石墨烯/聚吡咯复合材料与电化学应用研究进展

石墨烯由于其特殊的单原子层结构决定了其具有丰富而新奇的物理化学性质.在发现后的短短十年间,已在物理学、化学、材料科学与工程等领域产生了重要的影响,成为备受瞩目的国际研究前沿和热点.在石墨烯的研究和应用中,最重要的问题就是如何实现其可控制备,组装及功能化应用.近年来,包括本课题组在内的国内外很多研究人员一直在积极探索石墨烯及其功能复合物的制备及应用新途径,其中石墨烯与导电高分子聚吡咯(PPy)的复合是研究的重要内容之一,并且取得了一系列有价值的研究成果.本文对石墨烯/PPy复合结构的可控制备进行了系统的归纳与总结,也讨论了其在催化、驱动器、超级电容器和传感器等电化学应用领域的最新进展,并对相关领域的发展趋势做了展望.     

气相色谱-质谱法测定猪肉中盐酸克伦特罗残留量

按NY/T 468-2006所述方法在碱性条件下,用乙酸乙酯提取和用盐酸溶液反萃取制得含有盐酸克伦特罗的试样溶液,调节溶液的酸度至pH 4.5后,经SCX固相萃取柱净化。在经净化后的试液中加入1.6mg·L-1美托洛尔溶液40μL作为内标。将溶液置于60℃水浴中吹氮蒸干,加入甲苯200μL和BSTFA衍生试剂100μL,于80℃烘箱中衍生1h。冷却后再加甲苯200μL,经DB-5MS毛细管柱分离,在SIM模式下进行MS测定,选择监测离子为m/z86(定量离子)和m/z262,243,187(定性离子)。内标法定量。盐酸克伦特罗的线性范围为16~512μg·L-1,其检出限(3S/N)为1.0μg·kg-1。以空白样品为基体进行加标回收试验,测得回收率在79.7%~86.6%之间,测定值的相对标准偏差(n=6)在4.8%~6.7%之间。     

Rapid Isolation of a Facultative Anaerobic Electrochemically Active Bacterium Capable of Oxidizing Acetate for Electrogenesis and Azo Dyes Reduction

In this study, 27 strains of electrochemically active bacteria (EAB) were rapidly isolated and their capabilities of extracellular electron transfer were identified using a photometric method based on WO₃ nanoclusters. These strains caused color change of WO₃ from white to blue in a 24-well agar plate within 40 h. Most of the isolated EAB strains belonged to the genera of Aeromonas and Shewanella. One isolate, Pantoea agglomerans S5-44, was identified as an EAB that can utilize acetate as the carbon source to produce electricity and reduce azo dyes under anaerobic conditions. The results confirmed the capability of P. agglomerans S5-44 for extracellular electron transfer. The isolation of this acetate-utilizing, facultative EBA reveals the metabolic diversity of environmental bacteria. Such strains have great potential for environmental applications, especially at interfaces of aerobic and anaerobic environments, where acetate is the main available carbon source.     

Chemical Proteomic Profiling of Protein 4′-Phosphopantetheinylation in Mammalian Cells

Protein 4′-phosphopantetheinylation is an essential post-translational modification (PTM) in prokaryotes and eukaryotes. So far, only five protein substrates of this specific PTM have been discovered in mammalian cells. These proteins are known to perform important functions, including fatty acid biosynthesis and folate metabolism, as well as β-alanine activation. To explore existing and new substrates of 4′-phosphopantetheinylation in mammalian proteomes, we designed and synthesized a series of new pantetheine analogue probes, enabling effective metabolic labelling of 4′-phosphopantetheinylated proteins in HepG2 cells. In combination with a quantitative chemical proteomic platform, we enriched and identified all the currently known 4′-phosphopantetheinylated proteins with high confidence, and unambiguously determined their exact sites of modification. More encouragingly, we discovered, using targeted chemical proteomics, a potential 4′-phosphopantetheinylation site in the protein of mitochondrial dehydrogenase/reductase SDR family member 2 (DHRS2).     

自支撑NH2-MIL-125/聚噁二唑复合正渗透膜的制备及性能

合成了高强度亲水性含羧基聚噁二唑材料(POD-COOH)和含氨基金属有机框架材料(NH₂-MIL-125), 以NH₂-MIL-125为填料, 与POD-COOH基体材料进行溶液共混, 并通过溶液浇铸法制备系列新型自支撑复合正渗透膜, 研究NH₂-MIL-125的引入对复合正渗透膜结构和性能的影响. 研究结果表明, 所制备的系列复合正渗透膜均呈致密结构, 且随着NH₂-MIL-125含量的增加, 复合膜的表面亲水性增加、 电负性增强, 并保持良好的机械性能. 以去离子水为进料液, 1.5 mol/L硫酸钠溶液为汲取液, 对上述自支撑复合膜进行正渗透性能测试, 发现由于消除了传统正渗透膜支撑层的内浓差极化现象, 该新型复合正渗透膜在分离过程中具有优异的正渗透性能.     

溶剂诱导翻转Pickering乳液用于原位循环使用酶催化剂

Separation and recycling of catalysts are crucial for realizing the objectives of sustainable and green chemistry but remain a great challenge, especially for enzyme biocatalysts. In this work, we report a new solvent-induced reversible inversion of Pickering emulsions stabilized by Janus mesosilica nanosheets (JMSNs), which is then utilized as a strategy for the in situ separation and recycling of enzymes. The interfacial active solid particle JMSNs is carefully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption experiments, Fourier transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA).The JMSNs are demonstrated to show order-oriented mesochannels with a large specific surface area, and the hydrophobic octylgroup is selectively modified on one side of the nanosheets. Furthermore, the inversion is found to be a fast process that is strongly dependent on the interfacial activity of the solid emulsifier JMSNs. Such a phase inversion is also a general process that can be realized in various oil/water phasic systems, including ethyl acetate-water, octane-water, and cyclohexane-water systems. By carefully analyzing the capacity of JMSNs with different surface wettabilities for phase inversion, a triphase contact angle (θ) close to 90° and a critical oil-water ratio of 1 : 2 are identified as the key factors to achieve solvent-induced phase inversion via a catastrophic phase inversion mechanism. Importantly, this reversible phase inversion is suitable for the separation and recycling of enzyme biocatalysts that are sensitive to changes in the reaction medium. Specifically, during the reaction, the organic substrates are dissolved in the oil droplets and the water-soluble catalysts are dispersed in the water phase, while a majority of the product is released into the upper oil phase and the enzyme catalyst is confined inside the water droplets in the bottom layer after phase inversion. The perpendicular mesochannels of JMSNs provide a highly accessible reaction interface, and their excellent interfacial activity allows for more than 10 rounds of consecutive phase inversions by simply adjusting the ratio of oil to water in the system. Using the enzymatic hydrolysis kinetic resolution of racemic acetate as an example, our Pickering emulsion system shows not only a 3-fold enhanced activity but also excellent recyclability. Because no sensitive chemical reagents are used in this phase inversion process, the intrinsic activities of the catalysts can be preserved even after seven cycles. The current study provides an alternative strategy for the separation and recycling of enzymes, in addition to revealing a new innovative application for Janus-type nanoparticles.     

通过赝反伽伐尼反应实现金纳米粒子模块替换

通过可控的方式精确调控纳米粒子的结构仍是一个富有挑战性和鼓舞人心的课题.尽管单原子或两、三个金属原子的精细调控已经在金纳米粒子中实现,涉及三个以上金属原子的取代（模块取代）还没有报道.本工作报道了环己硫醇配体保护的Au₄₈（CHT）₂₆的合成及其通过赝反伽伐尼过程的模块取代.单晶结构揭示模块取代的产物与母体团簇共用一个相似的Au₃₁（CHT）₁₂主体,但剩余部分不同（Au₆（CHT）₁₁ vs.Au₁₆（CHT）₁₄）.一个有趣的发现是模块取代抑制了Au₄₈（CHT）₂₆的光热过程,却增强了它的发射,赋予了所合成团簇更好的双（多）功能应用潜力.光热效应的减弱和发射的增强也暗示了这两种作用能够彼此至少部分转化,对于研究这两种效应之间的相互影响也具有重要的启示.     

Co9S8/MoS2异质结构的构筑及电催化析氢性能研究

利用前驱物形貌导向法,成功制备了Co₉S₈/MoS₂异质结构催化剂,该催化剂在碱性析氢反应（HER）中表现出优异的催化活性及稳定性,其在10 mA·cm^-2处的过电势仅为84 mV.通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）、电子自旋共振（ESR）、拉曼光谱（Raman）、X射线光电子能谱（XPS）和同步辐射（XAFS）等表征,证明了CoS₂/MoS₂在H₂氛围下煅烧形成Co₉S₈/MoS₂的过程中,CoS₂中Co的配位模式从部分八面体向Co₉S₈中的四面体转变,这种转变可活化MoS₂的惰性平面,从而使其更有利于吸附H^*.除此之外,接触角数据表明：该催化剂具有良好的亲水性,有利于电解液渗透及气体分子的迅速扩散,从而促进HER反应速率.由于异质结构间具有强烈的相互作用,该催化剂可表现出良好的结构稳定性.本工作基于Co₉S₈/MoS₂异质结构的成功构筑及对其HER催化机理的充分探讨,为后续硫化物异质结及其在电催化中的应用提供了良好的思路和研究基础.     

基于气液相化学发光技术的臭氧在线检测方法

基于鲁米诺(luminol) 化学发光体系,采用自主研发的在线臭氧浓度检测仪,建立了一种实时在线检测臭氧浓度的方法,用于分析测定痕量浓度水平的臭氧气体。 考察了鲁米诺、氢氧化钾、部分醇类化合物和表面活性剂等因素对化学发光强度的影响。 结果表明,在鲁米诺(0.005 mol/L)、氢氧化钾(0.05 mol/L)体系中加入乙二醇(体积分数1.5%)、甲醇(体积分数1.5%)、乙醇(体积分数1.0%)、丙三醇(体积分数3.0%)能显著增强鲁米诺体系检测O₃的化学发光信号,而甲醛溶液 (体积分数3.0%)能有效抑制NO₂信号的干扰。 同时,测得检测臭氧的检出限为1.26 μg/m³、相对标准偏差为0.32%,相对误差为0.75%。 利用该体系测定臭氧,具有信号稳定、精密度好、准确度高、检出限低等优点,适用于大气中微量O₃的在线连续检测。     

微信平台辅助的农科有机化学实验课混合式教学实践

利用微信公众平台和移动网络辅助教学的优点,改革农科院校中非化学专业公共基础有机化学实验课传统教学模式,构建了“课前翻转教学,课中解惑内化,课后巩固提高”的三段混合式新型教学模式,并对此类教学模式的构建原则,特色微信公众平台建设、应用情况及注意事项进行实践研究。