Improving strength and toughness of graphene film through metal ion bridging.

The fangs, jaws, and mandibles of marine invertebrates such as Chiton and Glycera show excellent mechanical properties, which are mostly contributed to the interactions between metal (Fe, Cu, Zn, etc.) and oxygen-containing functional groups in proteins. Inspired by these load-bearing skeletal biomaterials, we improved tensile strength and toughness of graphene films through bridging graphene oxide (GO) nanosheets by metal ions. By optimizing the metal coordination form and density of cross-linking network. We revealed the relationship between mechanical properties and the unique spatial geometry of the GO nanosheets bridged by different valence metal ions. The results demonstrated that the divalent metal ions form tetrahedral geometry with carboxylate groups on the edges of the GO nanosheets, and the bond energy is relatively low, which is helpful for improving the toughness of resultant graphene films. While the trivalent metal ions are easily to form octahedral geometry with the GO nanosheets with higher bond energy, which is better for enhancing the tensile strength of graphene films. After reduction, the reduced GO (rGO) film bridged by divalent metal ions shows 43% improvement in toughness, while the rGO film bridged by trivalent metal ions shows 64% improvement in tensile strength. Our work reveals the mechanism of metal coordination bond energy and spatial geometry to improve the mechanical properties of graphene films, which lays a theoretical foundation for improving the tensile strength and toughness of resultant graphene films, and provides an avenue for fabricating high-performance graphene films and other two-dimensional nanocomposites.

Water Radiocatalysis for Selective Aqueous-Phase Methane Carboxylation with Carbon Dioxide into Acetic Acid at Room Temperature.

Methane (CH4) carboxylation with carbon dioxide (CO2) into acetic acid (CH3COOH) is an ideal chemical reaction to utilize both greenhouse gases with 100% atom efficiency but remains a great challenge under mild conditions. Herein, we introduce a concept of water (H2O) radiocatalysis for efficient and selective aqueous-phase CH4 carboxylation with CO2 into CH3COOH at room temperature. H2O radiolysis occurs under γ-ray radiation to produce ·OH radicals and hydrated electrons that efficiently react with CH4 and CO2, respectively, to produce ·CH3 radicals and ·CO2- species facilely coupling to produce CH3COOH. CH3COOH selectivity as high as 96.9 and 96.6% calculated respectively from CH4 and CO2 and a CH3COOH production rate of as high as 121.9 µmol·h-1 are acquired. The water radiocatalysis driven by γ-rays is also applicable to selectively produce organic acids from other hydrocarbons and CO2.

High quantum efficiency of hydrogen production from methanol aqueous solution with PtCu-TiO2 photocatalysts.

Methanol with 12.5 wt% H2 content is widely considered a liquid hydrogen medium. Taking into account water with 11.1 wt% H2 content, H2 synthesis from the mixture of water and methanol is a promising method for on-demand hydrogen production. We demonstrate an atomic-level catalyst design strategy using the synergy between single atoms and nanodots for H2 production. The PtCu-TiO2 sandwich photocatalyst achieves a remarkable H2 formation rate (2,383.9 µmol h-1) with a high apparent quantum efficiency (99.2%). Furthermore, the oxidation product is a high-value chemical formaldehyde with 98.6% selectivity instead of CO2, leading to a nearly zero-carbon-emission process. Detailed investigations indicate a dual role of the copper atoms: an electron acceptor to facilitate photoelectron transfer to Pt, and a hole acceptor for the selective oxidation of methanol to formaldehyde, thus avoiding over-oxidation to CO2. The synergy between Pt nanodots and Cu single atoms together reduces the activation energy of this process to 13.2 kJ mol-1.

Factors influencing the fate of chemical food safety hazards in the terrestrial circular primary food production system-A comprehensive review.

Food safety is recognized as a major hurdle in the transition toward circular food production systems due to the potential reintroduction and accumulation of chemical contaminants in these food systems. Effectively managing these hazardous contaminants in a risk-based manner requires quantitative insights into the factors influencing the presence and fate of contaminants in the entire circular food chain. A systematic literature review was performed to gain an up-to-date overview of the known factors and their influence on the transfer and accumulation of contaminants. This review focused on the terrestrial circular primary food production system, including the pathways between waste- or byproduct-based fertilizers, soil, crops, animal feed, and farmed animals. This review revealed an imbalance in research regarding the different pathways: studies on the soil-to-crop pathway were most abundant. The factors identified can be categorized as compound-related (intrinsic) factors, such as hydrophobicity, molecular weight, and chain length, and extrinsic factors, such as soil organic matter and carbon, pH, milk yield of cows, crop age, and biomass. Quantitative data on the influence of the identified factors were limited. Most studies quantified the influence of individual factors, whereas only a few studies quantified the combined effect of multiple factors. By providing a holistic insight into the influential factors and the quantification of their influence on the fate of contaminants, this review contributes to the improvement of food safety management for chemical hazards when transitioning to a circular food system.

γ-Ray Driven Aqueous-Phase Methane Conversions into Complex Molecules up to Glycine.

Fundamental understanding of initial evolutions of molecules in the universe is of great interest and importance. CH4 is one of the abundant simple molecules in the universe. Herein we report γ-ray, high-energy photons commonly existing in cosmic rays and unstable isotope decay, as an external energy to efficiently drives aqueous-phase CH4 conversions to various products with the presence of oxygen at room temperature. Glycine also forms with an additional introduction of ammonia. Both CH4 conversions and product distributions are modified by solid granules, and a CH3COOH selectivity as high as 82% is obtained when SiO2 is added. Our results point to γ-ray driven aqueous-phase CH4 conversions as a likely formation network of initial complex organic compounds in the universe and offer an alternative strategy for efficiently utilizing CH4 as the carbon source to produce value-added products at mild conditions, a long-standing challenging task in heterogeneous catalysis.

Direct Probing of Water Adsorption on Liquid-Phase Exfoliated WS2 Films Formed by the Langmuir-Schaefer Technique.

Tungsten disulfide, a transition metal dichalcogenide, has numerous applications as active components in gas- and chemical-sensing devices, photovoltaic sources, photocatalyst substrates, etc. In such devices, the presence of water in the sensing environment is a factor whose role has not been well-understood. To address this problem, the in situ probing of H2O molecule adsorption on WS2 films supported on solid substrates has been performed in a near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) setup. Instead, on the individual nanoflakes or spray-coated samples, the measurements were performed on highly transparent, homogeneous, thin films of WS2 nanosheets self-assembled at the interface of two immiscible liquids, water and toluene, transferred onto a solid substrate by the Langmuir-Schaefer technique. This experiment shows that edge defects in nanoflakes, tungsten dangling bond ensuing the exfoliation in the liquid phase, represent active sites for the WO3, WO3-x, and WO3·nH2O formation under ambient conditions. These oxides interact with water molecules when the WS2 films are exposed to water vapor in the NAP-XPS reaction cell. However, water molecules do not influence the W-S chemical bond, thus indicating the physisorption of H2O molecules at the WS2 film surface.

Aloin antagonizes stimulated ischemia/reperfusion-induced damage and inflammatory response in cardiomyocytes by activating the Nrf2/HO-1 defense pathway.

Myocardial ischemia/reperfusion injury (I/RI) frequently incurs in acute myocardial infarction with high morbidity and mortality worldwide and is characterized with cardiomyocyte apoptosis and inflammatory response. Aloin is a major anthraquinone from Aloe species and fulfills pleiotropic protective functions in several disease models including hepatic injury. Nevertheless, the potential of aloin in MI/RI remains elusive. Intriguingly, aloin had modest cytotoxicity in H9c2 cardiomyocytes. Importantly, aloin dose-dependently ameliorated cell viability that was inhibited in response to simulated ischemia/reperfusion (SI/R) stimulation. Moreover, the enhanced apoptosis in cells under SI/R conditions were reduced after aloin treatment, concomitant with the decrease in pro-apoptotic Bax protein levels and increase in anti-apoptotic Bcl-2 protein expression. Of interest, aloin administration attenuated SI/R-induced oxidant stress by decreasing reactive oxygen species (ROS) production, lactate dehydrogenase (LDH), and malondialdehyde (MDA) release and increasing activity of anti-oxidant stress enzyme superoxide dismutase (SOD). Additionally, the elevated pro-inflammatory cytokine levels were counteracted after aloin treatment in cells under SI/R conditions, including TNF-α, IL-6, and IL-1ß. Mechanically, aloin further enforced the activation of the NF-E2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling. Noticeably, blockage of this pathway by si-Nrf2 transfection blunted aloin-mediated cardioprotective efficacy against SI/R-evoked oxidative stress injury and inflammatory response. Thus, these findings corroborate that aloin may antagonize SI/R-induced cardiomyocyte injury by attenuating excessive oxidative stress and inflammation, thereby endorsing its potential as a promising therapeutic agent against myocardial infarction.

Interaction of Hydrogen with Ceria: Hydroxylation, Reduction, and Hydride Formation on the Surface and in the Bulk.

The study reports the first attempt to address the interplay between surface and bulk in hydride formation in ceria (CeO2 ) by combining experiment, using surface sensitive and bulk sensitive spectroscopic techniques on the two sample systems, i.e., CeO2 (111) thin films and CeO2 powders, and theoretical calculations of CeO2 (111) surfaces with oxygen vacancies (Ov ) at the surface and in the bulk. We show that, on a stoichiometric CeO2 (111) surface, H2 dissociates and forms surface hydroxyls (OH). On the pre-reduced CeO2-x samples, both films and powders, hydroxyls and hydrides (Ce-H) are formed on the surface as well as in the bulk, accompanied by the Ce3+ ↔ Ce4+ redox reaction. As the Ov concentration increases, hydroxyl is destabilized and hydride becomes more stable. Surface hydroxyl is more stable than bulk hydroxyl, whereas bulk hydride is more stable than surface hydride. The surface hydride formation is the kinetically favorable process at relatively low temperatures, and the resulting surface hydride may diffuse into the bulk region and be stabilized therein. At higher temperatures, surface hydroxyls can react to produce water and create additional oxygen vacancies, increasing its concentration, which controls the H2 /CeO2 interaction. The results demonstrate a large diversity of reaction pathways, which have to be taken into account for better understanding of reactivity of ceria-based catalysts in a hydrogen-rich atmosphere.

Structure Sensitivity of Au-TiO2 Strong Metal-Support Interactions.

Strong metal-support interactions (SMSI) is an important concept in heterogeneous catalysis. Herein, we demonstrate that the Au-TiO2 SMSI of Au/TiO2 catalysts sensitively depends on both Au nanoparticle (NP) sizes and TiO2 facets. Au NPs of ca. 5 nm are more facile undergo Au-TiO2 SMSI than those of ca. 2 nm, while TiO2 {001} and {100} facets are more facile than TiO2 {101} facets. The resulting capsulating TiO2-x overlayers on Au NPs exhibit an average oxidation state between +3 and +4 and a Au-to-TiO2-x charge transfer, which, combined with calculations, determines the Ti:O ratio as ca. 6:11. Both TiO2-x overlayers and TiO2-x -Au interface exhibit easier lattice oxygen activation and higher intrinsic activity in catalyzing low-temperature CO oxidation than the starting Au-TiO2 interface. These results advance fundamental understanding of SMSI and demonstrate engineering of metal NP size and oxide facet as an effective strategy to tune the SMSI for efficient catalysis.

A General Approach for Monolayer Adsorption of High Weight Loadings of Uniform Nanocrystals on Oxide Supports.

Monodispersed metal and semiconductor nanocrystals have attracted great attention in fundamental and applied research due to their tunable size, morphology, and well-defined chemical composition. Utilizing these nanocrystals in a controllable way is highly desirable especially when using them as building blocks for the preparation of nanostructured materials. Their deposition onto oxide materials provide them with wide applicability in many areas, including catalysis. However, so far deposition methods are limited and do not provide control to achieve high particle loadings. This study demonstrates a general approach for the deposition of hydrophobic ligand-stabilized nanocrystals on hydrophilic oxide supports without ligand-exchange. Surface functionalization of the supports with primary amine groups either using an organosilane ((3-aminopropyl)trimethoxysilane) or bonding with aminoalcohols (3-amino-1,2-propanediol) were found to significantly improve the interaction between nanocrystals and supports achieving high loadings (>10 wt. %). The bonding method with aminoalcohols guarantees the opportunity to remove the binding molecules thus allowing clean metal/oxide materials to be obtained, which is of great importance in the preparation of supported nanocrystals for heterogeneous catalysis.

Site Sensitivity of Interfacial Charge Transfer and Photocatalytic Efficiency in Photocatalysis: Methanol Oxidation on Anatase TiO2 Nanocrystals.

Photocatalytic oxidation of methanol on various anatase TiO2 nanocrystals was studied by in situ and time-resolved characterizations and DFT calculations. Surface site and resulting surface adsorbates affect the surface band bending/bulk-to-surface charge migration processes and interfacial electronic structure/interfacial charge transfer processes. TiO2 nanocrystals predominantly enclosed by the {001} facets expose a high density of reactive fourfold-coordinated Ti sites (Ti4c ) at which CH3 OH molecules dissociate to form the CH3 O adsorbate (CH3 O(a)Ti4c ). CH3 O(a)Ti4c localized density of states are almost at the valence band maximum of TiO2 surface, facilitating the interfacial hole transfer process; CH3 O(a)Ti4c with a high coverage promotes upward surface band bending, facilitating bulk-to-surface hole migration. CH3 O(a)Ti4c exhibits the highest photocatalytic oxidation rate constant. TiO2 nanocrystals enclosed by the {001} facets are most active in photocatalytic methanol oxidation.

Electronic Oxide-Metal Strong Interaction (EOMSI).

Strong metal-support interaction of supported metal catalysts is an important concept to describe the effect of metal-support interactions on the structures and catalytic performances of supported metal particles. By using an example of CeOx adlayers supported on Ag nanocrystals, herein a concept of electronic oxide-metal strong interaction (EOMSI) is put forward; this interaction significantly affects the electronic structures of oxide adlayers through metal-to-oxide charge transfer. The EOMSI can stabilize oxide adlayers in a low oxidation state under ambient conditions, which individually are not stable; moreover, the oxide adlayers experiencing the EOMSI are resistant to high-temperature oxidation in air to a certain extent. Such an EOMSI concept helps to generalize the strong influence of oxide-metal interactions on the structures and catalytic performance of oxide/metal inverse catalysts, which have been attracting increasing attention.

High-Temperature Synthesis of Small-Sized Pt/Nb Alloy Catalysts on Carbon Supports for Hydrothermal Reactions.

Catalytic biomass conversions are sustainable processes to produce value-added fuels and chemicals but need stable catalysts that can tolerate harsh hydrothermal conditions. Herein, we report a hydrothermally stable catalyst by alloying Pt with a high-melting-point metal Nb. The Pt/Nb alloy catalysts are prepared by H2 reduction at a high temperature of 900 °C with a high-surface-area carbon black support, which can suppress metal sintering at high temperatures and thus lead to small-sized alloyed Pt/Nb particles of only 2.2 nm. Taking the advantages of surface acid property provided by the Nb sites and the size effect, the prepared C-supported small-sized Pt/Nb alloy catalysts exhibit attractive activities for the hydrogenation of levulinic acid into γ-valerolactone and the water-gas shift reaction. More significantly, benefiting from the inherent stability of high-melting-point Nb, the Pt/Nb alloy catalysts show much enhanced hydrothermal stability compared to commercial Pt/C and Ru/C catalysts.

Surface chemistry of TiO2 connecting thermal catalysis and photocatalysis.

Chemical reactions catalyzed under heterogeneous conditions have recently expanded rapidly from traditional thermal catalysis to photocatalysis due to the rising concerns about sustainable development of energy and the environment. Adsorption of reactants on catalyst surfaces, subsequent surface reactions, and desorption of products from catalyst surfaces occur in both thermal catalysis and photocatalysis. TiO2 catalysts are widely used in thermal catalytic and photocatalytic reactions. Herein we review recent progress in surface chemistry, thermal catalysis and photocatalysis of TiO2 model catalysts from single crystals to nanocrystals with the aim of examining if the surface chemistry of TiO2 can bridge the fundamental understanding between thermal catalysis and photocatalysis. Following a brief introduction, the structures of major facets exposed on TiO2 catalysts, including surface reconstructions and defects, as well as the electronic structure and charge properties, are firstly summarized; then the recent progress in adsorption, thermal chemistry and photochemistry of small molecules on TiO2 single crystals and nanocrystals is comprehensively reviewed, focusing on manifesting the structure-(photo)activity relations and the commonalities/differences between thermal catalysis and photocatalysis; and finally concluding remarks and perspectives are given.

Surface chemistry and photochemistry of small molecules on rutile TiO2(001) and TiO2(011)-(2 × 1) surfaces: The crucial roles of defects.

Surface chemistry and photochemistry of small molecules on the rutile TiO2(001) and TiO2(011)-(2 × 1) surfaces were studied by low energy electron diffraction, thermal desorption spectroscopy, and x-ray photoelectron spectroscopy. It was found that the TiO2(001) surface mainly exhibits the defects of Ti interstitials in the near-surface region, while the TiO2(011)-(2 × 1) surface mainly exhibits the defects of double-oxygen vacancies. The defect structures of TiO2 surfaces strongly affect their adsorption and thermal/photodesorption behaviors. On the TiO2(001) surface, CH3OH and H2O dissociatively adsorb at the surface Ti sites near Ti interstitials; O2 molecularly adsorbs at the surface Ti sites adjacent to Ti interstitials, forming photoactive O2 species that undergoes a hole-mediated photodesorption process; CO adsorbs at the nearest surface Ti sites close to the Ti interstitials, but CO2 does not, and the resulting CO species is photoactive; and both CO and CO2 species adsorbed at the normal Ti4+ sites are photoinactive. On the TiO2(011)-(2 × 1) surface, O2 adsorbs only at the double-oxygen vacancy sites, and the resulting O2 species dissociates to form two oxygen atoms to refill in the oxygen vacancies upon heating; CO2 adsorbs at the double-oxygen vacancy sites, but CO does not, and the resulting CO2 species is photoactive; and both CO and CO2 species adsorbed at the surface Ti4+ sites are photoinactive. These results broaden the fundamental understandings of the chemistry and photochemistry of TiO2 surfaces, and the established structure-reactivity relation of small molecules on TiO2 surfaces is useful in probing complex structures of TiO2 powder catalysts.

MiR-224 Executes a Tumor Accelerative Role during Hepatocellular Carcinoma Malignancy by Targeting Cytoplasmic Polyadenylation Element-Binding Protein 3.

PURPOSE: The purpose of our study was to probe the mechanism of how miR-224/cytoplasmic polyadenylation element-binding protein 3 (CPEB3) axis is concerned with hepatocellular carcinoma (HCC). METHODS: The expressions and prognostic values of miR-224 and CPEB3 in HCC patients were analyzed based on the data acquired from the TCGA and GEO databases. qRT-PCR was conducted to test the mRNA expression levels of miR-224 and CPEB3. The expression level of miR-224 in SMMC-7721/HuH-7 cells was up-/downregulated by miR-224 mimic/inhibitor to explore its influence on HCC cell proliferation and motility by utilizing CCK8 and transwell assays, respectively. Luciferase activity assay was applied for verifying the target of miR-224. The relationship between miR-224 and CPEB3 was analyzed utilizing Pearson's correlation coefficient. The protein level of CPEB3 was tested by Western blotting. Rescue assay was performed to determine whether CPEB3 involved in the process of HCC cell phenotype changes caused by miR-224 alteration. RESULTS: MiR-224 was highly expressed and CPEB3 was lowly expressed in HCC tissues. Besides, the high expression of miR-224 and low expression of CPEB3 were correlated with worse prognosis in HCC patients. Up-/downregulation of miR-224 accelerated/restrained SMMC-7721/HuH-7 cell proliferation and motility. CPEB3 was predicted and proofed as a target gene of miR-224. We discovered that CPEB3 was negatively modulated by miR-224. We also found a sharply negative correlation between CPEB3 and miR-224. Using rescue assay, we showed that overexpression of CPEB3 suppressed the proliferation and motility of SMMC-7721 cells with overexpressed miR-224, while knockdown of CPEB3 facilitated the proliferation and motility of HuH-7 cells with downregulated miR-224. CONCLUSION: Our data provided evidences that miR-224 is implicated in HCC cell proliferation and motility via targeting CPEB3. The relationship between miR-224 and CPEB3 might be a novel finding, and miR-224/CPEB3 axis might be markers for providing therapeutic and prognostic information in HCC.

Relaxation techniques for depressive disorders in adults: a systematic review and meta-analysis of randomised controlled trials.

Objectives: The aim of this study was to identify, evaluate, and synthesise existing randomised controlled trials (RCTs) that examined the effect of relaxation techniques in the treatment of patients with depressive disorders.Methods: A systematic review of the literature was performed based on the Preferred Reporting Items for Systematic Reviews and Meta-analysis guidelines.Results: Nine studies were finally included in this meta-analysis. It was found that relaxation techniques might effectively reduce depressive symptoms among adults with depression (standardised mean difference (SMD) -0.42, 95% CI -0.72 to -0.11, p = 0.008).Conclusions: Relaxation techniques are cost-effective, safe, and low-risk techniques that can be easily taught and used. Consequently, they have several benefits if practised regularly daily for more than an 8-week period.KEY POINTS/HIGHLIGHTSThe implication of this study for practice is that these relaxation techniques, cost-effective, safe, and low-risk techniques that can be easily taught and used.Consequently, practitioners will access benefits if practised regularly daily for more than an 8-week period.The relaxation technique is not complex, does not need any special device or place, does not need any change in lifestyle and is easily learned.

Radical Chemistry and Reaction Mechanisms of Propane Oxidative Dehydrogenation over Hexagonal Boron Nitride Catalysts.

Although hexagonal boron nitride (h-BN) has recently been identified as a highly efficient catalyst for the oxidative dehydrogenation of propane (ODHP) reaction, the reaction mechanisms, especially regarding radical chemistry of this system, remain elusive. Now, the first direct experimental evidence of gas-phase methyl radicals (CH3 . ) in the ODHP reaction over boron-based catalysts is achieved by using online synchrotron vacuum ultraviolet photoionization mass spectroscopy (SVUV-PIMS), which uncovers the existence of gas-phase radical pathways. Combined with density functional theory (DFT) calculations, the results demonstrate that propene is mainly generated on the catalyst surface from the C-H activation of propane, while C2 and C1 products can be formed via both surface-mediated and gas-phase pathways. These observations provide new insights towards understanding the ODHP reaction mechanisms over boron-based catalysts.

Thermal Emitting Strategy to Synthesize Atomically Dispersed Pt Metal Sites from Bulk Pt Metal.

Developing a facile route to access active and well-defined single atom sites catalysts has been a major area of focus for single atoms catalysts (SACs). Herein, we demonstrate a simple approach to generate atomically dispersed platinum via a thermal emitting method using bulk Pt metal as a precursor, significantly simplifying synthesis routes and minimizing synthesis costs. The ammonia produced by pyrolysis of Dicyandiamide can coordinate with platinum atoms by strong coordination effect. Then, the volatile Pt(NH3) x can be anchored onto the surface of defective graphene. The as-prepared Pt SAs/DG exhibits high activity for the electrochemical hydrogen evolution reaction and selective oxidation of various organosilanes. This viable thermal emitting strategy can also be applied to other single metal atoms, for example, gold and palladium. Our findings provide an enabling and versatile platform for facile accessing SACs toward many industrial important reactions.

Electronic Metal-Support Interaction-Modified Structures and Catalytic Activity of CeOx Overlayers in CeOx /Ag Inverse Catalysts.

Electronic metal-support interactions (EMSIs) of oxide-supported metal catalysts strongly modifies the electronic structures of the supported metal nanoparticles. The strong influence of EMSIs on the electronic structures of oxide overlayers on metal nanoparticles employing cerium oxides/Ag inverse catalysts is reported herein. Ce2 O3 overlayers were observed to exclusively form on Ag nanocrystals at low cerium loadings and be resistant to oxidation treatments up to 250 °C, whereas CeO2 overlayers gradually developed as the cerium loading increased. Ag cubes enclosed by {001} facets with a smaller work function exert a stronger EMSI effect on the CeOx overlayers than Ag cubes enclosed by {111} facets. Only the CeO2 overlayers with a fully developed bulk CeO2 electronic structure significantly promote the catalytic activity of Ag nanocrystals in CO oxidation, whereas cerium oxide overlayers with other electronic structures do not. These results successfully extend the concept of EMSIs from oxide-supported metal catalysts to metal-supported oxide catalysts.