In situ Raman reveals the critical role of Pd in electrocatalytic CO2 reduction to CH4 on Cu-based catalysts.

Electrocatalytic CO2 reduction reaction (CO2RR) for CH4 production presents a promising strategy to address carbon neutrality, and the incorporation of a second metal has been proven effective in enhancing catalyst performance. Nevertheless, there remains limited comprehension regarding the fundamental factors responsible for the improved performance. Herein, the critical role of Pd in electrocatalytic CO2 reduction to CH4 on Cu-based catalysts has been revealed at a molecular level using in situ surface-enhanced Raman spectroscopy (SERS). A "borrowing" SERS strategy has been developed by depositing Cu-Pd overlayers on plasmonic Au nanoparticles to achieve the in situ monitoring of the dynamic change of the intermediate during CO2RR. Electrochemical tests demonstrate that Pd incorporation significantly enhances selectivity toward CH4 production, and the Faradaic efficiency (FE) of CH4 is more than two times higher than that for the catalysts without Pd. The key intermediates, including *CO2-, *CO, and *OH, have been directly identified under CO2RR conditions, and their evolution with the electrochemical environments has been determined. It is found that Pd incorporation promotes the activation of both CO2 and H2O molecules and accelerates the formation of abundant active *CO and hydrogen species, thus enhancing the CH4 selectivity. This work offers fundamental insights into the understanding of the molecular mechanism of CO2RR and opens up possibilities for designing more efficient electrocatalysts.

Promotion of Dentin Biomimetic Mineralization and Bonding Efficacy by Interfacial Control of an Experimental Citric Acid Dental Etching Agent.

Resin-bonded restorations are the most important caries treatment method in clinical practice. Thus, improving the durability of dentin bonding remains a pressing issue. As a promising solution, guided tissue remineralization can induce the formation of apatite nanocrystals to repair defects in the dentin bonding interface. In this study, we present an experimental 20 wt % citric acid (CA) dental etching agent that removes the smear layer. After CA-etching, approximately 3.55 wt % residual CA formed a strong bond with collagen fibrils, reducing the interfacial energy between the remineralizing solution and dentin. CA helped achieve almost complete intrafibrillar and extrafibrillar mineralization after 24 h of mineralization. CA also significantly promoted poly(amidoamine)-induced dentin biomimetic mineralization. The elastic modulus and microhardness of remineralized dentin were restored to that of sound dentin. The remineralized interface reduced microleakage and provided a stronger, longer-lasting bond than conventional phosphate acid-etching. The newly developed CA dental etching agents promoted rapid dentin biomimetic mineralization and improved bonding efficacy through interfacial control, representing a new approach with clinical practice implications.

Synergistic Effects of TiO2 and Carbon Black for Water Evaporation-Induced Electricity Generation.

Water evaporation-induced electricity generators (WEGs) have drawn widespread attention in the field of hydrovoltaic technology, which can convert atmospheric thermal energy into sustainable electric power. However, it is restricted in the wide application of WEGs due to the low power output, complex fabrication process, and high cost. Herein, we present a simple and effective approach to fabricate TiO2-carbon black film-based WEGs (TC-WEGs). A single TC-WEG device can sustainably output an open-circuit voltage of 1.9 V and a maximum power density of 40.9 µW/cm2. Moreover, it has been shown that TC-WEGs exhibit stable electrical energy output when operating in seawater, which can yield a short-circuit current of 1.2 µA. The superior electricity generation performance can be attributed to the intrinsic characteristics of the TC-WEGs, including hydrophilicity, porous structure, and electrical conductivity. This work provides an important reference for the constant harvesting of clean energy.

Identification of Lydicamycins as Main Antioomycete Compounds from the Biocontrol Agent Streptomyces sp. NEAU-S7GS2.

Oomycetes are well-known phytopathogens that seriously threaten many important crops worldwide. In this study, the endophytic actinobacterium Streptomyces sp. NEAU-S7GS2 demonstrated significant antagonistic activity against Phytophthora and Pythium and showed a potent biocontrol effect on suppression of soybean phytophthora root rot and pepper phytophthora blight. Two compounds were subsequently isolated as the main active components by bioassay-guided fractionation and identified as lydicamycins A and B. These two compounds showed high antioomycete activity against Phytophthora and Pythium with EC50 values of 0.73-2.67 µg/mL, which are equal to or lower than those of commercialized drug metalaxyl. In vivo bioassay using detached leaves demonstrated that lydicamycin A had a better control efficiency against soybean phytophthora root rot than metalaxyl. Taken together, these results suggest that the biocontrol agent Streptomyces sp. NEAU-S7GS2 and lydicamycins have the potential to be developed as promising pesticides to control diseases caused by oomycetes.

Highly Stable Lithium Metal Batteries Enabled by Tuning the Molecular Polarity of Diluents in Localized High-Concentration Electrolytes.

Electrolyte plays a crucial role in ensuring stable operation of lithium metal batteries (LMBs). Localized high-concentration electrolytes (LHCEs) have the potential to form a robust solid-electrolyte interphase (SEI) and mitigate Li dendrite growth, making them a highly promising electrolyte option. However, the principles governing the selection of diluents, a crucial component in LHCE, have not been clearly determined, hampering the advancement of such a type of electrolyte systems. Herein, the diluents from the perspective of molecular polarity are rationally designed and developed. A moderately fluorinated solvent, 1-(1,1,2,2-tetrafluoroethoxy)propane (TNE), is employed as a diluent to create a novel LHCE. The unique molecular structure of TNE enhances the intrinsic dipole moment, thereby altering solvent interactions and the coordination environment of Li-ions in LHCE. The achieved solvation structure not only enhances the bulk properties of LHCE, but also facilitates the formation of more stable anion-derived SEIs featured with a higher proportion of inorganic species. Consequently, the corresponding full cells of both Li||LiFePO4 and Li||LiNi0.8Co0.1Mn0.1O2 cells utilizing Li thin-film anodes exhibit extended long-term stability with significantly improved average Coulombic efficiency. This work offers new insights into the functions of diluents in LHCEs and provides direction for further optimizing the LHCEs for LMBs.

Synergistic effect of ion-releasing fillers on the remineralization and mechanical properties of resin-dentin bonding interfaces.

In modern restorative dentistry, adhesive resin materials are vital for achieving minimally invasive, esthetic, and tooth-preserving restorations. However, exposed collagen fibers are found in the hybrid layer of the resin-dentin bonding interface due to incomplete resin penetration. As a result, the hybrid layer is susceptible to attack by internal and external factors such as hydrolysis and enzymatic degradation, and the durability of dentin bonding remains limited. Therefore, efforts have been made to improve the stability of the resin-dentin interface and achieve long-term clinical success. New ion-releasing adhesive resin materials are synthesized by introducing remineralizing ions such as calcium and phosphorus, which continuously release mineral ions into the bonding interface in resin-bonded restorations to achieve dentin biomimetic remineralization and improve bond durability. As an adhesive resin material capable of biomimetic mineralization, maintaining excellent bond strength and restoring the mechanical properties of demineralized dentin is the key to its function. This paper reviews whether ion-releasing dental adhesive materials can maintain the mechanical properties of the resin-dentin bonding interface by supplementing the various active ingredients required for dentin remineralization from three aspects: phosphate, silicate, and bioactive glass.

Thymic tuft cells: potential "regulators" of non-mucosal tissue development and immune response.

As the leading central immune organ, the thymus is where T cells differentiate and mature, and plays an essential regulatory role in the adaptive immune response. Tuft cells, as chemosensory cells, were first found in rat tracheal epithelial, later gradually confirmed to exist in various mucosal and non-mucosal tissues. Although tuft cells are epithelial-derived, because of their wide heterogeneity, they show functions similar to cholinergic and immune cells in addition to chemosensory ability. As newly discovered non-mucosal tuft cells, thymic tuft cells have been demonstrated to be involved in and play vital roles in immune responses such as antigen presentation, immune tolerance, and type 2 immunity. In addition to their unique functions in the thymus, thymic tuft cells have the characteristics of peripheral tuft cells, so they may also participate in the process of tumorigenesis and virus infection. Here, we review tuft cells' characteristics, distribution, and potential functions. More importantly, the potential role of thymic tuft cells in immune response, tumorigenesis, and severe acute respiratory syndrome coronavirus 2(SARS-CoV-2) infection was summarized and discussed.

Anti-Phytophthora Activity of Halofuginone and the Corresponding Mode of Action.

Febrifugine, a natural alkaloid, exhibits specific anti-phytophthora activity; however, its mode of action is unclear. In this study, halofuginone, a synthetic derivative of febrifugine, showed significantly higher anti-phytophthora activities than those of febrifugine and the commercial drug metalaxyl against Phytophthora sojae, Phytophthora capsici, and Phytophthora infestans with effective concentration for 50% inhibition (EC50) values of 0.665, 0.673, and 0.178 µg/mL, respectively. Proline could alleviate the growth inhibition of halofuginone on P. capsici, implying that halofuginone might target prolyl-tRNA synthetase (PcPRS). The anti-phytophthora mechanism of halofuginone was then investigated by molecular docking, fluorescence titration, and enzymatic inhibition assays. The results revealed that halofuginone could bind to PcPRS and shared a similar binding site with the substrate proline. Point mutations at Glu316 and Arg345 led to 24.5 and 16.1% decreases in the enzymatic activity of PcPRS but 816.742- and 459.557-fold increases in the resistance to halofuginone, respectively. The results further confirmed that halofuginone was a competitive inhibitor of proline against PcPRS, and Glu316 and Arg345 played important roles in the binding of halofuginone and proline. Taken together, the results indicated that halofuginone is an alternative anti-phytophthora drug candidate and that PcPRS represents a potential target for the development of new pesticides.

Older Adults' Health Care Utilization a Year After Experiencing Fear or Distress from Hurricane Sandy.

OBJECTIVE: To determine whether self-reports of disaster-related psychological distress predict older adults' health care utilization during the year after Hurricane Sandy, which hit New Jersey on October 29, 2012. METHODS: Respondents were from the ORANJ BOWL Study, a random-digit dialed sample from New Jersey recruited from 2006 to 2008. Medicare hospital, emergency department (ED) and outpatient claims data from 2012 and 2013 were matched to 1607 people age 65 and older in 2012 who responded to follow-up surveys conducted from July 2013 to July 2015 to determine their hurricane-related experiences. RESULTS: In total, 7% (107) of respondents reported they experienced a lot versus 93% (1493) respondents reported they experienced little or no fear and distress from Hurricane Sandy. Those who experienced a lot versus little or no fear and distress had higher probability of all-cause hospital admissions and more ED visits through 3 months (hazard ratio [HR]: 2.19, 95% CI: 1.03-4.63; incidence ratio [IR]: 2.57, 95% CI: 1.21-5.35), and ED and outpatient visits (IR: 2.20, 95% CI: 1.44-3.37; IR: 1.37, 95% CI: 1.02-1.87) through the year after the hurricane. CONCLUSIONS: A self-reported assessment of disaster-related psychological distress is a strong predictor of older adults' health care needs the year after the disaster. The results indicate that disaster preparedness should extend beyond acute health care needs to address longer-term health consequences of disasters. (Disaster Med Public Health Preparedness. 2018;12:578-581).

Preoperative Sleep Disruption and Postoperative Delirium.

STUDY OBJECTIVES: To describe preoperative and postoperative sleep disruption and its relationship to postoperative delirium. DESIGN: Prospective cohort study with 6 time points (3 nights pre-hospitalization and 3 nights post-surgery). SETTING: University medical center. PATIENTS: The sample consisted of 50 English-speaking patients ≥ 40 years of age scheduled for major non-cardiac surgery, with an anticipated hospital stay ≥ 3 days. INTERVENTIONS: None. MEASUREMENTS AND RESULTS: Sleep was measured before and after surgery for a total of 6 days using a wrist actigraph to quantify movement in a continuous fashion. Postoperative delirium was measured by a structured interview using the Confusion Assessment Method. Sleep variables for patients with (n = 7) and without (n = 43) postoperative delirium were compared using the unpaired Student t-tests or χ(2) tests. Repeated measures analysis of variance for the 6 days was used to examine within-subject changes over time and between group differences. The mean age of the patients was 66 ± 11 years (range 43-91 years), and it was not associated with sleep variables or postoperative delirium. The incidence of postoperative delirium observed during any of the 3 postoperative days was 14%. For the 7 patients who subsequently developed postoperative delirium, wake after sleep onset (WASO) as a percentage of total sleep time was significantly higher (44% ± 22%) during the night before surgery compared to the patients who did not subsequently developed delirium (21% ± 20%, p = 0.012). This sleep disruption continued postoperatively, and to a greater extent, for the first 2 nights after surgery. Patients with WASO < 10% did not experience postoperative delirium. Self-reported sleep disturbance did not differ between patients with vs. without postoperative delirium. CONCLUSIONS: In this pilot study of adults over 40 years of age, sleep disruption was more severe before surgery in the patients who experienced postoperative delirium. A future larger study is necessary to confirm our results and determine if poor sleep is associated with delirium in larger samples and what specific sleep problems best predict postoperative delirium in older surgical patients.