HClO-Mediated Photoelectrochemical Epoxidation of Alkenes with Near 100 % Conversion Rate and Selectivity by Regulating Lattice Chlorine Cycle.

Directional organic transformation via a green, sustainable catalytic reaction has attracted a lot of attention. Herein, we report a photoelectrochemical approach for highly selective epoxidation of alkenes in a salt solution using Co2 (OH)3 Cl (CoOCl) as a bridge of photo-generated charge, where the lattice Cl- of CoOCl can be oxidized to generate HClO by the photo-generated holes of BiVO4 photoanode and be spontaneously recovered by Cl- of a salt solution, which then oxidizes the alkenes into the corresponding epoxides. As a result, a series of water-soluble alkenes, including 4-vinylbenzenesulfonic acid sodium, 2-methyl-2-propene-1-sulfonic acid sodium, and 3-methyl-3-buten-1-ol can be epoxidized with near 100 % conversion rate and selectivity. Through further inserting a MoOx protection layer between BiVO4 and CoOCl, the stability of CoOCl-MoOx /BiVO4 can be maintained for at least 120 hours. This work opens an avenue for solar-driven organic epoxidation with a possibility of on-site reaction around the abundant ocean.

Comparative Study of Proton Exchange in Tri- and Hexatitanates: Correlations between Stability and Electronic Properties.

A hydrothermal method is considered to be convenient and is extensively used in preparing titanate architectures, but the intermediate and final products are complicated and variable. To date, it is accepted that intermediates are tri- and hexatitanates. Here, atomic structures, energetics, and correlations between stability and electronic properties of proton exchange in tri- and hexatitanates, i.e., Na2-xHxTi3O7 and Na2-xHxTi6O13, are investigated by first-principles calculations. We found that the bond length of Na-O bonds plays a significant role in determining the activity of tunnel oxygen atoms, while the proton substitution sites are closely related to the activity of tunnel O atom in titanates. As H+ concentration increases, the formation energy of Na2-xHxTi3O7 and Na2-xHxTi6O13 decreases first and then increases, suggesting that completely protonated titanates, i.e., H2Ti3O7 and H2Ti6O13, are unstable. However, we found that H+ substitution would take place even in an alkaline solution both for Na2Ti3O7 and Na2Ti6O13. With a decrease in the pH, the process of H+ exchange becomes more energetically favorable. Compared to Na2Ti3O7, Na+ ions are more easily exchanged by H+ ions in Na2Ti6O13 at the same pH value. We found that there is a strong correlation between stability and electronic properties during the Na+-H+ exchange process. Finally, hydrogen bonds are observed in H2Ti3O7 and Na2-xHxTi6O13 complexes, which make them more stable than Na2-xHxTi3O7 complexes without H-bonds. All of these findings provide insight into understanding the geometry of possible intermediates in the preparation of titanates and suitable conditions for the synthesis of titanates.

g-C3N4/TiO2-B{100} heterostructures used as promising photocatalysts for water splitting from a hybrid density functional study.

Fabrication of heterostructures has been shown to be a good strategy to improve photocatalytic performance. By using first-principles calculation based on hybrid density functionals, the photocatalytic mechanism of g-C3N4/TiO2-B{100} heterostructures is investigated to understand the process of water decomposition. We find that the reduction of the band gap of g-C3N4/TiO2-B{100} heterostructures enhances the visible light response range. g-C3N4/TiO2-B{100} heterostructures have direct band gaps, staggered band alignment, electron flow from g-C3N4 to TiO2-B{100} surfaces and straddling water decomposition potential, and are potential Z-scheme photocatalysts. Photoinduced carriers can be effectively separated using the Z-scheme photocatalytic mechanism. Our results demonstrate that g-C3N4/TiO2-B{100} heterostructures can enhance light absorption, prolong the life of photoinduced carriers, and further improve the photocatalytic activity. We believe that our findings can provide a reference for explaining the enhancement mechanism of the g-C3N4/TiO2 photocatalyst as observed in the experiment.

Occurrence and Phase Distribution of Neutral and Ionizable Per- and Polyfluoroalkyl Substances (PFASs) in the Atmosphere and Plant Leaves around Landfills: A Case Study in Tianjin, China.

A total of 23 per- and polyfluoroalkyl substances (PFASs) were investigated in the air, dry deposition, and plant leaves at two different landfills and one suburban reference site in Tianjin, China. The potential of landfills as sources of PFASs to the atmosphere and the phase distribution therein were evaluated. The maximum concentrations of ∑PFASs in the two landfills were up to 9.5 ng/m3 in the air, 4.1 µg/g in dry deposition, and 48 µg/g lipid in leaves with trifluoroacetic acid and perfluoropropionic acid being dominant (71%-94%). Spatially, the distribution trend of ionizable and neutral PFASs in all three kinds of media consistently showed the central landfill > the downwind > the upwind > the reference sites, indicating that landfills are important sources to PFASs in the environment. Plant leaves were found effective in uptake of a variety of airborne PFASs including polyfluoroalkyl phosphoric acid diesters, thus capable of acting as a passive air sampling approach for air monitoring.

Progress of charge carrier dynamics and regulation strategies in 2D CxNy-based heterojunctions.

Two-dimensional carbon nitrides (CxNy) have gained significant attention in various fields including hydrogen energy development, environmental remediation, optoelectronic devices, and energy storage owing to their extensive surface area, abundant raw materials, high chemical stability, and distinctive physical and chemical characteristics. One effective approach to address the challenges of limited visible light utilization and elevated carrier recombination rates is to establish heterojunctions for CxNy-based single materials (e.g. C2N3, g-C3N4, C3N4, C4N3, C2N, and C3N). The carrier generation, migration, and recombination of heterojunctions with different band alignments have been analyzed starting from the application of CxNy with metal oxides, transition metal sulfides (selenides), conductive carbon, and Cx'Ny' heterojunctions. Additionally, we have explored diverse strategies to enhance heterojunction performance from the perspective of carrier dynamics. In conclusion, we present some overarching observations and insights into the challenges and opportunities associated with the development of advanced CxNy-based heterojunctions.

Supramolecular catalyst with [FeCl4] unit boosting photoelectrochemical seawater splitting via water nucleophilic attack pathway.

Propelled by the structure of water oxidation co-catalysts in natural photosynthesis, molecular co-catalysts have long been believed to possess the developable potential in artificial photosynthesis. However, the interfacial complexity between light absorber and molecular co-catalyst limits its structural stability and charge transfer efficiency. To overcome the challenge, a supramolecular scaffold with the [FeCl4] catalytic units is reported, which undergo a water-nucleophilic attack of the water oxidation reaction, while the supramolecular matrix can be in-situ grown on the surface of photoelectrode through a simple chemical polymerization to be a strongly coupled interface. A well-defined BiVO4 photoanode hybridized with [FeCl4] units in polythiophene reaches 4.72 mA cm-2 at 1.23 VRHE, which also exhibits great stability for photoelectrochemical seawater splitting due to the restraint on chlorine evolution reaction by [FeCl4] units and polythiophene. This work provides a novel solution to the challenge of the interface charge transfer of molecular co-catalyst hybridized photoelectrode.

Microstructural changes of the vestibulocochlear nerve in patients with Ménière's disease using diffusion tensor imaging.

Objective: To evaluate the microstructural changes of the vestibulocochlear nerve in patients with Ménière's disease. Methods: A total of 26 subjects, 13 patients with MD and 13 healthy controls, underwent diffusion tensor imaging (DTI) on a 3T scanner. The independent sample t-test was used to compare the differences in fractional anisotropy (FA) and apparent diffusion coefficient (ADC) between the two groups. A Pearson correlation was used between DTI and the dizziness handicap inventory (DHI) scores. Results: There was a significant decrease in FA and an increase in ADC of the vestibulocochlear nerve in MD patients compared with healthy controls (P = 0.04, P = 0.001). FA had negative correlations with the DHI score (r = -0.62, P = 0.02) and DHI-functional score (r = -0.64, P = 0.02). Conclusion: These results are the first evidence of possible changes in the microstructure of the vestibulocochlear nerves in patients with MD. DTI is a potential technique for evaluating the vestibulocochlear nerve in patients with MD.

Dynamic changes in atrazine and phenanthrene sorption behaviors during the aging of biochar in soils.

The objective of this study was to elucidate the dynamic changes in the properties of biochar-amended soil and their sorption capacity for typical organic contaminants with increasing contact time between biochar and soil. To do so, biochars that were produced from pig manure at two temperatures were added to two soils, and the sorption behaviors of atrazine and phenanthrene (Phen) on soil-biochar mixtures aged for different times were investigated. Soils freshly amended with biochars showed a dramatic increase in the sorption of atrazine (up to 23.4 times at C e = 0.01 S w) and Phen (up to 3.12 times at C e = 0.01 S w) compared to the bare soils without biochars. The physicochemical properties of soil-biochar mixtures changed with aging time, which in turn affected the sorption capacity. After the biochar produced at 300 °C (BC300) was aged in soil, the sorption of atrazine and Phen by black soil (BS) and fluvo-aquic soil (FS) both increased by different extents, except the sorption of Phen on BS. However, after the biochar produced at 700 °C (BC700) was aged in soil, the sorption of atrazine on the two soils decreased markedly, which was sill 56.3% higher than that on the original soil, while an opposite trend was observed for Phen on the two soils. The complex change patterns could be due to the different dominant sorption mechanisms for different biochars and chemicals.

[Research on thymopentin-loaded N-trimethyl chitosan nanoparticles administered through mouth].

OBJECTIVE: To prepare a peroral thymopentin-loaded N-trimethyl chitosan chloride-nanoparticle (Tp5-TMC-NP) ,and observe the pharmacodynamic action when the Tp5-TMC-NP is taken by way of the mouth. METHODS: N-trimethyl chitosan chloride was first synthesized, and then Tp5-TMC-NP was prepared with the formulation technology optimized by the Central Composite Design. The influence of Tp5-TMC-NP on the ratio of CD4+/CD8+ of T-lymphocytes were determined by flow cytometer. RESULTS: The regular global Tp5-TMC-NP prepared with the optimized formulation craft had the mean diameter of 110.6 nm and got the entrapment efficiency of 78.8%. The ratio of lymphocyte CD4+/CD8+ of Wistar rat administered with Tp5-TMC-NP perfusing stomach had 2.59 times higher than that with Tp5. CONCLUSION: Taken orally the Tp5-TMC-NP has much higher efficiency than Tp5.

Research on thymopentin loaded oral N-trimethyl chitosan nanoparticles.

Peptides, although high efficacy and specificity in their physiological function, usually have low therapeutical activities due to their poor bioavailability when administrated orally. Nanoparticles have been regarded as a useful vector for targeted drug delivery system because they can protect drug from being degraded quickly and pass the gastrointestinal barriers. Here we described a novel oral N-trimethyl chitosan nanoparticles formulation containing thymopentin (Tp5-TMC-NP). N-trimethyl chitosan (TMC) was synthesized and then used to prepare Tp5-TMC-NP by ionotropic gelation. A three-factor, five-level CCD (Central Composite Design) design was used in the optimization procedure, with HPLC as the analyzing method. The resulting Tp5-TMC-NP had a regular spherical surface and a narrow particle size range with a mean diameter of 110.6 nm. The average entrapment efficiency was 78.8%. The lyophilized Tp5-TMC-NP formulation was stable in 4 degrees C or -20 degrees C after storage of 3 months without obvious changes in morphology, particle size, pH and entrapment ratio. The results of the flow cytometer determination showed that the ratio of CD4+/CD8+ of Wistar female rat givenTp5-TMC-NP (ig) was 2.59 time that of the group given Tp5 (ig).