Fine Tuning Electronic Structure of Catalysts through Atomic Engineering for Enhanced Hydrogen Evolution

An efficient, durable, and low‐cost hydrogen evolution reaction (HER) catalyst is an essential requirement for practical hydrogen production. Herein, an effective approach to facilitate the HER kinetics of molybdenum carbide (Mo₂C) electrocatalysts is presented by tuning its electronic structure through atomic engineering of nitrogen implantation. Starting from the organoimido‐derivatized polyoxometalate nanoclusters with inherent Mo? N bonds, the formation of N‐implanted Mo₂C (N@Mo₂C) nanocrystals with perfectly adjustable amounts of N atoms is demonstrated. The optimized N@Mo₂C electrocatalyst exhibits remarkable HER performance and good stability over 20 h in both acid and basic electrolytes. Further density functional theory calculations show that engineering suitable nitrogen atoms into Mo₂C can regulate its electronic structure well and decrease Mo? H strength, leading to a great enhancement of the HER activity. It could be believed that this ligand‐controlled atomic engineering strategy might influence the overall catalyst design strategy for engineering the activation sites of nonprecious metal catalysts for energy conversions.     

基于生态红线划定的祁连山生态保护性开发研究

运用祁连山地区的自然环境数据和社会经济数据,基于GIS平台、加权求和多指标运算模型,选取了30个指标,从生态弹性力、生态敏感性和社会经济影响力3个方面,构建了生态红线评价指标体系,对祁连山生态保护性开发进行研究分析。结果表明:生态红、黄、绿线区,分别占研究区面积的32%、40%、28%。生态红线区主要分布于祁连山的西南段、托来山以南、青海湖区及区内所有冰川分布地区,应实行最严格的管控;生态黄线区是祁连山分布面积最广的区域,主要集中在祁连山中、西段,湟水谷地的中游及乌鞘岭南部,应以修复生态环境和提供部分农产品为主;生态绿线区主要分布在疏勒南山以东地区,应保护优先,以提供生态产品为主,分区开展各具民族特色的生态旅游。     

高温胁迫对紫花苜蓿的影响及其适应机制的相关研究

紫花苜蓿是优质的多年生豆科牧草,喜温暖半干旱气候。高温能使其植株生长缓慢、枯萎甚至死亡,病虫害增多,严重影响紫花苜蓿的产量和品质,是限制紫花苜蓿推广利用的一个重要环境因子之一。紫花苜蓿在高温胁迫后,细胞膜流动性、光合作用及呼吸效率等发生改变,产生大量的渗透调节物质、活性氧和热激蛋白等,提高了紫花苜蓿的耐热性,形成了适应高温应激的适应机制。本研究在分析紫花苜蓿特征特性的基础上,从高温对紫花苜蓿的影响、紫花苜蓿适应高温胁迫的机制及其耐热性评价指标的选择和可靠性评价的方法等方面综述了紫花苜蓿耐热性的研究现状,为开展进一步的研究工作提供参考。     

Multi-generational effects of simulated herbivory and habitat types on the invasive weed Alternanthera philoxeroides: implications for biological control

Long-term pre-release evaluations of how invasive plants respond to herbivory in introduced ranges can help identify the most effective biological control agents. However, most evaluations have been conducted within only one generation of introduced invasive species. This study tested effects across seven generations of simulated herbivory (i.e., defoliation) and habitat types on the invasive weed Alternanthera philoxeroides. We found total biomass of A. philoxeroides was decreased by defoliation during the first three generations when grown in a simulated aquatic habitat, but was decreased by defoliation only in the first generation when grown in a simulated terrestrial habitat. Defoliation significantly decreased stem diameter and collenchyma thickness and increased cortex thickness and total phenol production in A. philoxeroides grown in a simulated terrestrial or aquatic habitat during the first generation, but showed little effect during the following six successive generations. The associations between stem anatomical structural parameters and biomass significantly differed between non-defoliation and defoliation treatments in the simulated aquatic habitat, but not in the simulated terrestrial habitat. Our results suggest simulated herbivory exerted successful biological control on A. philoxeroides during the first generation in a simulated terrestrial habitat and the first three generations in a simulated aquatic habitat, but failed to restrain the vegetative offspring of A. philoxeroides. This failure of long-term biological control on A. philoxeroides might be caused by changes in the stem anatomical structure and compensatory growth. Our study highlights the need for long-term pre-release evaluation when testing the efficiency of biological control agents.

     

NADPH oxidase-2 derived ROS dictates murine DC cytokine-mediated cell fate decisions during CD4 T helper-cell commitment

NADPH oxidase-2 (Nox2)/gp91(phox) and p47(phox) deficient mice are prone to hyper-inflammatory responses suggesting a paradoxical role for Nox2-derived reactive oxygen species (ROS) as anti-inflammatory mediators. The molecular basis for this mode of control remains unclear. Here we demonstrate that IFNγ/LPS matured p47(phox-/-)-ROS deficient mouse dendritic cells (DC) secrete more IL-12p70 than similarly treated wild type DC, and in an in vitro co-culture model IFNγ/LPS matured p47(phox-/-) DC bias more ovalbumin-specific CD4(+) T lymphocytes toward a Th1 phenotype than wild type (WT) DC through a ROS-dependent mechanism linking IL-12p70 expression to regulation of p38-MAPK activation. The Nox2-dependent ROS production in DC negatively regulates proinflammatory IL-12 expression in DC by constraining p38-MAPK activity. Increasing endogenous H(2)O(2) attenuates p38-MAPK activity in IFNγ/LPS stimulated WT and p47(phox-/-) DC, which suggests that endogenous Nox 2-derived ROS functions as a secondary messenger in the activated p38-MAPK signaling pathway during IL-12 expression. These findings indicate that ROS, generated endogenously by innate and adaptive immune cells, can function as important secondary messengers that can regulate cytokine production and immune cell cross-talk to control during the inflammatory response.     

Impact of Anthropogenic Organic Matter on the Distribution Patterns of Sediment Microbial Community from the Yangtze River,China

Abstract

How microbes respond to substantial and increasing anthropogenic disturbance remains an open question in river systems. We tested the hypothesis that the source and distribution of anthropogenic organic matter (OM) were significant factors affecting the spatial variation of the microbial community composition of the Yangtze River sediments. Bulk geochemical proxies and lignin phenols suggested a general decrease of terrestrial C3 plants or soil OM input from the middle to the lower reaches. Fecal sterols inferred higher sewage contamination levels in the middle reaches. Polycyclic aromatic hydrocarbons (PAHs) distribution indicated a dominant biomass and coal combustion signal in the middle reaches, whereas a mixed source including petroleum combustion in the lower reaches. Phylogenetic analysis revealed a large portion of Methanobacteria and Verrucomicrobia enriched in the middle reaches, whereas OM-degrading bacteria, including Flavobacteria, Acidobacteria, and Alphaproteobacteria were dominant in the lower reaches. Quantitative PCR analyses and multivariate analysis further demonstrated that sources and distribution of OM had combined effects in shaping alpha and beta-diversity of sediment microbial communities. Sewage discharge and incomplete OM combustion, respectively, were associated with Methylococcaceae, Chloroflexi, and Bacteroidetes groups. This study provides a foundation for further understanding of the river sediment microbial composition, considering the continued increase of anthropogenic influences.     

Two new bromo-functionalized organoimido derivatives of hexamolybdate: Synthesis, crystal structure, spectroscopic and electrochemical studies

Two organic-inorganic hybrid compounds, (Bu₄N)₂[Mo₆O₁₈(NAr)] (Ar =  2-CH₃-4-BrC₆H₃ (1) or 2,6-CH₃-4-BrC₆H₂ (2)) have been synthesized via the DCC dehydrating protocol of the reaction of [α-Mo₈O₂₆]⁴⁻ with 2-methyl-4-bromoaniline hydrochloride or 2,6-dimethyl-4-bromoaniline hydrochloride in anhydrous acetonitrile, which have been characterized by UV-Vis spectra, ¹H NMR, IR, cyclic voltammetry and X-ray single-crystal diffraction study. Both compounds crystallize in the monoclinic space group , which are featured in a terminal phenylimido group linked to a Mo atom of a hexamolybdate cluster by a Mo-N triple bond. Interestingly, there are two conformational isomers of the cluster anions of 1 and 2 in the crystals. By cyclic voltammetry study, their special redox properties were also found in the end.     

CYLD and the NEMO Zinc Finger Regulate Tumor Necrosis Factor Signaling and Early Embryogenesis

NF-κB essential modulator (NEMO) and cylindromatosis protein (CYLD) are intracellular proteins that regulate the NF-κB signaling pathway. Although mice with either CYLD deficiency or an alteration in the zinc finger domain of NEMO (K392R) are born healthy, we found that the combination of these two gene defects in double mutant (DM) mice is early embryonic lethal but can be rescued by the absence of TNF receptor 1 (TNFR1). Notably, NEMO was not recruited into the TNFR1 complex of DM cells, and consequently NF-κB induction by TNF was severely impaired and DM cells were sensitized to TNF-induced cell death. Interestingly, the TNF signaling defects can be fully rescued by reconstitution of DM cells with CYLD lacking ubiquitin hydrolase activity but not with CYLD mutated in TNF receptor-associated factor 2 (TRAF2) or NEMO binding sites. Therefore, our data demonstrate an unexpected non-catalytic function for CYLD as an adapter protein between TRAF2 and the NEMO zinc finger that is important for TNF-induced NF-κB signaling during embryogenesis.     

Attempted immunotherapy for Mycobacterium tuberculosis with viral and protein vaccines based on Ag85B-ESAT6 in a mouse model

The increasing threat of drug-resistant strains of Mycobacterium tuberculosis (M. tb) and co-infection with human immunodeficiency virus (HIV) has worsened the international public health crisis and challenged conventional chemotherapy. Therapeutic vaccines, which possess the capacity to stimulate the immune system and affect the disease progression, deserve reconsideration to aid chemotherapy. Vaccines based on Ag85B-ESAT6 fusion protein were tested as potential immunotherapeutic vaccines against ongoing intravenous infection in a mouse model. Therapeutic efficacy was evaluated by enumeration of bacilli in infected tissues and by histological examination of the lungs. Ag85B-ESAT6 with the adjuvant dimethyl dioctadecylammonium bromide (DDA) - monophosphoryl lipid A (MPL) did not reduce bacterial load, however induced a sharp weight loss and worsened pathology. Recombinant virus-based vaccines failed to protect mice against tuberculosis either. More efforts should be taken to search for protective candidates and elucidate the mechanism for immunotherapy.     

Enhanced allelopathy and competitive ability of invasive plant Solidago canadensis in its introduced range

Aims Why invasive plants are more competitive in their introduced range than native range is still an unanswered question in plant invasion ecology. Here, we used the model invasive plant Solidago canadensis to test a hypothesis that enhanced production of allelopathic compounds results in greater competitive ability of invasive plants in the invaded range rather than in the native range. We also examined the degree to which the allelopathy contributes increased competitive ability of S. canadensis in the invaded range.Methods We compared allelochemical production by S. canadensis growing in its native area (the USA) and invaded area (China) and also by populations that were collected from the two countries and grown together in a 'common garden' greenhouse experiment. We also tested the allelopathic effects of S. canadensis collected from either the USA or China on the germination of Kummerowia striata (a native plant in China). Finally, we conducted a common garden, greenhouse experiment in which K. striata was grown in monoculture or with S. canadensis from the USA or China to test the effects of allelopathy on plant–plant competition with suitable controls such as adding activated carbon to the soil to absorb the allelochemicals and thereby eliminating any corresponding allopathic effects.Important findings Allelochemical contents (total phenolics, total flavones and total saponins) and allelopathic effects were greater in S. canadensis sampled from China than those from the USA as demonstrated in a field survey and a common garden experiment. Inhibition of K. striata germination using S. canadensis extracts or previously grown in soil was greater using samples from China than from the USA. The competitive ability of S. canadensis against K. striata was also greater for plants originating from China than those from the USA. Allelopathy could explain about 46% of the difference. These findings demonstrated that S. canadensis has evolved to be more allelopathic and competitive in the introduced range and that allelopathy significantly contributes to increased competitiveness for this invasive species.