α-Acyloxylation of Ketones/Cyclic Ethers Mediated by Hypervalent Iodine(III) Reagents as Oxidants and Nucleophilic Sources.

This study describes a catalyst-free α-acyloxylation of ketones and a KBr-mediated α-acyloxylation of cyclic ethers. These conversions are effectively mediated by hypervalent iodine(III) reagents serving dual roles as the oxidant and nucleophilic source. Consequently, esters are produced directly in moderate to excellent yields. The proposed method features good functional group compatibility, a broad substrate scope, and high synthetic efficiency and is remarkably environmentally friendly.

Metal-free iodination of arylaldehydes for total synthesis of aristogins A-F and hernandial.

Iodine is one of the most effective sources for iodination of aromatic compounds; however, its electrophilicity is insufficient for direct iodination. The selection of appropriate environmentally friendly and cost-effective oxidants in combination with iodine for the iodination of aromatic rings, along with its application in the synthesis of natural products, holds significant importance. A highly efficient method utilizing I(III) as the initiator has been successfully developed for monoiodination of arylaldehydes. The method demonstrates good compatibility with a wide range of (hetero)aromatic aldehydes, resulting in moderate to excellent yields, without the need for any toxic, volatile or explosive reagents. The synthesis of seven natural products, namely aristogins A-F and hernandial, was achieved through this iodination followed by Ullmann-type coupling.

Fermented Ophiocordyceps sinensis mycelium products for preventing contrast-associated acute kidney injury: a systematic review of randomized controlled trials.

BACKGROUND: To evaluate the efficacy, effectiveness and safety of fermented Ophiocordyceps sinensis mycelium (FOSM) products for preventing contrast-associated acute kidney injury (CA-AKI). METHODS: Randomized controlled trials were searched from four Chinese and four English electronic databases and three clinical trial registries up to July 2023. Methodological quality was assessed by using the Cochrane risk-of-bias tool 2.0. Risk difference (RD) or risk ratio (RR) and mean difference (MD) were calculated along with the 95% confidence intervals (CIs). RESULTS: Fourteen trials testing three types of FOSM products (Bailing, Zhiling, and Jinshuibao capsules) involving 1271 participants injected contrast agents were included. For the risk of bias, all trials were rated as some concerns. Compared with routine preventive procedure (RPP) (saline hydration and alprostadil), FOSM products plus RPP showed beneficial effects in reducing the incidence of CA-AKI (14.62% and 5.35%, respectively; RD -0.06, 95% CI -0.09 to -0.03). Subgroup analysis showed that Bailing/Jinshuibao plus RPP demonstrated lower incidence of CA-AKI compared to RPP. However, there was no statistically significant difference between Zhiling with RPP and RPP in the incidence of CA-AKI. Additionally, only when FOSM products were taken before injection of the contrast, it was superior to RPP in reducing the incidence of CA-AKI. There was no statistical difference in adverse events between these two groups. CONCLUSIONS: Low certainty evidence suggests that preventive oral use of FOSM products as an adjuvant agent was safe and might decrease the incidence of CA-AKI. However, high-quality placebo-controlled trials are needed to confirm its benefit.

Triggering Dual Two-electron Pathway for H2 O2 Generation by Multiple [Bi-O]n Interlayers in Ultrathin Bi12 O17 Cl2 towards Efficient Piezo-self-Fenton Catalysis.

Piezo-self-Fenton system (PESF) has been emerging as a promising water treatment technology but suffering from unsatisfied H2 O2 production efficiency. Herein, we rationally design a Bi12 O17 Cl2 piezo-catalyst with multiple [Bi-O]n interlayers towards highly efficient H2 O2 production. The introduction of [Bi3 O4.25 ] layers initiates dual two-electron pathway for H2 O2 generation by altering the interlayer properties. It is found that the additional [Bi3 O4.25 ] layers not only enhance the polarization electric field but also serve as active sites for triggering dual pathways of two-electron O2 reduction and H2 O oxidation reaction for H2 O2 production. Therefore, the Bi12 O17 Cl2 exhibits an ultrahigh rate of H2 O2 generation (7.76 mM h-1 g-1 ) in pure water. Based on the adequate H2 O2 yield, a PESF was constructed for acetaminophen (ACE) degradation with an apparent rate constant of 0.023 min-1 . This work not only presents a potential strategy of tuning the activity of bismuth based piezo-catalysts but also provides a good example on the construction of highly efficient PESF for environmental remediation by using natural mechanical energy.

Is it true that negative emotions cause more utilitarian judgements? from the influence of emotion and cognition.

ABSTRACTThe affect-as-information (AAI) model proposes that emotions influence the accessibility and value of information (Avramova & Inbar, 2013). Furthermore, according to the dual-process model of moral judgement, emotions and cognition influence moral judgement (Greene, 2007; Greene et al., 2001, 2008); however, there is no direct evidence of a causal chain to support this model's proposition. By using a 3 (emotions: positive vs. neutral vs. negative) × 2 (primed rule: save lives vs. do not kill) between-participants design, we examined two hypotheses in two experiments: supraliminal (Experiment 1) and subliminal (Experiment 2) priming. Our results partially supported the AAI model and confirmed that emotions and cognition independently influence moral judgement. Specifically, the positive emotions group made more utilitarian decisions after being primed with the "save lives" rule and more deontological decisions after being primed with the do not kill rule. However, priming did not affect moral judgement in the negative emotion condition. Further, irrespective of whether priming was done, the negative emotion group mostly made utilitarian decisions. Accordingly, we propose a dynamic dual-process model of moral judgement, that can help clarify how emotion and cognition influence moral judgement.

Highly Efficient FeIII -initiated Self-cycled Fenton System in Piezo-catalytic Process for Organic Pollutants Degradation.

Piezo-catalytic self-Fenton (PSF) system has been emerging as a promising technique for wastewater treatment, while the competing O2 reductive hydrogen peroxide (H2 O2 ) production and FeIII reduction seriously limited the reaction kinetics. Here, we develop a two-electron water oxidative H2 O2 production (WOR-H2 O2 ) coupled with FeIII reduction over a FeIII /BiOIO3 piezo-catalyst for highly efficient PSF. It is found that the presence of FeIII can simultaneously initiate the WOR-H2 O2 and reduction of FeIII to FeII , thereby enabling a rapid reaction kinetics towards subsequent Fenton reaction of H2 O2 /FeII . The FeIII initiating PSF system offers exceptional self-recyclable degradation of pollutants with a degradation rate constant for sulfamethoxazole (SMZ) over 3.5 times as that of the classic FeII -PSF system. This study offers a new perspective for constructing efficient PSF systems and shatters the preconceived notion of FeIII in the Fenton reaction.

In Situ Reconstructed Zn doped Fex Ni(1- x ) OOH Catalyst for Efficient and Ultrastable Oxygen Evolution Reaction at High Current Densities.

Developing FeOOH as a robust electrocatalyst for high output oxygen evolution reaction (OER) remains challenging due to its low conductivity and dissolvability in alkaline conditions. Herein, it is demonstrated that the robust and high output Zn doped NiOOH-FeOOH (Zn-Fex Ni(1-x) )OOH catalyst can be derived by electro-oxidation-induced reconstruction from the pre-electrocatalyst of Zn modified Ni metal/FeOOH film supported by nickel foam (NF). In situ Raman and ex situ characterizations elucidate that the pre-electrocatalyst undergoes dynamic reconstruction occurring on both the catalyst surface and underneath metal support during the OER process. That involves the Fe dissolution-redeposition and the merge of Zn doped FeOOH with in situ generated NiOOH from NF support and NiZn alloy nanoparticles. Benefiting from the Zn doping and the covalence interaction of FeOOH-NiOOH, the reconstructed electrode shows superior corrosion resistance, and enhanced catalytic activity as well as bonding force at the catalyst-support interface. Together with the feature of superaerophobic surface, the reconstructed electrode only requires an overpotential of 330 mV at a high-current-density of 1000 mA cm-2 and maintains 97% of its initial activity after 1000 h. This work provides an in-depth understanding of electrocatalyst reconstruction during the OER process, which facilitates the design of high-performance OER catalysts.

Antituberculosis Drugs (Rifampicin and Isoniazid) Induce Liver Injury by Regulating NLRP3 Inflammasomes.

Patients being treated for pulmonary tuberculosis often suffer liver injury due to the effects of anti-TB drugs, and the underlying mechanisms for those injuries need to be clarified. In this study, rats and hepatic cells were administrated isoniazid (INH) and rifampin (RIF) and then treated with NLRP3-inflammasome inhibitors (INF39 and CP-456773) or NLRP3 siRNA. Histopathological changes that occurred in liver tissue were examined by H&E staining. Additionally, the levels IL-33, IL-18, IL-1ß, NLRP3, ASC, and cleaved-caspase 1 expression in the liver tissues were also determined. NAT2 and CYP2E1 expression were identified by QRT-PCR analysis. Finally, in vitro assays were performed to examine the effects of siRNA targeting NLRP3. Treatment with the antituberculosis drugs caused significant liver injuries, induced inflammatory responses and oxidative stress (OS), activated NLRP3 inflammasomes, reduced the activity of drug-metabolizing enzymes, and altered the antioxidant defense system in rats and hepatic cells. The NLRP3 inflammasome was required for INH- and RIF-induced liver injuries that were produced by inflammatory responses, OS, the antioxidant defense system, and drug-metabolizing enzymes. This study indicated that the NLRP3 inflammasome is involved in antituberculosis drug-induced liver injuries (ATLIs) and suggests NLRP3 as a potential target for attenuating the inflammation response in ATLIs.

The Peculiar Role of the Au3 Unit in Aum Clusters: σ-Aromaticity of the Au5Zn+ Ion.

The stability of small Aum (m = 4-7) clusters is investigated by analyzing their energetic, geometric, vibrational, magnetic, and electron density properties. Gold clusters can be constructed from stable cyclic 3-center-2-electron (3c-2e) Au3+ units (3-rings) with σ-aromaticity. The stabilization requires a flow of negative charge from internal 3-rings with electron-deficient bonding to peripheral 3-ring units with stronger Au-Au bonds. The valence-isoelectronic clusters Au6 and Au5Zn+ have similar electronic properties: Au5Zn+ is a strongly σ-aromatic molecule. An understanding of the structure of Aum clusters is obtained by deriving a Clar's Rule equivalent for polycyclic gold clusters: The structure with the larger number of rings with dominant 3c-2e character and a smaller degree of 3c-3e character occupies the global minimum of the Aum potential energy surface.

Most effective way to improve the hydrogen storage abilities of Na-decorated BN sheets: applying external biaxial strain and an electric field.

Density functional calculations were used to investigate the hydrogen storage abilities of Na-atoms-decorated BN sheets under both external biaxial strain and a vertical electric field. The Na atom generally has the weakest binding strength to a given substrate compared with the other elements in the periodic table [PANS, 2016, 113, 3735]. Consequently, it is understudied in comparison to other elements and there are few reports about the hydrogen storage abilities of Na-decorated nanomaterials. We calculated that the average binding energy (Eb) of Na atoms to the pure BN sheet is 1.08 eV, which is smaller than the cohesive energy of bulk Na (1.11 eV). However, the Eb can be increased to 1.15 eV under 15% biaxial strain, and further up to 1.53 eV with the control of both 15% biaxial strain and a 5.14 V nm-1 electric field (E-field). Therefore, the application of biaxial strain and an external upward E-field can prevent clustering of the Na atoms on the surface of a BN sheet, which is crucial for the hydrogen storage. Each Na atom on the surface of a BN sheet can adsorb only one H2 molecule when no strain or E-field is applied; however, the absorption increases to five H2 molecules under 15% biaxial strain and six H2 molecules under both 15% biaxial strain combined with a 5.14 V nm-1E-field. The average adsorption energies for H2 of BN-(Na-mH2) (m = 1-6) are within the range of practical applications (0.2-0.6 eV). The hydrogen gravimetric density of the periodic BN-(Na-6H2)4 structure is 9 wt%, which exceeds the 5.5 wt% value that should be met by 2017 as specified by the US Department of Energy. On the other side, removal of the biaxial strain and E-field can help to desorb the H2 molecule. These findings suggest a new route to design hydrogen storage materials under near-ambient conditions.

CDK6 mediates the effect of attenuation of miR-1 on provoking cardiomyocyte hypertrophy.

MicroRNA-1 (miR-1) is approved involved in cardiac hypertrophy, but the underlying molecular mechanisms of miR-1 in cardiac hypertrophy are not well elucidated. The present study aimed to investigate the potential role of miR-1 in modulating CDKs-Rb pathway during cardiomyocyte hypertrophy. A rat model of hypertrophy was established with abdominal aortic constriction, and a cell model of hypertrophy was also achieved based on PE-promoted neonatal rat ventricular cardiomyocytes (NRVCs). We demonstrated that miR-1 expression was markedly decreased in hypertrophic myocardium and hypertrophic cardiomyocytes. Dual luciferase reporter assays revealed that miR-1 interacted with the 3'UTR of CDK6, and miR-1 was verified to inhibit CDK6 expression at the posttranscriptional level. CDK6 protein expression was observed increased in hypertrophic myocardium and hypertrophic cardiomyocytes. Morover, miR-1 mimic, in parallel to CDK6 siRNA, could inhibit PE-induced hypertrophy of NRVCs, with decreases in cell size, newly transcribed RNA, expressions of ANF and ß-MHC, and the phosphorylated pRb. Taken together, our results reveal that derepression of CDK6 and activation of Rb pathway contributes to the effect of attenuation of miR-1 on provoking cardiomyocyte hypertrophy.

Tandem Fields Facilitating Directional Carrier Migration in Van der Waals Heterojunction for Efficient Overall Piezo-Synthesis of H2O2.

Piezo-synthesis of H2O2 utilizing sustainable mechanical energy as well as earth-abundant water and oxygen is a green, cost-effective, and promising approach. However, achieving simultaneous two-electron water oxidation reaction (2e- WOR) and two-electron oxygen reduction reaction (2e- ORR) faces huge challenges due to insufficient synergistic active sites and slow/messy carrier transfer. Herein, a novel 2D/2D van der Waals heterojunction consisting of BiOIO3 and carbon nitride (BIO/CN) is elaborately designed for highly efficient overall H2O2 piezo-synthesis. Theoretical/experimental results reveal that a Z-scheme electron transfer is formed and facilitated by the tandem interfacial electric field and the bulk piezo-polarization field. On this basis, the carriers are efficiently separated while the oxidation/reduction capacity is preserved, thus providing the strong driving force for the 2e- WOR and 2e- ORR on BIO and CN, respectively. Furthermore, the kinetic and thermodynamic processes of WOR and ORR for H2O2 synthesis improve remarkably. Therefore, BIO/CN exhibits an excellent H2O2 yield of 259.8 µM within 30 min in pure water and air atmosphere (without any sacrificial agents and aeration). This study provides a new idea on strategically controlling electron transfer toward high-efficiency H2O2 piezo-synthesis and expands the avenue for developing effective environmental purification materials.

Unraveling a volcanic relationship of Co/N/C@PtxCo catalysts toward oxygen electro-reduction.

The cathodic oxygen reduction reaction (ORR) has been continuously attracting worldwide interest due to the increasing popularity of proton exchange membrane (PEM) fuel cells. So far, various Pt-group metal (PGM) or PGM-free catalysts have been developed to facilitate the ORR. However, there is still a gap to achieve the expected goals as proposed by the U.S. Department of Energy (DoE). Recently, PGM-free@PGM hybrid catalysts, such as the M/N/C@PtM catalyst, have achieved the milestones of oxygen reduction, as reviewed in our recent work. It is, nevertheless, still challenging to unravel the underlying structure-property relationships. Here, by applying different Pt/Co ratios, a series of Co/N/C@PtxCo catalysts are synthesized. Interestingly, the ORR activity and stability are not linear with the Pt content, but show a volcano-like curve with increased Pt usage. This relationship has been deeply unraveled to be closely related to the contents of pyrrolic N, pyridinic N, and graphitized carbon in catalysts. This work provides guidelines to rationally design the coupled PGM-free@PGM catalysts toward the ORR by appropriate surface engineering.

Hydrogen Bond and Dipole-Dipole Interaction Enabling Ultrastable, Quick Responding, and Self-Healing Proton Exchange Membranes for Fuel Cells.

Proton exchange membranes (PEMs) are subject to mechanical degradation, such as microcracks and pinhole formation, under real-world fuel cell operating conditions, which leads to great issues in terms of device death and safety concerns. Therefore, PEMs with self-healing features are imperative but have rarely been used for proton exchange membrane fuel cells (PEMFCs). Here, a dimensionally stable and self-healing PEM is developed by tuning the hydrogen bond and dipole-dipole interactions between the mature perfluorinated sulfonic acid (PFSA) and a self-healing copolymer, which is specifically synthesized with hexafluorobutyl acrylate (HFBA) and acrylic acid (AA). This hexafluorobutyl acrylate-acrylic acid copolymer (HFBA-co-AA) is suggested as the key to improving the self-healing efficiency of the blended PFSA/HFBA-co-AA membrane. This PFSA/HFBA-co-AA membrane can recover 43.6% of the original tensile strength within only 20 min at 80 °C. This study may pave an avenue toward the development of reliable and durable PEM for fuel cells.

Similarities and Differences between Gas Diffusion Layers Used in Proton Exchange Membrane Fuel Cell and Water Electrolysis for Material and Mass Transport.

Proton-exchange membrane fuel cells (PEMFCs) and water electrolysis (PEMWE) are rapidly developing hydrogen energy conversion devices. Catalyst layers and membranes have been studied extensively and reviewed. However, few studies have compared gas diffusion layers (GDLs) in PEMWE and PEMFC. This review compares the differences and similarities between the GDLs of PEMWE and PEMFC in terms of their material and mass transport characteristics. First, the GDL materials are selected based on their working conditions. Carbon materials are prone to rapid corrosion because of the high anode potential of PEMWEs. Consequently, metal materials have emerged as the primary choice for GDLs. Second, the mutual counter-reactions of the two devices result in differences in mass transport limitations. In particular, water flooding and the effects of bubbles are major drawbacks of PEMFCs and PEMWE, respectively; well-designed structures can solve these problems. Imaging techniques and simulations can provide a better understanding of the effects of materials and structures on mass transfer. Finally, it is anticipated that this review will assist research on GDLs of PEMWE and PEMFC.

Fabrication of lignosulfonate-derived porous carbon via pH-tunable self-assembly strategy for efficient atrazine removal.

Herein, a straightforward protocol was developed for the one-pot synthesis of N-doped lignosulfonate-derived carbons (NLDCs) with a tunable porous structure using natural amino acids-templated self-assembly strategy. Specifically, histidine was employed as a template reagent, leading to the preparation of 10-NLDC-21 with remarkable characteristics, including the large specific surface area (SBET = 1844.5 m2/g), pore volume (Vmes = 1.22 cm3/g) and efficient adsorption for atrazine (ATZ) removal. The adsorption behavior of ATZ by NLDCs followed the Langmuir and pseudo-second-order models, suggesting a monolayer chemisorption nature of ATZ adsorption with the maximum adsorption capacity reached up to 265.77 mg/g. Furthermore, NLDCs exhibited excellent environmental adaptability and recycling performance. The robust affinity could be attributed to multi-interactions including pore filling, electrostatic attraction, hydrogen bonding and π-π stacking between the adsorbents and ATZ molecules. This approach offers a practical method for exploring innovative bio-carbon materials for sewage treatment.

Group bias under uncertain environment: A perspective of third-party punishment.

Third-party punishment (TPP) effectively promotes social cooperation and maintains social norms in which equity plays a decisive role. When third-party and players are affiliated with different groups, there are two distinct phenomena-in-group favoritism (IGF) and black sheep effect (BSE)-in a certain environment. Equity loses its function as a benchmark when the environment is uncertain (de Kwaadsteniet et al., 2013). Thus, we hypothesized that individuals have a stronger IGF because there is more room for interpretations of their behaviors when an uncertain environment results in ambiguous social norms. We utilized a common resource dilemma (CRD) to manipulate the environmental uncertainty by varying the range of the resource size: a certain environment is represented by a resource size of fixed tokens (i.e., 500 tokens) and an uncertain one is represented by that of 300 to 700 tokens. Additionally, group affiliation is manipulated by the alumni relation between the third-party and players. The present study revealed that the uncertain environment led to stricter costly punishment. The experiment confirms the IGF rather than the BSE. We found boundary conditions between IGF and out-group derogation (OGD). When the players' harvest was not obviously violated, the size of TPP for a control group without group affiliation manipulation anchored those of the in-group and OGD occurred. Opposite, when the harvest was obviously violated, the size of TPP for the control group anchored those of the out-group and IGF occurred. The gender of the third-party affects its decision to punish, with men anchoring the control group's punishment to the in-group and showing OGD, whereas women anchoring the control group's punishment to the out-group and showing IGF.

Luminescent Amorphous Silicon Oxynitride Systems: High Quantum Efficiencies in the Visible Range.

In recent years, researchers have placed great importance on the use of silicon (Si)-related materials as efficient light sources for the purpose of realizing Si-based monolithic optoelectronic integration. Previous works were mostly focused on Si nanostructured materials, and, so far, exciting results from Si-based compounds are still lacking. In this paper, we have systematically demonstrated the high photoluminescence external quantum efficiency (PL EQE) and internal quantum efficiency (PL IQE) of amorphous silicon oxynitride (a-SiNxOy) systems. Within an integration sphere, we directly measured the PL EQE values of a-SiNxOy, which ranged from approximately 2% to 10% in the visible range at room temperature. Then, we calculated the related PL IQE through temperature-dependent PL measurements. The obtained PL IQE values (~84% at 480 nm emission peak wavelength) were very high compared with those of reported Si-based luminescent thin films. We also calculated the temperature-dependent PL EQE values of a-SiNxOy systems, and discussed the related PL mechanisms.

Theoretically identifying the electrocatalytic activity and mechanism of Zn doped 2D h-BN for nitrate reduction to NH3.

Developing efficient electrocatalysts for nitrate reduction in wastewater is of great urgency now. High electrocatalytic activity of Zn@BN toward the electrocatalytic NO3RR to NH3 has been identified by density functional calculations, for which the most energy favourable pathway is energy downhill. The electron localization function is significantly correlated with the hydrogenation selectivity of the *NO intermediate.

Effective high-throughput screening of two-dimensional layered materials for potential lithium-ion battery anodes.

Lithium-ion batteries (LIBs) are considered the promising next-generation advanced energy storage devices. It is very important to quickly screen out ideal anode materials for LIBs with excellent performance. In this work, an effective procedure is designed for the high-throughput screening of the three kinds of LIB anode materials from 131 613 inorganic compounds in the Materials Project database. The high throughput screen procedure was not only reliable but was also easily realized. Three ideal anode materials were obtained by considering remarkable thermodynamic stability, Li capacity larger than 372 mA h g-1, band gap smaller than 1.0 eV, and two-dimensional constraint. Furthermore, open-circuit voltage, volume expansion ratio, and the diffusion energy barrier were calculated by the DFT-D corrected density functional method. We believe that our high throughput screen procedure can effectively and accurately search for other kinds of anode materials, which can strongly support the theoretical basis for experimental research.