Solar-Driven Reforming of Methane and Nitrogen to Methanol and Ammonium on Iron-Modified Zeolite under Ambient Conditions in Water.

Artificial photosynthesis from selective methane oxidation or nitrogen reduction to value-added chemicals provides a promising pathway for the sustainable chemical industry, while still remaining a great challenge due to the extreme difficulty in C-H and N≡N bond cleavage under ambient conditions. Catalysts that can cocatalyze these two reactions simultaneously are rarely reported. Here, Fe-ZSM-5 with highly dispersed extra-framework Fe-oxo species enables efficient and selective photocatalytic conversion of methane and nitrogen to coproduce methanol and ammonia using H2O as the redox reagent under ambient conditions. The optimized Fe-ZSM-5 photocatalyst achieves up to 0.88 mol/molFe·h of methanol products with 97% selectivity. Meanwhile, the productivity of ammonia is 0.61 mol/molFe·h. In situ EPR and DRIFT studies disclose that water serves as a redox reagent to provide hydroxyl radicals for methane oxidation and protons for nitrogen hydrogenation. Quantum chemical calculations revealed that Fe-oxo species play a significant role in the coactivation of methane and nitrogen molecules, which lowers the energy barriers of rate-determining steps for methanol and ammonia generation.

Fabrication of Flexible Mesoporous Black Nb2 O5 Nanofiber Films for Visible-Light-Driven Photocatalytic CO2 Reduction into CH4.

Achieving high selectivity and conversion efficiency simultaneously is a challenge for visible-light-driven photocatalytic CO2 reduction into CH4 . Here, a facile nanofiber synthesis method and a new defect control strategy at room-temperature are reported for the fabrication of flexible mesoporous black Nb2 O5 nanofiber catalysts that contain abundant oxygen-vacancies and unsaturated Nb dual-sites, which are efficient towards photocatalytic production of CH4 . The oxygen-vacancy decreases the bandgap width of Nb2 O5 from 3.01-2.25 eV, which broadens the light-absorption range from ultraviolet to visible-light, and the dual sites in the mesopores can easily adsorb CO2 , so that the intermediate product of CO* can be spontaneously changed into *CHO. The formation of a highly stable NbCHO* intermediate at the dual sites is proposed to be the key feature determining selectivity. The preliminary results show that without using sacrificial agents and photosensitizers, the nanofiber catalyst achieves 64.8% selectivity for CH4 production with a high evolution rate of 19.5 µmol g-1 h-1 under visible-light. Furthermore, the flexible catalyst film can be directly used in devices, showing appealing and broadly commercial applications.

MRI-based Bosniak Classification of Cystic Renal Masses, Version 2019: Interobserver Agreement, Impact of Readers' Experience, and Diagnostic Performance.

Background The 2019 Bosniak classification (version 2019) of cystic renal masses (CRMs) provides a systematic update to the currently used 2005 Bosniak classification (version 2005). Further validation is required before widespread application. Purpose To evaluate the interobserver agreement of MRI criteria, the impact of readers' experience, and the diagnostic performance between version 2019 and version 2005. Materials and Methods From January 2009 to December 2018, consecutive patients with CRM who had undergone renal MRI and surgical-pathologic examination were included in this retrospective study. On the basis of version 2019 and version 2005, all CRMs were independently classified by eight radiologists with different levels of experience. By using multirater κ statistics, interobserver agreement was evaluated with comparisons between classifications and between senior and junior radiologists. Diagnostic performance between classifications by dichotomizing classes I-IV into lower (I-IIF) and higher (III-IV) classes was compared by using the McNemar test. P < .05 was considered to indicate a statistically significant difference. Results A total of 207 patients (mean age ± standard deviation, 49 years ± 12; 139 male and 68 female patients) with CRMs were included. Overall, interobserver agreement was higher with version 2019 than version 2005 (weighted κ = 0.64 vs 0.50, respectively; P < .001). Interobserver agreement between senior and junior radiologists did not differ between version 2019 (weighted κ = 0.65 vs 0.64, respectively; P = .71) and version 2005 (weighted κ = 0.54 vs 0.46; P < .001). Diagnostic specificity for malignancy was higher with version 2019 than with version 2005 (83% [92 of 111] vs 68% [75 of 111], respectively; P < .001), without any difference in sensitivity (89% [85 of 96] vs 84% [81 of 96]; P = .34). Conclusion In the updated Bosniak classification, interobserver agreement improved and was unaffected by observers' experience. The diagnostic performance with version 2019 was superior to that with version 2005, with higher specificity. Published under a CC BY 4.0 license. Online supplemental material is available for this article. See also the editorial by Choyke in this issue.

Single-Electron-Trapped Oxygen Vacancy on Ultrathin WO3·0.33H2O {100} Facets Suppressing Backward Reaction for Promoted H2 Evolution in Pure Water Splitting.

Solar water splitting to produce hydrogen is a promising solution for global energy issues. One of the main bottlenecks in this technology is the spontaneous fast backward reaction (2H2 + O2 → H2O, Δ G < 0), limiting the solar energy conversion efficiency. How to suppress backward reaction is vitally important but rarely reported. Here we found that single-electron-trapped oxygen vacancy (Vo·) can suppress spontaneous backward reaction in pure water splitting. Taking WO3·0.33H2O catalyst as an example, ultrathin WO3·0.33H2O {100} facets with large amount of surface Vo· realized a continuous H2 evolution from pure water splitting with a productivity of 9.9 µmol/g·h without the assistance of any sacrifice agent and noble metal cocatalyst. Quantum chemical calculations revealed that the backward-reaction suppression ability of Vo· is attributed to the high concentration of localized electrons around Vo·, stimulating unidirectional simultaneous water dissociation into H and OH under light irradiation.

Ultrathin WO3·0.33H2O Nanotubes for CO2 Photoreduction to Acetate with High Selectivity.

Artificial photosynthesis from CO2 reduction is severely hampered by the kinetically challenging multi-electron reaction process. Oxygen vacancies (Vo) with abundant localized electrons have great potential to overcome this limitation. However, surface Vo usually have low concentrations and are easily oxidized, causing them to lose their activities. For practical application of CO2 photoreduction, fabricating and enhancing the stability of Vo on semiconductors is indispensable. Here we report the first synthesis of ultrathin WO3·0.33H2O nanotubes with a large amount of exposed surface Vo sites, which can realize excellent and stable CO2 photoreduction to CH3COOH in pure water under solar light. The selectivity for acetum generation is up to 85%, with an average productivity of about 9.4 µmol g-1 h-1. More importantly, Vo in the catalyst are sustainable, and their concentration was not decreased even after 60 h of reaction. Quantum chemical calculations and in situ DRIFT studies revealed that the main reaction pathway might be CO2 → •COOH → (COOH)2 → CH3COOH.

Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

Oxygen reduction reaction (ORR) for generating H2 O2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H2 O2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H2 O2 (28 µmol h-1 ) only from O2 and H2 O, which is above the average level of H2 O2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O2 and H2 O, then to form H2 O2 .

Anti-exudation effects of sodium ferulate and oxymatrine combination via modulation of aquaporin 1.

The present study aimed to investigate the anti-exudative effects of sodium ferulate combined with oxymatrine in a mouse model of acetic acid-induced peritonitis. Furthermore, the underlying mechanisms were explored by determining the effects of these drugs on the volume and aquaporin 1 (AQP1) expression in vascular endothelial cells on omentum majus and human umbilical vein endothelial cells (HUVEC). Treatment with sodium ferulate combined with oxymatrine was shown to significantly inhibit acetic acid-induced vascular permeability in the peritonitis model mice and furthermore to significantly decrease the optical density of Evans blue, the leukocyte number and the levels of interleukin-6, C-reactive protein and interferon-γ in peritoneal lavage fluid. Pathological analysis of the omentum majus revealed that sodium ferulate and oxymatrine combination treatment significantly alleviated vascular endothelial cell edema and capillary loss. In vitro, flow cytometry revealed that the volume of HUVECs was significantly reduced in the drug treatment groups, as reflected in the forward scatter value. The optical density of AQP1 on the membrane of the vascular endothelial cells on omentum majus and HUVECs were significantly increased in the drug treatment groups compared with the model group. These results indicated that sodium ferulate and oxymatrine combination treatment possessed prominent anti-exudative effects and that the underlying mechanisms are likely to include the improvement of vascular endothelial cellular edema, possibly by upregulation of AQP1 expression on their membrane, which requires further exploration.

Efficient Solar-Driven Nitrogen Fixation over Carbon-Tungstic-Acid Hybrids.

Ammonia synthesis under mild conditions is of supreme interest. Photocatalytic nitrogen fixation with water at room temperature and atmospheric pressure is an intriguing strategy. However, the efficiency of this method has been far from satisfied for industrialization, mainly due to the sluggish cleavage of the N≡N bond. Herein, we report a carbon-tungstic-acid (WO3 ⋅H2 O) hybrid for the co-optimization of N2 activation as well as subsequent photoinduced protonation. Efficient ammonia evolution reached 205 µmol g-1 h-1 over this hybrid under simulated sunlight. Nitrogen temperature-programmed desorption revealed the decisive role of carbon in N2 adsorption. Photoactive WO3 ⋅H2 O guaranteed the supply of electrons and protons for subsequent protonation. The universality of carbon modification for enhancing the N2 reduction was further verified over various photocatalysts, shedding light on future materials design for ideal solar energy utilization.

(-)-SCR1693 Protects against Memory Impairment and Hippocampal Damage in a Chronic Cerebral Hypoperfusion Rat Model.

Chronic cerebral hypoperfusion (CCH) is one of the most common causes of vascular dementia (VaD) and is recognised as an etiological factor in the development of Alzheimer's disease (AD). CCH can induce severe cognitive deficits, as assessed by the water maze task, along with neuronal loss in the hippocampus. However, there are currently no effective, approved pharmacological treatments available for VaD. In the present study, we created a rat model of CCH using bilateral common carotid artery occlusion and found that (-)-SCR1693, a novel compound, prevented rats from developing memory deficits and neuronal damage in the hippocampus by rectifying cholinergic dysfunction and decreasing the accumulation of the phospho-tau protein. These results strongly suggest that (-)-SCR1693 has therapeutic potential for the treatment of CCH-induced VaD.

Solar-Light-Driven Pure Water Splitting with Ultrathin BiOCl Nanosheets.

A suitable photocatalyst for overall water splitting has been produced by overcoming the disadvantage of the band structure in bulk BiOCl by reducing the thickness to the quantum scale. The ultrathin BiOCl nanosheets with surface/subsurface defects realized the solar-driven pure water splitting in the absence of any co-catalysts or sacrificial agent. These surface defects cannot only shift both the valence band and conduction band upwards for band-gap narrowing but also promote charge-carrier separation. The amount of defects in the outer layer surface of BiOCl results in an enhancement of carrier density and faster charge transport. First-principles calculations provide clear evidence that the formation of surface oxygen vacancies is easier for the ultrathin BiOCl nanosheets than for its thicker counterpart. These defects can serve as active sites to effectively adsorb and dissociate H2 O molecules, resulting in a significantly improved water-splitting performance.

The Protective Effect of Sodium Ferulate and Oxymatrine Combination on Paraquat-induced Lung Injury.

Experimental evidence suggested that sodium ferulate (SF) and oxymatrine (OMT) combination had synergistic anti-inflammatory and antioxidant effects. We hypothesized that SF and OMT combination treatment might have protective effects on paraquat-induced acute lung injury. In our study, the Swiss mice were randomly divided into seven groups, including control, paraquat (PQ), SF (6.2 mg/Kg/day); OMT (13.8 mg/Kg/day) and three SF+OMT groups (3.1 + 6.9; 6.2 + 13.8 and 12.3 + 27.7 mg/Kg/day). The mortality and death time were monitored. Sprague-Dawley rats were randomly divided into seven groups including control, PQ, SF (3.1 mg/Kg/day); OMT (6.9 mg/Kg/day) and three SF+OMT groups (1.6 + 3.4; 3.1 + 6.9 and 6.2 + 13.8 mg/Kg/day). The lung wet/dry weight (W/D) ratio, lung histopathologic changes, C-reactive protein (CRP), interleukin-6 (IL-6), nuclear factor κB (NF-κB), malondialdehyde (MDA) and superoxidase dismutase (SOD) were analysed. Compared with PQ group, the mortality significantly decreased and the death time prolonged in SF and OMT combination treatment groups of mice. Also in SF and OMT combination treatment groups of rats, the increased lung W/D ratio and histopathological score induced by PQ injection were significantly decreased; the levels of CRP, IL-6, NF-κB and MDA in serum and lung homogenate were significantly decreased; the SOD activities in serum and lung homogenate were improved. These results suggested that SF and OMT combination had an obvious protective effect on PQ-induced lung injury. The anti-inflammatory and antioxidant effect might be involved in the mechanism.

Protective effects of the combination of sodium ferulate and oxymatrine on cecal ligation and puncture-induced sepsis in mice.

The aim of this study was to investigate the effects of the combination of sodium ferulate (SF) and oxymatrine (OMT) on mice with cecal ligation and puncture (CLP)-induced sepsis. Swiss male mice were randomly divided into a control group, CLP group, three SF + OMT groups (3.1+6.9; 6.2+13.8 and 12.3+27.7 mg/kg), SF (6.2 mg/kg) group and OMT (13.8 mg/kg) group. Eight hours after the administration of the drugs, the survival rates and survival times of the animals were monitored. In addition, the lung wet/dry weight (W/D) ratio; alanine aminotransferase (ALT), aspartate aminotransferase (AST) and lactate dehydrogenase (LDH) levels in the serum; the C-reactive protein (CRP), interleukin-6 (IL-6) and interferon-γ (IFN-γ) levels in the serum and lung and liver homogenates; and the malondialdehyde (MDA) and superoxidase dismutase (SOD) levels in the lung and liver homogenates were measured. The bacterial load in the serum was also studied. Following treatment with the combination of SF and OMT, the survival rate increased and the survival time was prolonged; CLP-induced increases in the lung W/D ratio and the levels of ALT, AST, LDH, CRP, IL-6, IFN-γ and MDA were significantly reduced; and the SOD activity levels were increased, compared with those of the untreated animals with CLP-induced sepsis. These results indicated that the combination of SF and OMT induced protective effects against CLP-induced lethal sepsis of mice. The possible mechanism of these effects may be associated with the alleviation of systemic inflammation and diminishment of oxidative injury.

Highly selective defect-mediated photochemical CO2 conversion over fluorite ceria under ambient conditions.

A highly selective defect-mediated photochemical CO2 conversion to CO over defective CeO2 nanorods under ambient conditions (CO2 400 ppm) is presented. The local strain and surface oxygen vacancies embedded in the defect-rich CeO2 are suggested to play a decisive role in mediating the photochemical CO2 conversion.

The design and realization of a large-area flexible nanofiber-based mat for pollutant degradation: an application in photocatalysis.

This work demonstrates a novel multifunctional nanofibrous mat for photocatalytic applications based on TiO2 nanocables functionalized by Ag nanoparticles and coated with a thin (~2 nm) graphitic shell. In this mat, which was realized by an electrospinning technique, each component serves a unique function: the carbon coating acts as both an adsorption material for capturing pollutants and as a charge-transfer material, the Ag nanoparticles act as a visible-light sensitizing agent and also as a charge-transfer material, finally the TiO2 nanocable mat acts as a UV sensitive photocatalytic matrix and as the flexible substrate for the other functional components. This multicomponent nanocable mat exhibits excellent photocatalytic activity under simulated solar irradiation for the degradation of model pollutants including RhB and phenol. The significant photocatalytic properties are attributed to the synergetic effect of the three functional components and the unique charge transport "freeway" property of the nanofibrous mat. In addition, the porous carbon coating infiltrated into the nanocable matrix endows the mat with excellent flexibility and enables robust, large-area (10 × 10 cm) fabrication, representing a significant advantage over previous brittle ceramic nanofibrous mat photocatalyst substrates. This study provides new insight into the design and preparation of an advanced, yet commercially practical and scaleable photocatalytic composite membrane material. The as-prepared photocatalytic mat might also be of interest in solar cell, catalysis, separation technology, biomedical engineering, and nanotechnology.

Enhancement of visible-light photocatalysis by coupling with narrow-band-gap semiconductor: a case study on Bi2S3/Bi2WO6.

To overcome the drawback of low photocatalytic efficiency brought by electron-hole recombination and narrow photoresponse range, we designed a novel Bi(2)S(3)/Bi(2)WO(6) composite photocatalyst. The composite possesses a wide photoabsorption until 800 nm, which occupies nearly the whole range of the visible light. Compared with bare Bi(2)WO(6), the Bi(2)S(3)/Bi(2)WO(6) composite exhibits significantly enhanced photocatalytic activity for phenol degradation under visible light irradiation. On the basis of the calculated energy band positions, the mechanism of enhanced photocatalytic activity was proposed. The present study provides a new strategy to design composite materials with enhanced photocatalytic performance.

Heterostructured bismuth molybdate composite: preparation and improved photocatalytic activity under visible-light irradiation.

A heterostructured photocatalyst containing the same Bi, Mo, and O elements (Bi(3.64)Mo(0.36)O(6.55)/Bi(2)MoO(6)) was realized by a facile hydrothermal method. The heterostructured composite was characterized by powder X-ray diffraction, selected-area electron diffraction, scanning electron microscopy, and high-resolution electron microscopy. The Bi(3.64)Mo(0.36)O(6.55)/Bi(2)MoO(6) composite exhibited notable enhanced photocatalytic activity compared to Bi(2)MoO(6) or Bi(3.64)Mo(0.36)O(6.55) in the photocatalytic degradation of rhodamine B and phenol under visible-light irradiation. More interestingly, it is found that the heterostructured composite could mineralize organic substances into CO(2) efficiently. This study offered a clue for the design of an efficient photocatalyst in the application of environmental treatment.

Nanoscale Kirkendall effect for the synthesis of Bi2MoO6 boxes via a facile solution-phase method.

A one-pot surfactant-free method has been successfully developed to synthesize Bi(2)MoO(6) boxes using MoO(3) nanorods as templates. A formation mechanism involving the nanoscale Kirkendall effect has been proposed. Our work demonstrates the generic feature of a mild solution-phase-mediated nanoscale Kirkendall effect for the synthesis of multicomponent materials with box-like structures.

Photocatalytic activity of silver vanadate with one-dimensional structure under fluorescent light.

One-dimensional ß-AgVO(3) nanobelts (SVN) were realized by a facile hydrothermal method. It indicates the anisotropic crystallographic characteristics through the characterization. With the additive PEG, the sample was restrained in the one-dimensional preferential orientation (SV-P) effectively. The photocatalytic activity studies reveal that the photocatalyst ß-AgVO(3) exhibits excellent photocatalytic activity in the inactivation of Escherichia coli under fluorescent light. In addition, it is found that the morphology has effect on the photocatalytic activity. The ß-AgVO(3) photocatalyst with one-dimensional structure has the potential and promising application in bacterial disinfection indoor using fluorescent light.

General strategy for a large-scale fabric with branched nanofiber-nanorod hierarchical heterostructure: controllable synthesis and applications.

The preparation and characterization of a branched nanofiber-nanorod hierarchical heterostructure fabric (TiO(2)/NiO, TiO(2)/ZnO, and TiO(2)/SnO(2)) are described. The nanomaterial was synthesized on a large scale by an inexpensive, generalizable, facile, and controllable approach by combining the electrospinning technique with a hydrothermal method. The controllable formation process and factors (assistance by hexamethylenetetramine and metal oxide nuclei) influencing the morphology of the branched hierarchical heterostructure are discussed. In addition, photocurrent and photocatalytic studies suggest that the branched hierarchical heterostructure fabric shows higher mobility of charge carriers and enhanced photocatalytic activity relative to a bare TiO(2) nanofibrous mat and other heterostructures under irradiation by light. This work demonstrates the possibility of growing branched heterostructure fabrics of various uniform, one-dimensional, functional metal oxide nanorods on a TiO(2) nanofibrous mat, which has a tunable morphology by changing the precursor. The study may open a new channel for building hierarchical heterostructure device fabrics with optical and catalytic properties, and allow the realization of a new class of nano-heterostructure devices.