Highly Efficient Nitrogen Reduction to Ammonia through the Cooperation of Plasma and Porous Metal-Organic Framework Reactors with Confined Water.

While the ambient N2 reduction to ammonia (NH3) using H2O as hydrogen source (2N2+6H2O=4NH3+3O2) is known as a promising alternative to the Haber-Bosch process, the high bond energy of N≡N bond leads to the extremely low NH3 yield. Herein, we report a highly efficient catalytic system for ammonia synthesis using the low-temperature dielectric barrier discharge plasma to activate inert N2 molecules into the activated nitrogen species, which can efficiently react with the confined and concentrated H2O molecules in porous metal-organic framework (MOF) reactors with V3+, Cr3+, Mn3+, Fe3+, Co2+, Ni2+ and Cu2+ ions. Specially, the Fe-based catalyst MIL-100(Fe) causes a superhigh NH3 yield of 22.4 mmol g-1 h-1. The investigation of catalytic performance and systematic characterizations of MIL-100(Fe) during the plasma-driven catalytic reaction unveils that the in situ generated defective Fe-O clusters are the highly active sites and NH3 molecules indeed form inside the MIL-100(Fe) reactor. The theoretical calculation reveals that the porous MOF catalysts have different adsorption capacity for nitrogen species on different catalytic metal sites, where the optimal MIL-100(Fe) has the lowest energy barrier for the rate-limiting *NNH formation step, significantly enhancing efficiency of nitrogen fixation.

Plasma-Driven Efficient Conversion of CO2 and H2O into Pure Syngas with Controllable Wide H2/CO Ratios over Metal-Organic Frameworks Featuring In Situ Evolved Ligand Defects.

While the mild production of syngas (a mixture of H2 and CO) from CO2 and H2O is a promising alternative to the coal-based chemical engineering technologies, the inert nature of CO2 molecules, unfavorable splitting pathways of H2O and unsatisfactory catalysts lead to the challenge in the difficult integration of high CO2 conversion efficiency with produced syngas with controllable H2/CO ratios in a wide range. Herein, we report an efficient plasma-driven catalytic system for mild production of pure syngas over porous metal-organic framework (MOF) catalysts with rich confined H2O molecules, where their syngas production capacity is regulated by the in situ evolved ligand defects and the plasma-activated intermediate species of CO2 molecules. Specially, the Cu-based catalyst system achieves 61.9 % of CO2 conversion and the production of pure syngas with wide H2/CO ratios of 0.05 : 1-4.3 : 1. As revealed by the experimental and theoretical calculation results, the in situ dynamic structure evolution of Cu-containing MOF catalysts favors the generation of coordinatively unsaturated metal active sites with optimized geometric and electronic characteristics, the adsorption of reactants, and the reduced energy barriers of syngas-production potential-determining steps of the hydrogenation of CO2 to *COOH and the protonation of H2O to *H.

Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron-based Metal-Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis.

Engineering advantageous defects to construct well-defined active sites in catalysts is promising but challenging to achieve efficient photocatalytic NH3 synthesis from N2 and H2O due to the chemical inertness of N2 molecule. Here, we report defective Fe-based metal-organic framework (MOF) photocatalysts via a non-thermal plasma-assisted synthesis strategy, where their NH3 production capability is synergistically regulated by two types of defects, namely, bridging organic ligands and terminal inorganic ligands (OH- and H2O). Specially, the optimized MIL-100(Fe) catalysts, where there are only terminal inorganic ligand defects and coexistence of dual defects, exhibit the respective 1.7- and 7.7-fold activity enhancement comparable to the pristine catalyst under visible light irradiation. As revealed by experimental and theoretical calculation results, the dual defects in the catalyst induce the formation of abundant and highly accessible coordinatively unsaturated Fe active sites and synergistically optimize their geometric and electronic structures, which favors the injection of more d-orbital electrons in Fe sites into the N2 π* antibonding orbital to achieve N2 activation and the formation of a key intermediate *NNH in the reaction. This work provides a guidance on the rational design and accurate construction of porous catalysts with precise defective structures for high-performance activation of catalytic molecules.

Orai1-mediated store-operated Ca2+ entry promotes cervical cancer progression through IL-6 signaling.

Cervical cancer is a major cause of cancer-associated mortality among women in developing countries. Orai1-mediated store-operated Ca2+ entry (SOCE) is the primary mechanism underlying most of the non-excitable calcium influx into cells. There is at present limited evidence showing that Orai1 can function as an oncogene or a tumor suppressor depending on the cancer type. Furthermore, the exact biological functions of Orai1 in cervical cancer and the underlying mechanisms are still poorly understood. In this study, we found that Orai1 was upregulated in cervical cancer tissues, and promoted the growth of human cervical cancer cells both in vitro and in vivo. Gene silencing of Orai1 in cervical cancer cells significantly decreased interleukin (IL)-6 secretion. Interestingly, exogenous IL-6 abrogated the effects of Orai1 silencing and restored the clonogenicity of cervical cancer cells. Furthermore, we also observed a positive correlation between Orai1 and IL-6 expression in human cervical cancer samples. Taken together, our findings indicate that Orai1 functions as an oncogene in cervical cancer and is a promising therapeutic target.

Structural elucidation of galactomannan from seeds of Crotalaria mucronata Desv. by atomic force microscopy.

A non-ionic water-soluble galactomannan, isolated from the seed endosperm of Crotalaria mucronata Desv., may be an ideal thickener to increase food viscosity. The present study hypothesized that the viscous property of Crotalaria galactomannan may be associated with its spatial structure. Therefore, the structure of Crotalaria galactomannan was elucidated using an atomic force microscope. The results of the present study demonstrated that the polysaccharide consisted of a D­mannose backbone with D­galactose branches, and the D­mannose/D­galactose ratio was 2.375:1. In the three­dimensional structure of Crotalaria galactomannan, the helix was a common secondary structure, containing numerous ring structures of different sizes. In addition, multiple helixes may link together via hydrogen bonding and van der Waals forces, forming aggregations with small rings or spiral windings. The results of the present study indicated that the multiple­branching construction of Crotalaria galactomannan may underlie its viscosity­enhancing properties in the water phase.

Statistical optimization of culture medium for production of exopolysaccharide from endophytic fungus Bionectria ochroleuca and its antitumor effect in vitro.

Endophytic fungi have been recognized as possible useful sources of bioactive metabolites. However, exopolysaccharide (EPS) production from endophytic fungi and its antitumor activity have been less explored. In the present study, endophtic fungus Bionectria ochroleuca M21 was exploited for the production of EPS in submerged culture. Among tested medium components, glucose, yeast extract, MgSO4 and Tween80 were found to be effective and significant on EPS production. Response surface methodology (RSM) was employed to optimize medium composition. The results showed that the significant factors were glucose, yeast extract and Tween80. The optimal medium was observed at the composition of glucose 55.7 g/L, yeast extract 6.04 g/L, MgSO4 0.25g/L and Tween80 0.1 % (v/v). Using the optimized medium, EPS production was achieve at 2.65 ± 0.16 g/L after 4 days fermentation in a 5L bioreactor. Examination of cytotoxicity showed that the EPS from B. ochroleuca M21 did not have cytotoxic activity on human liver HL-7702 cells at concentration 0.025-1.6 mg/mL. In contrast, the EPS exhibited antiproliferative activities against cell lines of liver cancer (HepG2), gastric cancer (SGC-7901) and colon cancer (HT29) in a dose- and time-dependent manner in the concentration ranges of 0.1-0.45 mg/mL.

A new ent-kaurane diterpenoid from Rabdosia pseudo-irrorata C. Y. Wu.

A new ent-kaurane diterpenoid, Pseurata H (1), was isolated from the aerial parts of Rabdosia pseudo-irrorata C. Y. Wu, along with three known compounds, Pseurata B (2), Pseurata C (3) and Pseurata F (4). Their structures were established by extensive spectroscopic techniques (MS, IR, 1D and 2D NMR experiments).

[Allelopathy of aqueous extract from Ligularia virgaurea, a dominant weed in psychro-grassland, on pasture plants].

Ligularia virgaurea is a noxious weed widely distributed in the alpine grassland of east Qinghai-Tibet Plateau of China. This paper studied the allelopathy of its aqueous extract on the pasture plants Festuca sinensis, Bromus magnus, Elymus nutans, Poa annua, and F. ovina in the region. The mean response index (RI) values of the pasture plants were calculated, and used to quantitatively assess the allelopathic sensitivity of the receptors at three levels, i. e., growth items, development stages, and species. Corresponding values of the weed were also treated in similar way to assess the allelopathic potential of the donor. The results showed that the allelopathic sensitivity was in the order of P. annua > B. magnus > F. sinensis > F. ovina > E. nutans. Both the seed germination and the seedling growth of test pasture plants were inhibited at species level, suggesting that rain eluviation was one of the means by which the weed released allelochemicals. The aqueous extracts from L. virgaurea root and leaf had a significant inhibitory effect at species level, and the effect of root extract was stronger than that of leaf extract, suggesting the competition among species on the underground resources in natural grassland. Allelopathy played an important role in L. virgaurea invasion, and might be responsible to the formation of mono-dominant community and the degeneration of grassland.