Fused Functional Organic Material with the Alternating Conjugation of Quinone-Pyrazine as Cathode for Aqueous Zinc Ion Batteries.

Organic cathode materials for aqueous rechargeable zinc batteries (ARZBs) are rapidly gaining prominence, while the exploration of compounds with affordable synthesis, satisfactory electrochemical performance, and understandable mechanisms still remains challenging. In this study, 6,8,15,17-tetraaza-heptacene-5,7,9,14,16,18-hexaone (TAHQ) as an easily synthesized organic cathode material with novel quinone/pyrazine alternately conjugated molecule structure is presented. This organic electrode exhibits good capacity with highly reversible redox reactions, and the influence of multi-active structures on the Zn2+ /H+ loading behavior is systematically investigated by ex situ spectroscopy, electrochemical tests, and computation. Both experimental and theoretical studies effectively address the Zn2+ /H+ intercalation/deintercalation kinetics. Benefitting from the fused active functionalities, the assembled Zn//TAHQ battery displays a maximum discharge specific capacity of 254.3 mAh g-1 at 0.5 A g-1 , and it maintains remarkable cycle performance with 71% capacity retention after 1000 cycles under 5 A g-1 .

Engineering Low-Cost Organic Cathode for Aqueous Rechargeable Battery and Demonstrating the Proton Intercalation Mechanism for Pyrazine Energy Storage Unit.

Seeking organic cathode materials with low cost and long cycle life that can be employed for large-scale energy storage remains a significant challenge. This work has synthesized an organic compound, triphenazino[2,3-b](1,4,5,8,9,12-hexaazatriphenylene) (TPHATP), with as high as 87.16% yield. This compound has a highly π-conjugated and rigid molecular structure, which is synthesized by capping hexaketocyclohexane with three molecules of 2,3-diaminophenazine derived from low-cost o-phenylenediamine, and is used as a cathode material for assembling aqueous rechargeable zinc ion batteries. Both experiments and DFT calculations demonstrate that the redox mechanism of TPHATP is predominantly governed by H+ storage. The Zn-intercalation product of nitride-type compound, is too unstable to form in water. Moreover, the TPHATP cathode exhibits a capacity of as high as 318.3 mAh g-1 at 0.1 A g-1 , and maintained a stable capacity of 111.9 mAh g-1 at a large current density of 10 A g-1 for 5000 cycles with only a decay of 0.000512% per cycle. This study provides new insights into understanding pyrazine as an active redox group and offers a potential affordable aqueous battery system for grid-scale energy storage.

Ultra-Small High-Entropy Alloy Nanoparticles: Efficient Nanozyme for Enhancing Tumor Photothermal Therapy.

High-entropy alloys nanoparticles (HEANPs) are receiving extensive attention due to their broad compositional tunability and unlimited potential in bioapplication. However, developing new methods to prepare ultra-small high-entropy alloy nanoparticles (US-HEANPs) faces severe challenges owing to their intrinsic thermodynamic instability. Furthermore, there are few reports on studying the effect of HEANPs in tumor therapy. Herein, the fabricated PtPdRuRhIr US-HEANPs act as bifunctional nanoplatforms for the highly efficient treatment of tumors. The US-HEANPs are engineered by the universal metal-ligand cross-linking strategy. This simple and scalable strategy is based on the aldol condensation of organometallics to form the target US-HEANPs. The synthesized US-HEANPs exhibit excellent peroxidase-like (POD-like) activity and can catalyze the endogenous hydrogen peroxide to produce highly toxic hydroxyl radicals. Furthermore, the US-HEANPs possess a high photothermal conversion effect for converting 808 nm near-infrared light into heat energy. In vivo and in vitro experiments demonstrated that under the synergistic effect of POD-like activity and photothermal action, the US-HEANPs can effectively ablate cancer cells and treat tumors. It is believed that this work not only provides a new perspective for the fabrication of HEANPs, but also opens the high-entropy nanozymes research direction and their biomedical application.

High capacity adsorption of antimony in biomass-based composite and its consequential utilization as battery anode.

Antimony is more than an emerging pollutant in water but a scare resource. In this study, we report an adsorbent with the record capacity so far from the balanced view of Sb(III) and Sb(V). The composite adsorbent was fabricated by encapsulating hollow Fe3O4 nanosphere with the EDTA grafted chitosan, and it has superhigh adsorption capacity of for 657.1 mg/g for Sb(III) and 467.3 mg/g for Sb(V), respectively. The mechanism study reveals that the adsorption of Sb initializes from the Fe3O4, propagates along the chitosan with hydrogen bond, and terminates at the inner sphere complex with the EDTA moiety in the adsorbent. In view of the ultra-high adsorption capacity of the adsorbent, the recovered adsorbent that contains abundant (>36.4%) highly dispersed antimony nanoparticles (600-FCSE-Sb) is applied to Li-ion battery anode after reduction. This article provides a new idea for connecting water treatment and electric energy storage.

Intelligent wearable devices based on nanomaterials and nanostructures for healthcare.

Emerging classes of flexible electronic sensors as alternatives to conventional rigid sensors offer a powerful set of capabilities for detecting and quantifying physiological and physical signals from human skin in personal healthcare. Unfortunately, the practical applications and commercialization of flexible sensors are generally limited by certain unsatisfactory aspects of their performance, such as biocompatibility, low sensing range, power supply, or single sensory function. This review intends to provide up-to-date literature on wearable devices for smart healthcare. A systematic review is provided, from sensors based on nanomaterials and nanostructures, algorithms, to multifunctional integrated devices with stretchability, self-powered performance, and biocompatibility. Typical electromechanical sensors are investigated with a specific focus on the strategies for constructing high-performance sensors based on nanomaterials and nanostructures. Then, the review emphasizes the importance of tailoring the fabrication techniques in order to improve stretchability, biocompatibility, and self-powered performance. The construction of wearable devices with high integration, high performance, and multi-functionalization for multiparameter healthcare is discussed in depth. Integrating wearable devices with appropriate machine learning algorithms is summarized. After interpretation of the algorithms, intelligent predictions are produced to give instructions or predictions for smart implementations. It is desired that this review will offer guidance for future excellence in flexible wearable sensing technologies and provide insight into commercial wearable sensors.

P-induced bottom-up growth of Fe-doped Ni12P5 nanorod arrays for urea oxidation reaction.

Synthesis of regular morphology catalysts with self-growing substrates is one of the effective methods to solve the problem of easy shedding of heterogeneous catalysts. In this study, Fe-doped Ni12P5 nanorods were prepared by depositing 1,1' -bis (diphenylphosphine) ferrocene (DPPF) on N-doped C/NF. The bottom-up growth of the nanorod is ascribed to the preferential adsorption of DPPF with a P site to NF that is surface-doped with the solid-solving C, and the length of nanorods can reach tens of microns and has good robustness. The N-doped carbon-constrained rod-shaped Fe-doped Ni12P5 catalyst (Fe-Ni12P5/NdC/NF-800) that grows on NF has excellent catalytic performance for the urea oxidation reaction. In addition, the current density can be maintained as high as 100 mA cm-2 and the current attenuation is weak for 12 h, and the rod shape remains good. This work provides a new idea for synthesizing self-growing catalysts with regular morphology to improve the performance of heterogeneous catalysts.

Fe, Ni-modified ZIF-8 as a tensive precursor to derive N-doped carbon as Na and Li-ion batteries anodes.

Carbon materials derived from metal-organic frameworks have attracted increasing attention as anodes for energy storage. In this study, Fe, Ni-doped ZIF-8 is carbonized at high temperature to obtain bimetallic Fe and Ni modified tension -relaxed carbon (FeNi@trC). Fe and Ni have opposite structural modification effects when the metal ions are doped into the ZIF-8 dodecahedron. The obtained carbon material maintains the regular dodecahedron morphology, which means the relaxation of tension and strong thermal stability during annealing. Moreover, the presence of nickel enhances the carbonization degree and electrochemical stability of FeNi@trC, while the calcination of the tensive ZIF-8 precursor offers more defect sites. The discharge capacities of FeNi@trC materials are stable at 182.9 mAh·g-1and 567.9 mAh·g-1for sodium-ion batterie (SIB) and lithium-ion batterie (LIB) at 0.05 A·g-1. Compared with the current density of 0.05 A·g-1, the discharge capacity of SIB and LIB attenuates by 29.4% and 55.9% at 1 A·g-1, respectively, and the FeNi@trC shows good performance stability in the following cycles.

P-Induced Permeation of Nickel into WO3 Octahedra to Form a Synergistic Catalyst for Urea Oxidation.

Small-molecule induction can lead to the oriented migration of metal elements, which affords functional materials with synergistic components. In this study, phosphating nickel foam (NF)-supported octahedral WO3 with phosphine affords P-WO3 /NF electrocatalyst. Ni is found to form Ni-P bonds that migrate from NF to WO3 under the induction of P, resulting in the complex oxides W1.3 Ni0.24 O4 and Ni2 P2 O7 in the particle interior and nickel phosphide on the octahedral grain surface. The catalytic activity of P-WO3 /NF in the urea oxidation reaction (UOR) is improved by synergistic action of the components in the synthesized hybrid particles. A current density of 10 mA cm-2 can be reached at a potential of 1.305 V, the double layer capacitance of the catalyst is significantly increased, and the electron transfer impedance in catalytic UOR is reduced. This work demonstrates that small-molecule induction is suitable for constructing co-catalysts with complex components in a simple protocol, which provides a new route for the design of highly efficient urea oxidation electrocatalysts.

A semi-encapsulated PdRh alloy heterojunction for the selective catalytic hydrogenation of nitrophenylacetylene to nitrostyrene.

Semi-hydrogenation usually requires an effective catalyst to ensure selectivity, especially when reducible groups coexist in a molecule. Pd is widely used in the semi-hydrogenation of alkynes to synthesize alkenes, but the selectivity control is still challenging. Herein, we design a catalyst with a semi-encapsulated PdRh alloy heterojunction in a carbon layer for the selective semi-hydrogenation of 3-nitrophenylacetylene (3-NPA). Benefiting from the presence of a PdRh alloy heterojunction and a semi-encapsulated structure, the catalyst delivers good selectivity and maintains high activity. In addition, the carbon shell can ensure the stability of the catalyst and prolong the service life. This study provides ideas for the rational design of a catalyst to achieve a selective hydrogenation reaction for practical applications.

Engineering monodispersed 2 nm Sb2S3 particles embedded in a porphyrin-based MOF-derived mesoporous carbon network via an adsorption method to construct a high-performance sodium-ion battery anode.

Sodium ion batteries (SIBs) are expected to replace lithium ion batteries (LIBs) as the next generation of large-scale energy storage applications because of their superior cost performance. However, the larger ionic radius of Na+ causes a remarkable volume expansion than that of Li+ during charge and discharge, which reduces the performance of the battery. In this work, we engineered a composite material in that monodispersed 2 nm Sb2S3 particles are uniformly loaded into a carbon matrix (Sb2S3/CZM), which is obtained by carbonization of a zirconium-based MOF with adsorption of Sb. The obtained composite material has a high specific surface area in favor of mass transfer, and the porous structure can resist many volume changes in the circulation process. Moreover, the ultrafine Sb2S3 particles are well-distributed in the composite material, which increases the utilization of the active substance and is promising for the storage of Na+. Based on its unique structure, the Sb2S3/CZM composite shows a specific capacity of 550 mA h g-1 at 100 mA g-1 and an excellent cycling stability of 88.9% retention after 1000 cycles at 3 A g-1. The excellent electrochemical performance provides enlightenment for the rational design of hierarchical heterostructures for energy storage applications.

Qi-Tai-Suan, an oleanolic acid derivative, ameliorates ischemic heart failure via suppression of cardiac apoptosis, inflammation and fibrosis.

Although anti-thrombotic therapy has been successful for prevention of deaths from acute myocardial infarction (MI), by far, there are few preventive and therapeutic options for ischemic heart failure (IHF) after MI. Qi-Tai-Suan (QTS) is an oleanolic acid (OA) derivative which once underwent a clinical trial for treating hepatitis. In this study, we investigated the potential cardioprotective effect of QTS on IHF. IHF mouse model was constructed by coronary artery ligation in male C57BL/6J mice, and the protective effects of QTS on IHF were examined by echocardiography measurement, histological and TUNEL analysis, etc. We found that QTS exhibited promising cardioprotective effect on IHF. QTS treatment significantly improved cardiac function of IHF mice and the symptoms of heart failure. Notably, QTS had much better oral bioavailability (F = 41.91%) in mice than its parent drug OA, and took effects mainly as its original form. Mechanistically, QTS ameliorated ischemic heart failure likely through suppression of cardiac apoptosis, inflammation and fibrosis. Taken together, QTS holds great promise as a preventive and therapeutic agent for ischemic heart failure and related diseases.

Oligo-layer graphene stabilized fully exposed Fe-sites for ultra-sensitivity electrochemical detection of dopamine.

Neurotransmitter dopamine (DA) has been implicated in a variety of physiological and pathological processes, realizing its low detection limit and high sensitivity analysis is of great significance for early disease diagnosis. Herein, we propose a simple pyrolysis approach for dispersing Fe-sites onto the N-doped graphene support (denoted as Fe/N-GR) to construct an electrochemical biosensor for DA detection. The fully exposed Fe-sites guaranteed the well-defined active center for electrochemical oxidation of DA. The Fe/N-GR electrochemical biosensor achieves an ultra-low detection limit for DA of 27 pM with a linear range of 50 pM-15 nM. Specifically, the Fe/N-GR electrochemical biosensor exhibits favorable sensitivity and enzyme-level molecular identification ability in the selective detection of DA versus other typical redox-active interferents. What's more, the detection of dopamine in real human serum samples verifies the applicability of the developed sensor. Our results demonstrate a promising means of using fully exposed metal-site subnanometric catalysts for electrochemical sensing applications.

Biochar microtube interconnected hydrotalcite nanosheets for the adsorption of aqueous Sb(III).

Actuated by the non-ionic heavy metal of antimony (Sb) contaminants with undesired toxicity to the environment and human health, capturing Sb is urgent to remedy contaminated water. Herein, the lamellar MnCo hydrotalcite was grown on catkin-derived biochar through the in situ etching of ZIF-L to construct a hierarchical microtube@nanosheet hybrid (CLMH) for Sb immobilization. The adsorption behaviour and mechanism of trivalent antimony (Sb (III)) on the CLMH were investigated. The CLMH shows good pH applicability for capturing Sb(III) at pH from 2 to 9. The excellent adsorption capacity of CLMH for Sb(III) is 247.62 mg g-1at 303 K, and the endothermic process is proved by the positive value of ΔH0(10.54 kJ mol-1). The adsorption process is fitted with the intra-particle diffusion model, which can be described with external mass transfer, intraparticle diffusion in pores, and equilibrium stage. The adsorption mechanism is proved, which includes the bind of Metal-O-Sb bonds by inner-sphere complex, the embedding of Sb in the intercalation of hydrotalcite, redox between Mn and Sb, and functional groups dependent anchoring effect. The work benefits the understanding of the antimony removal behaviour over the hierarchical microtube@nanosheet hybrids.

Efficacy, Safety, and Retention Rate of Extended-Release Divalproex Versus Conventional Delayed-Release Divalproex: A Meta-Analysis of Controlled Clinical Trials.

Purpose: A novel once-daily divalproex-extended release (ER) dose formulation has been developed; this formulation prolongs the therapeutic serum levels of the drug, compared with the twice-daily conventional divalproex-delayed release (DR) formulation. This study aimed to systematically examine and compare the efficacy, safety, and retention rates of the ER divalproex (VPA-ER) and conventional DR divalproex (VPA-DR) formulations. Methods: Randomized control trials (RCTs) reporting the efficacy, adverse events (AEs), and medication compliance of ER and DR divalproex were searched in online databases, including PubMed, Embase, and Cochrane Library databases, by searching MeSH words and term words. Observational studies with potential biases were excluded. The meta-analysis was performed using Stata 16.0 software. Findings: Thirteen RCTs, involving 1,028 participants, were included in this meta-analysis. Efficacy, AEs, and drug retention rates were the main study outcomes. According to our study, VPA-ER presented clinically significant benefits compared with the placebo in the population with bipolar disorder (BD) (39.5% versus 27.2%, p < 0.001). A similar efficacy of VPA-ER and VPA-DR in controlling seizures was observed in epilepsy patients (87.4% versus 86.5%, p = 0.769). A significantly lower incidence of AEs was reported in the VPA-ER group than in the placebo group (26.8% versus 34.8%, p = 0.003). By contrast, there was no evidence of difference in safety between VPA-ER and VPA-DR (29.4% versus 30.5%, p = 0.750). In addition, the drug retention rate was significantly lower in the VPA-ER group than in the placebo group (76.0% versus 82.7%, p = 0.020), especially in migraine patients (p = 0.022) and in patients who were treated for fewer than 4 weeks (p = 0.018). Implications: The efficacy of VPA-ER was significantly superior to that of the placebo treatment, which provided efficacy similar to that of conventional VPA-DR. VPA-ER is well tolerated with a low rate of AEs compared to the placebo. In addition, the acceptable medicine compliance of VPA-ER was conducive to the long-term maintenance treatment of chronic diseases. Although we analyzed open labels and crossover design RCTs, large-scale multicenter studies on the efficacy and medicine compliance of new ER formulations with less AEs are required to validate our conclusion.

Iron Catalyzed Cascade Construction of Molybdenum Carbide Heterointerfaces for Understanding Hydrogen Evolution.

The intercrystalline interfaces have been proven vital in heterostructure catalysts. However, it is still challenging to generate specified heterointerfaces and to make clear the mechanism of a reaction on the interface. Herein, this work proposes a strategy of Fe-catalyzed cascade formation of heterointerfaces for comprehending the hydrogen evolution reaction (HER). In the pure solid-phase reaction system, Fe catalyzes the in situ conversion of MoO2 to MoC and then Mo2 C, and the consecutive formation leaves lavish intercrystalline interfaces of MoO2 -MoC (in Fe-MoO2 /MoC@NC) or MoC-Mo2 C (in Fe-MoC/ß-Mo2 C@NC), which contribute to HER activity. The improved HER activity on the interface leads to further checking of the mechanism with density functional theory calculation. The computation results reveal that the electroreduction (Volmer step) produced H* prefers to be adsorbed on Mo2 C; then two pathways are proposed for the HER on the interface of MoC-Mo2 C, including the single-molecular adsorption pathway (Rideal mechanism) and the bimolecular adsorption pathway (Langmuir-Hinshelwood mechanism). The calculation results further show that the former is favorable, and the reaction on the MoC-Mo2 C heterointerface significantly lowers the energy barriers of the rate-determining steps.

Effect of different physical activity training methods on epilepsy: A protocol for systematic review and meta-analysis.

BACKGROUND: Over the past few decades, people with epilepsy were advised not to engage in sports based on the fear that sporting activity may cause injuries, potentially induce seizures, and have a negative effect on disease course. However, in recent years, numerous studies have indicated a positive role of physical exercise in reducing the frequency of seizures and improving health condition of patients with epilepsy. The purpose of this study was to compare the effects of different physical exercise programs on the symptomatology and health condition of individuals with epilepsy and provide guidance for selecting the optimal modality of physical exercise for patients with epilepsy via a meta-analysis of available literature. METHODS: A literature search was carried out in MEDLINE via PubMed, Cochrane Library, EBSCO, Embase, China National Knowledge (CNKI), and Wan fang databases to gather relevant data about different physical exercise modalities and epilepsy. We will use Endnote X9 software for studies selection and Stata16.0 software for the data analysis. RESULTS: This present study aimed to provide the most up to date evidence and recommendations for clinicians and epilepsy patients to choose an optimal type of exercise. CONCLUSION: Aerobic exercise and resistance exercises both had a positive effect on epilepsy patients. Persons with epilepsy should be encouraged to participate in sports activities.INPLASY registration number: INPLASY202220070.

Direct sulfhydryl ligand derived UiO-66 for the removal of aqueous mercury and its subsequent application as a catalyst for transfer vinylation.

The treatment of mercury pollutants in water has been wide concern. Adsorption is a promising method for mercury removal that has been extensively studied. Nevertheless, the secondary application of the immobilized Hg is seldom investigated. In this paper, the Hg adsorption behavior of UiO-66 bearing sulfhydryl groups is studied. The research shows that the porous structure and sulfhydryl groups of UiO-66-SH can effectively promote the removal of mercury from water. In addition, this work also pushes forward the sequential application of the recovered adsorbent, which contains the adsorbed mercury that may cause secondary pollution. The recovered waste adsorbent, UiO-66-S-Hg, was successfully used as an efficient catalyst for transfer vinylation, which produces value-added products, vinyl benzoates. Eight vinyl esters have been successfully synthesized with a yield of up to 89%. This methodology provides a promising way for not only the treatment of mercury contamination, but also secondary pollution protection and the resource utilization of immobilized Hg.

Encapsulating Electron-Rich Pd NPs with Lewis Acidic MOF: Reconciling the Electron-Preference Conflict of the Catalyst for Cascade Condensation via Nitro Reduction.

Cascade reactions take advantage of step-saving and facile operation for obtaining chemicals. Herein, catalytic hydrogenation of nitroarene coupled condensation with ß-diketone to afford ß-ketoenamines is achieved by an integrated nanocatalyst, Pd-e@UiO-66. The catalyst has the structure of an acid-rich metal-organic framework (MOF), UiO-66-encapsulated electron-rich Pd nanoparticles, and it reconciles the electron-effect contradiction of cascade catalytic reactions: catalytic hydrogenation requires an electron-rich catalyst, while condensation requires electron-deficient Lewis acid sites. The catalyst showed good activity, high chemoselectivity, and universal applicability for the synthesis of ß-ketoenamines using nitroarenes. More than 30 ß-ketoenamines have been successfully prepared with up to 99% yield via the methodology of relay catalysis. The catalyst exhibited excellent stability to maintain its catalytic performance for more than five cycles. Furthermore, we conducted an in-depth exploration of the reaction mechanism with theoretical calculations.

Investigation of antimony adsorption on a zirconium-porphyrin-based metal-organic framework.

A zirconium-porphyrin based organic framework PCN-222 was employed for investigating the adsorption performance of Sb(III) in aqueous solution. It is proved that the adsorbent has the advantages of rapid adsorption and high capacity. Interestingly, we discover that PCN-222 shows pH-dependent adsorption performance, with higher capacity at pH = 2 and 8 than at pH = 5. According to XPS and FT-IR analyses, an adsorption model of PCN-222 with pH = 2, 5, and 8 is proposed, that is, zirconium clusters combine with antimony at different pH values with bidentate complexes, monodentate complexes, and alkaline monodentate complexes, thus producing an excellent adsorption effect. Moreover, the porphyrin ring is also beneficial for the adsorption of antimony. In addition, PCN-222 shows good regeneration and recycling performance, and it is a promising adsorbent as well as a platform for investigating the removal of Sb(III) in water treatment.