Dual-vacancies modulation of 1T/2H heterostructured MoS2-CdS nanoflowers via radiolytic radical chemistry for efficient photocatalytic H2 evolution.

Precise defect engineering of photocatalysts is highly demanding but remains a challenge. Here, we developed a facile and controllable γ-ray radiation strategy to assemble dual-vacancies confined MoS2-CdS-γ nanocomposite photocatalyst. We showed the solvated electron induced homogeneous growth of defects-rich CdS nanoparticles, while the symbiotic •OH radicals etched flower-like 1T/2H MoS2 substrate surfaces. The optimal MoS2-CdS-γ exhibited a H2 evolution rate of up to 37.80 mmol/h/g under visible light irradiation, which was 36.7 times higher than that of bare CdS-γ, and far superior to those synthesized by hydrothermal method. The microscopic characterizations and theoretical calculations revealed the formation of such unprecedented dual-sulfur-vacancies ensured the tight interfacial contact for fast charge separation. Besides, the existence of 1T-MoS2 phase further improved the conductivity and strengthened the adsorption interaction with H+ intermediate. Therefore, the radiolytic radical chemistry offered a facile, ambient and effective synthetic strategy to improve the catalytic performances of photocatalytic materials.

Ambient γ-Rays-Mediated Noble-Metal Deposition on Defect-Rich Manganese Oxide for Glycerol-Assisted H2 Evolution at Industrial-Level Current Density.

Developing novel synthesis technologies is crucial to expanding bifunctional electrocatalysts for energy-saving hydrogen production. Herein, we report an ambient and controllable γ-ray radiation reduction to synthesize a series of noble metal nanoparticles anchored on defect-rich manganese oxides (M@MnO2-x , M=Ru, Pt, Pd, Ir) for glycerol-assisted H2 evolution. Benefiting from the strong penetrability of γ-rays, nanoparticles and defect supports are formed simultaneously and bridged by metal-oxygen bonds, guaranteeing structural stability and active site exposure. The special Ru-O-Mn bonds activate the Ru and Mn sites in Ru@MnO2-x through strong interfacial coordination, driving glycerol electrolysis at low overpotential. Furthermore, only a low cell voltage of 1.68 V is required to achieve 0.5 A cm-2 in a continuous-flow electrolyzer system along with excellent stability. In situ spectroscopic analysis reveals that the strong interfacial coordination in Ru@MnO2-x balances the competitive adsorption of glycerol and OH* on the catalyst surface. Theoretical calculations further demonstrate that the defect-rich MnO2 support promotes the dissociation of H2 O, while the defect-regulated Ru sites promote deprotonation and hydrogen desorption, synergistically enhancing glycerol-assisted hydrogen production.

Selective CO2 reduction to CH3OH over atomic dual-metal sites embedded in a metal-organic framework with high-energy radiation.

The efficient use of renewable X/γ-rays or accelerated electrons for chemical transformation of CO2 and water to fuels holds promise for a carbon-neutral economy; however, such processes are challenging to implement and require the assistance of catalysts capable of sensitizing secondary electron scattering and providing active metal sites to bind intermediates. Here we show atomic Cu-Ni dual-metal sites embedded in a metal-organic framework enable efficient and selective CH3OH production (~98%) over multiple irradiated cycles. The usage of practical electron-beam irradiation (200 keV; 40 kGy min-1) with a cost-effective hydroxyl radical scavenger promotes CH3OH production rate to 0.27 mmol g-1 min-1. Moreover, time-resolved experiments with calculations reveal the direct generation of CO2•‒ radical anions via aqueous electrons attachment occurred on nanosecond timescale, and cascade hydrogenation steps. Our study highlights a radiolytic route to produce CH3OH with CO2 feedstock and introduces a desirable atomic structure to improve performance.

Clinical analysis of anastomotic fistula after anal preservation in 358 cases of rectal cancer and construction of risk prediction model: a single-center retrospective study.

OBJECTIVE: To develop and validate a simple prediction model for postoperative anastomotic leakage (AL) in patients with rectal cancer who underwent Dixon surgery by combining preoperative and intraoperative risk factors. METHODS: We conducted a retrospective study on 358 patients who underwent Dixon surgery for rectal cancer in the Affiliated Hospital of Youjiang Medical University for Nationalities (Guangxi Zhuang Autonomous Region, China). Based on logistic regression, the prediction model of AL after Dixon surgery was established and verified. RESULTS: The incidence of postoperative AL in these patients was 9.2% (33/358). The results of logistic regression analysis showed that age ≥60 years, male, Tumor-Node-Metastasis (TNM) stage ≥IIIa, preoperative obstruction, and the distance from the tumor to the anus ≤7 cm were the risk factors for AL after Dixon surgery, and intraoperative defunctioning stoma was the protective factor for AL after rectal Dixon surgery (all P<0.05). The prediction model construction: Risk score =-4.275 + 0.851 × age + 1.047 × sex + 0.851 × distance + 0.934 × stage + 0.983 × obstruction. The area under receiver operating characteristic curve (ROC-AUC) was 0.762 (95% CI: 0.667-0.856). The best cutoff, sensitivity and specificity were 0.14, 79.60%, and 83.10%, respectively. Hosmer-Lemeshow: X2=6.876, P=0.550. Clinical validation results: the sensitivity, specificity, and accuracy of the model were 82.05%, 80.06%, and 80.25%, respectively. CONCLUSIONS: Both preoperative and intraoperative risk factors were used in the prognostic model. The prediction model established on this basis was well differentiated and highly calibrated, providing a good reference for the clinical prediction model of postoperative AL in rectal cancer patients undergoing Dixon surgery.

Comparing monetary gain and loss in the monetary incentive delay task: EEG evidence.

What is more effective to guide behavior: The desire to gain or the fear to lose? Electroencephalography (EEG) studies have yielded inconsistent answers. In a systematic exploration of the valence and magnitude parameters in monetary gain and loss processing, we used time-domain and time-frequency-domain analyses to uncover the underlying neural processes. A group of 24 participants performed a monetary incentive delay (MID) task in which cue-induced anticipation of a high or low magnitude of gain or loss was manipulated trial-wise. Behaviorally, the anticipation of both gain and loss expedited responses, with gain anticipation producing greater facilitation than loss anticipation. Analyses of cue-locked P2 and P3 components revealed the significant valence main effect and valence × magnitude interaction: amplitude differences between high and low incentive magnitudes were larger with gain vs. loss cues. However, the contingent negative variation component was sensitive to incentive magnitude but did not vary with incentive valence. In the feedback phase, the RewP component exhibited reversed patterns for gain and loss trials. Time-frequency analyses revealed a large increase in delta/theta-ERS oscillatory activity in high- vs. low-magnitude conditions and a large decrease of alpha-ERD oscillatory activity in gain vs. loss conditions in the anticipation stage. In the consumption stage, delta/theta-ERS turned out stronger for negative than positive feedback, especially in the gain condition. Overall, our study provides new evidence for the neural oscillatory features of monetary gain and loss processing in the MID task, suggesting that participants invested more attention under gain and high-magnitude conditions vs. loss and low-magnitude conditions.

Nickel/Photoredox-Catalyzed Direct Amidation of Aldehydes with Nitroarenes via Fully Catalytic Process.

A fully catalytic nickel-photoredox process for the direct amidation of aldehydes with nitroarenes was developed. In this system, aldehydes and nitroarenes were catalytically activated by the photocatalytic cycle without the addition of an additional reductant or oxidants, which facilitated the Ni-mediated cross-coupling of the C-N bond under mild conditions. A preliminary mechanistic study indicates a reaction pathway in which nitrobenzene is directly reduced to aniline as the nitrogen source.

Radiolytic Water Splitting Sensitized by Nanoscale Metal-Organic Frameworks.

High-energy radiation that is compatible with renewable energy sources enables direct H2 production from water for fuels; however, the challenge is to convert it as efficiently as possible, and the existing strategies have limited success. Herein, we report the use of Zr/Hf-based nanoscale UiO-66 metal-organic frameworks as highly effective and stable radiation sensitizers for purified and natural water splitting under γ-ray irradiation. Scavenging and pulse radiolysis experiments with Monte Carlo simulations show that the combination of 3D arrays of ultrasmall metal-oxo clusters and high porosity affords unprecedented effective scattering between secondary electrons and confined water, generating increased precursors of solvated electrons and excited states of water, which are the main species responsible for H2 production enhancement. The use of a small quantity (<80 mmol/L) of UiO-66-Hf-OH can achieve a γ-rays-to-hydrogen conversion efficiency exceeding 10% that significantly outperforms Zr-/Hf-oxide nanoparticles and the existing radiolytic H2 promoters. Our work highlights the feasibility and merit of MOF-assisted radiolytic water splitting and promises a competitive method for creating a green H2 economy.

Intestinal flora induces depression by mediating the dysregulation of cerebral cortex gene expression and regulating the metabolism of stroke patients.

Post-stroke depression (PSD) is a common cerebrovascular complication characterized by complex pathogenesis and poor treatment effects. Here, we tested the influence of differentially expressed genes (DEGs), non-targeted metabolites, and intestinal microbes on the occurrence and development of PSD. We acquired gene expression profiles for stroke patients, depression patients, and healthy controls from the Gene Expression Omnibus database. After screening for DEGs using differential expression analysis, we identified common DEGs in stroke and depression patients that were considered to form the molecular basis of PSD. Functional enrichment analysis of DEGs also revealed that the majority of biological functions were closely related to metabolism, immunity, the nervous system, and microorganisms, and we also collected blood and stool samples from healthy controls, stroke patients, and PSD patients and performed 16S rDNA sequencing and untargeted metabolomics. After evaluating the quality of the sequencing data, we compared the diversity of the metabolites and intestinal flora within and between groups. Metabolic pathway enrichment analysis was used to identify metabolic pathways that were significantly involved in stroke and PSD, and a global metabolic network was constructed to explore the pathogenesis of PSD. Additionally, we constructed a global regulatory network based on 16S rDNA sequencing, non-targeted metabolomics, and transcriptomics to explore the pathogenesis of PSD through correlation analysis. Our results suggest that intestinal flora associates the dysregulation of cerebral cortex gene expression and could potentially promote the occurrence of depression by affecting the metabolism of stroke patients. Our findings may be helpful in identifying new targets for the prevention and treatment of PSD.

Natural borneol enhances the anti-cerebral ischaemia efficacy of formononetin in MCAO/R rats by promoting its delivery in the brain.

Objectives Due to its high morbidity, high mortality, and high disability, stroke has been the first cause of death and the major cause of adult disability in China. Natural borneol has been widely utilized in Traditional Chinese Medicine to promote drug absorption. Formononetin is a natural isoflavonoid with potent neuroprotective activity but poor brain delivery. Methods This study aimed to screen the optimum proportion that natural borneol promotes formononetin entry into the brain, evaluate the anti-cerebral ischaemia efficacy of formononetin/natural borneol combination in middle cerebral artery occlusion/reperfusion model rats, and clarify the possible mechanism for natural borneol's promoting formononetin delivery in the brain. Key findings Our studies exhibited that natural borneol remarkably promoted formononetin entry into the brain when combined with formononetin in a 1 : 1 molar ratio and notably improved neuro-behavioural scores and reduced the infarct of middle cerebral artery occlusion/reperfusion model rats. This study further discovered that the enhanced anti-cerebral ischaemia effect resulted from natural borneol increasing the permeability of the blood-brain barrier to elevate formononetin concentration in the brain rather than the pharmacodynamic synergy or addition between formononetin and natural borneol. Conclusions The study provides a good strategy to screen drug combinations for the treatment of brain disease by combining natural borneol with other drugs.

Design, Synthesis and Antifungal Evaluation of Novel Pyrylium Salt In Vitro and In Vivo.

Nowadays, discovering new skeleton antifungal drugs is the direct way to address clinical fungal infections. Pyrylium salt SM21 was screened from a library containing 50,240 small molecules. Several studies about the antifungal activity and mechanism of SM21 have been reported, but the structure-activity relationship of pyrylium salts was not clear. To explore the chemical space of antifungal pyrylium salt SM21, a series of pyrylium salt derivatives were designed and synthesized. Their antifungal activity and structure-activity relationships (SAR) were investigated. Compared with SM21, most of the synthesized compounds exhibited equivalent or improved antifungal activities against Candida albicans in vitro. The synthesized compounds, such as XY10, XY13, XY14, XY16 and XY17 exhibited comparable antifungal activities against C. albicans with MIC values ranging from 0.47 to 1.0 µM. Fortunately, a compound numbered XY12 showed stronger antifungal activities and lower cytotoxicity was obtained. The MIC of compound XY12 against C. albicans was 0.24 µM, and the cytotoxicity decreased 20-fold as compared to SM21. In addition, XY12 was effective against fluconazole-resistant C. albicans and other pathogenic Candida species. More importantly, XY12 could significantly increase the survival rate of mice with a systemic C. albicans infection, which suggested the good antifungal activities of XY12 in vitro and in vivo. Our results indicated that structural modification of pyrylium salts could lead to the discovery of new antifungal drugs.

Radiolytic Approach for Efficient, Selective and Catalyst-free CO2 Conversion at Room Temperature.

The present study proposes a new approach for direct CO2 conversion using primary radicals from water irradiation. In order to ensure reduction of CO2 into CO2-. by all the primary radiation-induced water radicals, we use formate ions to scavenge simultaneously the parent oxidizing radicals H. and OH. producing the same transient CO2-. radicals. Conditions are optimized to obtain the highest conversion yield of CO2 . The goal is achieved under mild conditions of room temperature, neutral pH and 1 atm of CO2 pressure. All the available radicals are exploited for selectively converting CO2 into oxalate that is accompanied by H2 evolution. The mechanism presented accounts for the results and also sheds light on the data in the literature. The radiolytic approach is a mild and scalable route of direct CO2 capture at the source in industry and the products, oxalate salt and H2 , can be easily separated.

Thermolysis Synthesis of MoS2 Microrods for Noble Metal-Free Catalytic Reduction of 4-Nitrophenol.

MoS2 microrods constructed by ultrathin nanosheets have been synthesized, for the first time, by thermal decomposition of intermediate (NH4)2MoS4 crystals, which could not only provide the single-source for both the molybdenum and sulfur atoms, but also served as the self-sacrificed template. The well-defined microstructure was characterized by XRD, SEM, TEM, XPS, BET, respectively. The results indicated that MoS2 microrods with uniform morphology were assembled by defective ultrathin nanosheets. Moreover, these MoS2 microrods exhibit superior catalytic activity with the apparent rate constant (κapp) of 0.161 min-1 for the reduction of 4-nitrophenol (4-NP) by NaBH4. Encouragingly, the MoS2 microrods still show evident activity for the reduction of 4-NP after five cycle tests, which has significant importance for the application in the reduction of 4-NP to p-aminophenol (4-AP). Also, this method can be extended to construct other kinds of metal dichalcogenides (TMDs).

Feasibility of the UV/AA process as a pretreatment approach for bioremediation of dye-laden wastewater.

Biodegradability and toxicity are two important indexes in considering the feasibility of a chemical process for environmental remediation. The acetylacetone (AA) mediated photochemical process has been proven as an efficient approach for dye decolorization. Both AA and its photochemical degradation products had a high bioavailability. However, the biocompatibility and ecotoxicology of the UV/AA treated solutions are unclear yet. In the present work, we evaluated the biocompatibility and toxicity of the UV/AA treated solutions at both biochemical and organismal levels. The biodegradability of the treated solution was evaluated with the ratio of 5-d biological oxygen demand (BOD5) to chemical oxygen demand (COD) and a 28-d activated sludge assay (Zahn-Wellens tests). The UV/AA process significantly improved the biodegradability of the tested dye solutions. Toxicity was assessed with responses of microorganisms (microbes in activated sludge and Daphnia magna) and plants (bok choy, rice seed, and Arabidopsis thaliana) to the treated solutions, which showed that the toxicity of the UV/AA treated solutions was lower or comparable to that of the UV/H2O2 counterparts. The results are helpful for us to determine whether the UV/AA process is applicable to certain wastewaters and how the UV/AA process could be effectively combined into a sequential chemical-biological water treatment.