The adsorption and electrooxidation of CO molecules at well‐defined Pt(hkl) single‐crystal electrode surfaces is a key step towards addressing catalyst poisoning mechanisms in fuel cells. Herein, we ...employed in situ electrochemical shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) coupled with theoretical calculation to investigate CO electrooxidation on Pt(hkl) surfaces in acidic solution. We obtained the Raman signal of top‐ and bridge‐site adsorbed CO* molecules on Pt(111) and Pt(100). In contrast, on Pt(110) surfaces only top‐site adsorbed CO* was detected during the entire electrooxidation process. Direct spectroscopic evidence for OH* and COOH* species forming on Pt(100) and Pt(111) surfaces was afforded and confirmed subsequently via isotope substitution experiments and DFT calculations. In summary, the formation and adsorption of OH* and COOH* species plays a vital role in expediting the electrooxidation process, which relates with the pre‐oxidation peak of CO electrooxidation. This work deepens knowledge of the CO electrooxidation process and provides new perspectives for the design of anti‐poisoning and highly effective catalysts.
CO electrooxidation on Pt(hkl) surfaces in acidic solution has been investigated using in situ shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS). Direct spectroscopic evidence for OH* and COOH* species was observed and further confirmed by deuterium isotopic experiments and DFT calculations.
All molecules consist of chemical bonds, and much can be learned from mapping the spatiotemporal dynamics of these bonds. Since its invention a decade ago, stimulated Raman scattering (SRS) ...microscopy has become a powerful modality for imaging chemical bonds with high sensitivity, resolution, speed and specificity. We introduce the fundamentals of SRS microscopy and review innovations in SRS microscopes and imaging probes. We highlight examples of exciting biological applications, and share our vision for potential future breakthroughs for this technology.
Layered double hydroxides (LDHs) are a class of functional anionic clays, which consist of positively charged host layers (brucite‐like M(OH)6 octahedra) and interlayer anions. By virtue of their ...unique combination of structural features (including the tunability of both host layers and interlayer guest anion, exfoliation property, structure topological transformation, confinement effect), LDHs have many potential applications in heterogeneous catalysis—as catalysts themselves, catalyst supports, or catalyst precursors. In addition, the properties of LDH‐based catalysts can be tailored for specific purposes by facile modulation of their surface/interface defect structure (e.g., oxygen vacancy defects or metal defects), controlling the concentration/strength of surface acid/base sites, tuning the geometric/electronic structure of active sites, or by taking advantage of the confinement effect intrinsic to 2D materials. In addition, by utilizing the topological structural transformation of LDH precursors, supported metal catalysts can be obtained (as single metals, bimetallic alloys or heterostructures, and intermetallic compounds) with tunable particle size/morphology and intriguing electronic properties. The main focus of this review is on recent advances in structure design, preparation, and catalytic applications of LDH‐based heterogeneous catalysts. In addition, future challenges and development strategies are discussed from the viewpoints of modulation of intrinsic active sites and establishment of scalable fabrication processes.
By virtue of the unique structural merits of layered double hydroxides (LDHs) (e.g., tunability of both host layers and interlayer guest anion, exfoliation property, structure topological transformation, confinement effect), LDHs show extensive applications as catalysts, supports, or catalyst precursors (e.g., single‐metal, bimetallic alloy or heterostructure, and intermetallic compounds) in heterogeneous catalysis.
Breast cancer is an all too common disease in women, making how to effectively predict it an active research problem. A number of statistical and machine learning techniques have been employed to ...develop various breast cancer prediction models. Among them, support vector machines (SVM) have been shown to outperform many related techniques. To construct the SVM classifier, it is first necessary to decide the kernel function, and different kernel functions can result in different prediction performance. However, there have been very few studies focused on examining the prediction performances of SVM based on different kernel functions. Moreover, it is unknown whether SVM classifier ensembles which have been proposed to improve the performance of single classifiers can outperform single SVM classifiers in terms of breast cancer prediction. Therefore, the aim of this paper is to fully assess the prediction performance of SVM and SVM ensembles over small and large scale breast cancer datasets. The classification accuracy, ROC, F-measure, and computational times of training SVM and SVM ensembles are compared. The experimental results show that linear kernel based SVM ensembles based on the bagging method and RBF kernel based SVM ensembles with the boosting method can be the better choices for a small scale dataset, where feature selection should be performed in the data pre-processing stage. For a large scale dataset, RBF kernel based SVM ensembles based on boosting perform better than the other classifiers.
1,2,3,5-Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) is a typical donor-acceptor fluorophore, with carbazolyl as an electron donor and dicyanobenzene as an electron acceptor. It has emerged as ...a powerful organophotocatalyst since 2016. Excellent redox window, good chemical stability and broad applicability make 4CzIPN an attractive metal-free photocatalyst. In this review, the recent advances of the application of 4CzIPN as a photoredox catalyst in the past three years (2016-2018) for various organic reactions are summarized.
In this review, the recent advances of the application of 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) as a photoredox catalyst in the past three years (2016-2018) for various organic reactions are summarized.
We used the Immunochip array to analyze 2,816 individuals with juvenile idiopathic arthritis (JIA), comprising the most common subtypes (oligoarticular and rheumatoid factor-negative polyarticular ...JIA), and 13,056 controls. We confirmed association of 3 known JIA risk loci (the human leukocyte antigen (HLA) region, PTPN22 and PTPN2) and identified 14 loci reaching genome-wide significance (P < 5 × 10(-8)) for the first time. Eleven additional new regions showed suggestive evidence of association with JIA (P < 1 × 10(-6)). Dense mapping of loci along with bioinformatics analysis refined the associations to one gene in each of eight regions, highlighting crucial pathways, including the interleukin (IL)-2 pathway, in JIA disease pathogenesis. The entire Immunochip content, the HLA region and the top 27 loci (P < 1 × 10(-6)) explain an estimated 18, 13 and 6% of the risk of JIA, respectively. In summary, this is the largest collection of JIA cases investigated so far and provides new insight into the genetic basis of this childhood autoimmune disease.
Summary
Aims
Baicalin (BAI), a flavonoid compound isolated from the root of Scutellaria baicalensis Georgi, has been established to have potent anti‐inflammation and neuroprotective properties; ...however, its effects during Alzheimer's disease (AD) treatment have not been well studied. This study aimed to investigate the effects of BAI pretreatment on cognitive impairment and neuronal protection against microglia‐induced neuroinflammation and to explore the mechanisms underlying its anti‐inflammation effects.
Methods
To determine whether BAI plays a positive role in ameliorating the memory and cognition deficits in APP (amyloid beta precursor protein)/PS1 (presenilin‐1) mice, behavioral experiments were conducted. We assessed the effects of BAI on microglial activation, the production of proinflammatory cytokines, and neuroinflammation‐mediated neuron apoptosis in vivo and in vitro using Western blot, RT‐PCR, ELISA, immunohistochemistry, and immunofluorescence. Finally, to elucidate the anti‐inflammation mechanisms underlying the effects of BAI, the protein expression of NLRP3 inflammasomes and the expression of proteins involved in the TLR4/NF‐κB signaling pathway were measured using Western blot and immunofluorescence.
Results
The results indicated that BAI treatment attenuated spatial memory dysfunction in APP/PS1 mice, as assessed by the passive avoidance test and the Morris water maze test. Additionally, BAI administration effectively decreased the number of activated microglia and proinflammatory cytokines, as well as neuroinflammation‐mediated neuron apoptosis, in APP/PS1 mice and LPS (lipopolysaccharides)/Aβ‐stimulated BV2 microglial cells. Lastly, the molecular mechanistic study revealed that BAI inhibited microglia‐induced neuroinflammation via suppression of the activation of NLRP3 inflammasomes and the TLR4/NF‐κB signaling pathway.
Conclusion
Overall, the results of the present study indicated that BAI is a promising neuroprotective compound for use in the prevention and treatment of microglia‐mediated neuroinflammation during AD progression.
Pre-compacted bentonite bricks are often considered as sealing/backfill elements in deep geological repositories for high level radioactive waste. A good understanding of their microstructure changes ...upon hydration is essential as the microstructure changes are directly related to the macroscopic hydro-mechanical behaviour. In this study, the microstructure features of the compacted MX80 bentonite used as a sealing material in a field experiment were characterized by means of both mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Emphasis was put on the effects of final dry density (density after swelling) and hydration time. The results obtained show that the changes in soil porosity upon swelling are mainly due to the increase in large-pores of about 50µm diameter and medium-pores of 1µm diameter. In addition, the microstructure changed over time due to the water re-distribution that occurred among each level of pores: the volume of both the large-pores and small-pores decreased along as the volume of the medium-pores increased. A uniform microstructure can be then expected in the long term. Furthermore, it was observed that the higher the final dry density, the slower the microstructure changes.
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