Synthesis,Anticancer Activity,Structure-Activity Relationship and Mechanistic Investigations of Falcarindiol Analogues

Forty samples of optically active falcarindiol analogues are synthesized by using the easily available C2 symmetric (R)- and (S)-1,1’-binaphth-2-ol (BINOL) in combination with Ti(OⁱPr)₄, Zn powder and EtI. Their anticancer activities on Hccc-9810, HepG2, MDA-MB-231, Hela, MG-63 and H460 cells are assayed to elucidate their structure-activity relationships. These results showed that the falcarindiol analogue (3R,8S)- 2 i with the terminal double bond has the most potent anti-proliferation effect on Hccc-9810 cells with IC₅₀ value of 0.46 μM. The falcarindiol analogue (3R,8S)- 2 i can induce obvious Hccc-9810 cell apoptosis in a concentration-dependent manner by Hoechst staining and flow cytometry analysis. The proposed mechanism suggests that the falcarindiol analogue (3R,8S)- 2 i increases LDH release and MDA content, and reduces the levels of SOD activity, which lead to the accumulation of oxidative stress and induce apoptosis in Hccc-9810 cells.     

Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT-Derived Polycatenar Molecules

First examples of multichain (polycatenar) compounds, based on the π-conjugated [1]benzothieno[3,2-b]benzothiophene unit are designed, synthesized, and their soft self-assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan-shaped 2-brominated 3,4,5-trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non-dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.     

Charging strategy through analysis of charging influence factors of ultra-light hydrogen storage with polyethylene terephthalate liner

A lightweight type 4 vessel with a polyethylene terephthalate (PET) liner is analyzed. The derived heat transfer coefficients between the gas and wall are applied, and a parametric study is performed. An optimized charging strategy is also developed. Firstly, when the injected hydrogen temperature decreases, the charging time increases, and the charged gas temperature decreases. Secondly, the higher the ambient temperature, the shorter the charging time, and the higher the charged gas temperature. Thirdly, the larger the mass flow rate, the shorter the charging time, and the higher charged gas temperature. Fourthly, as the initial pressure inside the vessel increases, the charging time shortens, and the charged gas temperature decreases. Fifthly, using the formulated charging strategy, during summer, the charged gas temperature decreases by approximately 9 °C. In winter, the charging time is reduced by approximately 58 s. The results provide important information of temperature control for ensuring vessel safety.     

Hydrogen evolution reaction on in-plane platinum and palladium dichalcogenides via single-atom doping

Searching for the catalysts with excellent catalytic activity and high chemical stability is the key to achieve large-scale production of hydrogen (H₂) through hydrogen evolution reaction (HER). Two-dimensional (2D) platinum and palladium dichalcogenides with extraordinary electrical properties have emerged as the potential candidate for HER catalysts. Here, chemical stability, HER electrocatalytic activity, and the origin of improved HER performance of Pt/Pd-based dichalcogenides with single-atom doping (B, C, N, P, Au, Ag, Cu, Co, Fe, Ni, Zn) and vacancies are explored by first-principles calculations. The calculated defect formation energy reveals that most defective structures are thermodynamically stable. Hydrogen evolution performance on basal plane is obviously improved by single-atoms doping and vacancies. Particularly, Zn-doped and Te vacancy PtTe₂ have a ΔG_H value close to zero. Moreover, defect engineering displays a different performance on HER catalytic activity in sulfur group elements, in order of S < Te < Se in Pd-based chalcogenides, and S < Se < Te in Pt-based chalcogenides. The origin of improved hydrogen evolution performance is revealed by electronic structure and charge transfer. Our findings of the highly activating defective systems provide a theoretical basis for HER applications of platinum and palladium dichalcogenides.     

Employing one-step coupling cold plasma and thermal polymerization approach to construct nitrogen defect-rich carbon nitrides toward efficient visible-light-driven hydrogen generation

Construction of structural defects in photocatalysts is a powerful tool for regulating their photocatalytic performance. In this work, we develop a facile one-step coupling cold plasma and thermal polymerization approach to synthesize a series of nitrogen defect-rich graphitic carbon nitrides (C₃N_4-x), which are used for visible-light-driven hydrogen generation from water. The nitrogen defect-induced band structure regulation of C₃N_4-x catalysts can be carried out through controlling the bombardment time and excitation power of generator during the plasma modification process. The defective C₃N_4-x catalysts have the extended visible light absorption and improved separation efficiency of photogenerated charge carriers, which results in the boosted hydrogen generation activity. Particularly, the optimal C₃N_4-x possesses a hydrogen generation rate of 2.46 mmol h^?1 g^?1, which is about 4.5 times higher than the pristine C₃N₄ synthesized by the single thermal polymerization of urea. The cold plasma modification-based one-step synthesis approach guides us for rationally designing defective nanomaterials with excellent catalytic performance.     

柴油车尾气处理液颗粒原料尿素指标研究

以颗粒尿素为原料生产的柴油车尾气处理液,在气温低的地区使用易出现沉淀物问题,通过对尿素生产工艺的研究和试验分析得知,沉淀物产生的原因为尿素生产蒸发造粒时产生的副产物缩二脲等所造成,当颗粒尿素中的副产物含量偏高时,遇低温就会析出,且该析出反应不可逆;通过进一步试验确定,当固体尿素为原料生产柴油车尾气处理液选用的颗粒尿素原料缩二脲≤0.80％时,是生产尾气处理液产品不出现析出物的关键性指标.目前,该指标已为大多数以颗粒尿素生产柴油车尾气处理液的生产厂家所选用采纳.     

Synthesis and photocatalytic performance of MoS2/Polycrystalline black phosphorus heterojunction composite

As a promising catalyst for solar hydrogen production, black phosphorus (BP) has received widespread attention due to variable band gaps, high carrier mobility, and strong light absorption performance. Herein, we use MoS₂ as a cocatalyst to synthesize BP/MoS₂ catalyst with polycrystalline BP to improve photocatalytic performance under visible light irradiation. A small amount of MoS₂ can reduce the recombination of electron-hole pairs in the composite, increase carrier transport efficiency, and then improve photocatalytic performance. As expected, the 10/0.5 ratio of BP/MoS₂ catalyst exhibits the highest photocatalytic hydrogen evolution performance with a hydrogen evolution rate of 575.4 μmol h^?1 g^?1, which is 2.5 times of pure BP. Based on the results above, a simple method is provided to synthesize low-cost black phosphorus-based photocatalysts.     

Improving storability,physiological disorders,and antioxidant properties of ‘Bartlett’ and ‘d’Anjou’ pears (Pyrus communis L.) by pre-harvest 1-methylcyclopropene spraying

Ethylene continues to be a major factor influencing quality of European pears during storage. Although research has been done on the effect of pre-harvest 1-methylcyclopropene (1-MCP) on physiological characteristics in pears, a full understanding of cultivar response and antioxidant metabolism remains elusive. Spraying 1-MCP on ‘Bartlett’ and ‘d’Anjou’ pears was studied with respect to physiology, storage and eating quality, disorders, and antioxidant properties at two harvest date (H1 and H2) during storage and ripening. Treatment with 1-MCP extended the harvest window of ‘Bartlett’ and ‘d’Anjou’ pears 3 and 4 days, respectively, without reducing storage or eating quality. Treatment with 1-MCP reduced ethylene production (EPR) and respiration rates (RR), maintained fruit firmness and green colour during storage and retarded development of desirable melting texture in both cultivars. Additionally, 1-MCP lowered the incidence of disorders by alleviating membrane lipid peroxidation, retaining high total flavonoids (TF) and antioxidant capacity, and enhancing superoxide dismutase (SOD), catalase (CAT) and ascorbate peroxidase (APX) activity in both cultivars. Overall, pre-harvest 1-MCP applications could extend storage time of ‘Bartlett’ and ‘d’Anjou’ pears to 5 and 6 months, respectively, at −1.1 ± 0.5 °C, by reducing ethylene synthesis and enhancing antioxidant metabolism.