3 and 168.89 µg/m3, respectively, exceeding the national second-level average annual air quality standard (GB3095-2012). Both of them were the highest in winter and the lowest in summer and had a significant positive correlation. The atmospheric particles in the study area were mainly composed of fly ash particles, soot aggregates, mineral particles (sulfate mineral particles, carbonate mineral particles, etc.), which mainly came from coal burning, dust, automobile exhaust and secondary products. The results of the health risk assessment showed that the mass concentration of PM2.5 and PM10 in the atmosphere of the eastern part of Chengdu exceeded the IT-1 target. The average annual air quality index was 185.84, and the air quality index was level 4, classified as medium pollution. PM10 and PM2.5 were both excessive pollutants, and PM10 was the primary pollutant. Relevant measures should be taken to control particulate matter sources to some extent.