Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single‐Layer Graphene

Spinel‐structured LiMn₂O₄ (LMO) is a desirable cathode material for Li‐ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single‐layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene‐coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X‐ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmission electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single‐layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn³⁺ at the LMO electrode surface, promoting an oxidation state change to Mn⁴⁺, which suppresses dissolution.     

The Effect of Fungal Morphology on Ligninolytic Enzyme Production by a Recently Isolated Wood-Degrading Fungus Trichophyton Rubrum LSK-27

The morphology and ligninolytic enzyme production of a recently isolated wood-degrading fungus Trichophyton rubrum LSK-27 was investigated. In submerged cultures, the organism appeared to be an efficient manganese peroxidase (MnP) producer. When grown in baffled and unbaffled shake flasks with three different working volume/total volume ratios (WV/TV 10, 25 and 50%), the organism displayed notable morphological differences, with variations in pellet shape and size. Cultivation in baffled flasks with 25% WV/TV resulted in higher MnP and also laccase production as well as an earlier appearance of these enzymes in culture broth. However, oxygen limitation conditions inhibited MnP and laccase production and resulted in considerable changes in the morphology of this fungus.     

锰矿修复区植物生态系统自由能与化学势分析

基于热力学理论建立了生态系统Gibbs自由能方程,用以计算湘潭锰矿生态修复区植被系统的自由能(G)和物种化学势(μ)。生态修复区(及对照区)以泡桐(Paulownia fortunei)和栾树(Koelreuteria bipinnata)作为建群植物,总面积为4 hm~2,修复区泡桐和栾树的根际施用了含有自试验点废弃矿渣中筛选出的耐性菌株的有机菌肥,目的是为植物生长提供必要养分和降低根际土壤重金属毒性,对照区泡桐和栾树的根际施用了等量的化肥。泡桐和栾树种植后5 a期间,修复区与对照区均自然萌发生长了许多本土植物种类。试验结果表明,修复区植物种类数达到48,为对照区的3.7倍;修复区的总生物量、锰吸收量分别达到23324 kg/hm~2和4280 g/hm~2,为对照区对应值的20.6和2.6倍;修复区系统自由能G远远大于对照区的值,说明有机菌肥具有显著的改良污染土壤根际环境的效果。修复区和对照区植物种类之间的化学势μ均存在显著差异(P0.001),μ值差异范围分别为-3.79—6.76和-3.42—3.59,该一差异反映不同物种适应和修复锰污染环境的能力。G和μ值包含了生态系统生产力、生物多样性,植物种类生长势、重金属富集能力、生态学行为等综合信息,能反映生态系统与立地环境的关系和修复植物的生态学特性,可作为重金属污染区植被修复效果评价和修复植物筛选的重要指标。     

Potentially Active Iron,Sulfur, and Sulfate Reducing Bacteria in Skagerrak and Bothnian Bay Sediments

In many marine surface sediments, the reduction of manganese (Mn) and iron (Fe) oxides is obscured by sulfate reduction, which is regarded as the predominant anaerobic microbial respiration process. However, many dissimilatory sulfate and sulfur reducing microorganisms are known to utilize alternative electron acceptors such as metal oxides. In this study, we tested whether sulfate and sulfur reducing bacteria are linked to metal oxide reduction based on biogeochemical modeling of porewater concentration profiles of Mn²⁺ and Fe²⁺ in Bothnian Bay (BB) and Skagerrak (SK) sediments. Steady-state modeling of Fe²⁺ and Mn²⁺ porewater profiles revealed zones of net Fe (0–9 cm BB; ～10 and 20 cm SK) and Mn (0–5 cm BB; 2–8 cm SK) species transformations. 16S rRNA pyrosequencing analysis of the in-situ community showed that Desulfobacteraceae, Desulfuromonadaceae and Desulfobulbaceae were present in the zone of Fe-reduction of both sediments. Rhodobacteraceae were also detected at high relative abundance in both sediments. BB sediments appeared to harbor a greater diversity of potential Fe-reducers compared to SK. Additionally, when the upper 10 cm of sediment from the SK was incubated with lepidocrocite and acetate, Desulfuromonas was the dominant bacteria. Real-time quantitative polymerase chain reaction (qPCR) results showed decreasing dsrA gene copy numbers with depth coincided with decreased Fe-reduction activity. Our results support the idea that sulfur and sulfate reducing bacteria contribute to Fe-reduction in the upper centimeters of both sediments.     

动物血红素过氧化物酶参与细菌氧化Mn(Ⅱ)的研究进展

锰氧化物是自然环境中一种重要的高活性矿物,在多种元素的生物地球化学循环中起着重要作用。细菌对锰氧化物的形成具有推动作用。截至目前,研究者已从环境中分离出多株锰氧化细菌,并在氧化机理的研究上取得了一定的进展。目前细菌中已知的锰氧化酶包括多铜氧化酶和动物血红素过氧化物酶。与多铜氧化酶相比,动物血红素过氧化物酶在蛋白结构与氧化方式上都具有自己的特点。本文结合国内外最新研究结果,在氧化菌株、氧化酶和基因、氧化方式及影响因素等方面对动物血红素过氧化物酶参与细菌氧化Mn(Ⅱ)的研究进行了总结,对未来研究方向进行了展望。     

锰超氧化物歧化酶的催化原理与酶活性调节机制

锰超氧化物歧化酶(MnSOD)催化两分子超氧自由基歧化为分子氧和过氧化氢。超氧自由基被Mn³⁺SOD氧化成分子氧的反应以扩散的方式进行。超氧自由基被Mn²⁺SOD还原为过氧化氢的反应以快循环和慢循环两条途径平行进行。在慢循环途径中,Mn²⁺SOD与超氧自由基形成产物抑制复合物,然后该复合物被质子化而缓慢释放出过氧化氢。在快循环途径中,超氧自由基直接被Mn²⁺SOD转化为产物过氧化氢,快速循环有利于酶的复活与周转。本文提出温度是调节锰超氧化物歧化酶进入慢速或者快速循环催化途径的关键因素。随着在生理温度范围内的温度升高,慢速循环成为整个催化反应的主流,因而生理范围内的温度升高反而抑制该酶的活性。锰超氧化物歧化酶的双相酶促动力学特性可以用该酶保守活性中心的温度依赖性配位模型进行合理化解释。当温度降低时,1个水分子(或者OH^-)接近Mn、甚至与Mn形成配位键,从而干扰超氧自由基与Mn形成配位键而避免形成产物抑制。因此在低温下该酶促反应主要在快循环通路中进行。最后阐述了几种化学修饰模式对...     

The effect of postnatal manganese exposure on the NMDA receptor signaling pathway in rat hippocampus

Overexposure to manganese (Mn) is associated with neurological disorders in children. Evidence indicated that N‐methyl‐d ‐aspartate (NMDA) receptor signaling pathway was critical for neurobehavioral function. However, whether NMDA receptor signaling pathway contributes to Mn‐induced neurotoxicity remains unknown. In this study, newborn Sprague–Dawley rats were randomly assigned to four groups exposed to 0, 10, 20, and 30 mg/kg of Mn²⁺ by intraperitoneal injection (n = 10/group: five males and five females). After 3 weeks of Mn exposure, messenger RNA (mRNA) and protein expression of NMDA receptor subunits (NR1, NR2A, and NR2B), cAMP‐response element binding protein (CREB), and brain‐derived neurotrophic factor (BDNF) in hippocampus were measured by real‐time quantitative RT‐PCR and Western blot. In Mn‐exposed rats, decreased mRNA and protein expression of NR1, NR2A, and NR2B, CREB, and BDNF was observed. The results imply that downregulated NMDA receptor signaling pathway may be of vital importance in the neuropathological process of Mn‐induced neurotoxicity.     

锰对大豆若干生理特性的影响

利用水培法研究锰对浙春2号和浙春3号大豆根系活力及叶片脯氨酸、丙二醛和蛋白质的影响。结果表明,适量锰处理可提高大豆根系活力,降低叶片中脯氨酸、蛋白质和丙二醛含量;锰过量,不利于大豆生长。两个大豆品种对锰的反应有差异,浙春3号对锰的敏感性大于浙春2号。     

Lignocellulosic residues: Biodegradation and bioconversion by fungi

The ability of fungi to degrade lignocellulosic materials is due to their highly efficient enzymatic system. Fungi have two types of extracellular enzymatic systems; the hydrolytic system, which produces hydrolases that are responsible for polysaccharide degradation and a unique oxidative and extracellular ligninolytic system, which degrades lignin and opens phenyl rings. Lignocellulosic residues from wood, grass, agricultural, forestry wastes and municipal solid wastes are particularly abundant in nature and have a potential for bioconversion. Accumulation of lignocellulosic materials in large quantities in places where agricultural residues present a disposal problem results not only in deterioration of the environment but also in loss of potentially valuable material that can be used in paper manufacture, biomass fuel production, composting, human and animal feed among others. Several novel markets for lignocellulosic residues have been identified recently. The use of fungi in low cost bioremediation projects might be attractive given their lignocellulose hydrolysis enzyme machinery.