Using Terpene Synthase Plasticity in Catalysis: On the Enzymatic Conversion of Synthetic Farnesyl Diphosphate Analogues

Four synthetic farnesyl diphosphate analogues were enzymatically converted with three bacterial sesquiterpene synthases, including β-himachalene synthase (HcS) and (Z)-γ-bisabolene synthase (BbS) from Cryptosporangium arvum, and germacrene A synthase (SmTS6) from Streptomyces mobaraensis. These enzyme reactions not only yielded several previously unknown compounds, showing that this approach opened the door to a new chemical space, but substrates with blocked or altered reactivities also gave interesting insights into the cyclisation mechanisms and the potential to catalyse reactions with different initial cyclisation modes.     

综合传动装置起动扭矩测试试验研究

低温环境起动性能是表征车辆动力性能的一项重要指标。对液力机械传动车辆而言,由于综合传动装置自身技术特点,改善车辆起动性能除应当考虑发动机自身起动阻力外,还应当考虑综合传动装置的起动阻力。在系统分析综合传动装置技术特点和功率流向的基础上,总结了发动机起动过程的主要特征,提出采用稳态试验与动态试验相结合的台架试验方法进行综合传动装置起动扭矩测试。以某高速履带车辆为研究对象,进行了综合传动装置起动扭矩测试。试验结果表明,传动油温的变化和各类油泵的功率消耗是决定综合传动装置起动扭矩大小的关键因素,为改进车辆总体设计和提高车辆起动性能提供了依据。     

Complex thermal evaluation for 2,2′-azobis(isobutyronitrile) by non-isothermal and isothermal kinetic analysis methods

Azo compounds are widely used in dyes, pigments, blowing agents, and initiators. Unfortunately, these compounds contain the bivalent –N–N– composition which might be cleavaged readily even under high ambient temperature. The self-accelerating decomposition might cause a runaway reaction and lead to a fire or explosion when the cooling system fails or other upsets occur. To investigate the thermal stability parameters of 2,2′-azobis(isobutyronitrile) with thermal hazard and mechanism, differential scanning calorimetry and thermal activity monitor III were applied with non-isothermal method and isothermal method to obtain onset temperature (T ₀), maximum temperature (T _max), and heat of decomposition (ΔH _d). Thermal stability parameters play a pivotal role in thermal analysis, leading particularly to complex evaluation of the inherently safer design during preparation, processing, transport, or storage. The results provide sufficient thermokinetic parameters for process safety in terms of proactive loss prevention program.     

Fiber‐Based Flexible All‐Solid‐State Asymmetric Supercapacitors for Integrated Photodetecting System

Integrated nanodevices with the capability of storing energy are widely applicable and have thus been studied extensively. To meet the demand for flexible integrated devices, all‐solid‐state asymmetric supercapacitors that simultaneously realize energy storage and optoelectronic detection were fabricated by growing Co₃O₄ nanowires on nickel fibers, thus giving the positive electrode, and employing graphene as both the negative electrode and light‐sensitive material. The as‐assembled integrated systems were characterized by an improved energy storage, enhanced power density (at least by 1860 % enhanced) by improving the potential window from 0–0.6 V to 0—1.5 V, excellent photoresponse to white light, and superior flexibility of both the fiber‐based asymmetric supercapacitor and the photodetector. Such flexible integrated devices might be used in smart and self‐powered sensory, wearable, and portable electronics.     

纤维二糖与葡萄糖催化转化制备乙二醇(英文)

选用纤维二糖作为探针分子,探索纤维素催化转化制备乙二醇过程的反应路径.分别考察了纤维二糖和葡萄糖在双组分催化剂H2WO4和Ru/C下的催化反应活性.结果表明,乙二醇不仅来自于纤维二糖水解产物葡萄糖的逆羟醛缩合作用,同时也可以来自于纤维二糖的直接逆羟醛缩合过程.而且,纤维二糖的直接逆羟醛缩合作用对糖苷键的水解也有一定的促进作用.比较发现,钨基催化剂作用下纤维二糖的逆羟醛缩合反应活性比葡萄糖要低,因此乙醇醛可以缓慢产生并在Ru/C催化剂上迅速加氢生成乙二醇.使得以纤维二糖作为原料比以葡萄糖作为原料时获得更高的乙二醇收率.     

微波法制备还原氧化石墨烯负载Pt_3Co纳米合金(英文)

微波辐射法可以在数分钟内将高度分散的Pt3Co合金颗粒负载于还原氧化石墨烯表面上.表征结果发现,与传统的溶剂热法和浸渍法相比,微波法制备的催化剂中贵金属的利用率高,合金颗粒的分布均匀,组成可控,同时氧化石墨烯的再石墨化现象也得到有效地抑制.采用微波法制备的Pt3Co/RGO-MW催化剂在肉桂醛加氢反应中具有较高的活性和和产物选择性.Pt3Co/RGO-MW中每一个Pt原子在70℃的转化频率高达23.8 min-1.     

α-Al_2O_3比表面积标准物质的研制

选择市售α-Al2O3粉体作为比表面积标准物质候选材料,采用交叉缩分方法对标准物质样品进行分装。检验结果表明α-Al2O3标准物质样品具有良好的均匀性和稳定性(18个月)。采用国际公认的氮气物理吸附BET方法,联合测量能力经过确认的8家实验室对α-Al2O3标准物质样品进行定值,标准值比表面积为5.47 m2/g,不确定度为0.22 m2/g(k=2)。     

Single-Atom Iron Catalysts on Overhang-Eave Carbon Cages for High-Performance Oxygen Reduction Reaction

Single-atom catalysts have drawn great attention, especially in electrocatalysis. However, most of previous works focus on the enhanced catalytic properties via improving metal loading. Engineering morphologies of catalysts to facilitate mass transport through catalyst layers, thus increasing the utilization of each active site, is regarded as an appealing way for enhanced performance. Herein, we design an overhang-eave structure decorated with isolated single-atom iron sites via a silica-mediated MOF-templated approach for oxygen reduction reaction (ORR) catalysis. This catalyst demonstrates superior ORR performance in both alkaline and acidic electrolytes, comparable to the state-of-the-art Pt/C catalyst and superior to most precious-metal-free catalysts reported to date. This activity originates from its edge-rich structure, having more three-phase boundaries with enhanced mass transport of reactants to accessible single-atom iron sites (increasing the utilization of active sites), which verifies the practicability of such a synthetic approach.     

Oxygen- and Nitrogen-Embedded Zigzag Hydrocarbon Belts

Despite the aesthetically appealing structures and tantalizing physical and chemical properties, zigzag hydrocarbon belts and their heteroatom-embedded analogues remain challenging synthetic targets. We report herein the synthesis of diverse O/N-doped zigzag hydrocarbon belts based on selective bridging of the fjords of resorcin[4]arene derivatives through intramolecular S_NAr and palladium-catalyzed intermolecular C−N bond formation reactions. Preorganized conformations of mono-macrocyclic, half-belt and quasi-belt compounds were revealed to facilitate cyclization reactions to construct heteroatom-linked octahydrobelt[8]arenes. The acquired products had strained square-prism-shaped belt structures in which all six-membered heterocyclic rings adopted an unusual boat conformation with equatorially configured alkyl groups. The unprecedented heteroatom-bearing belts also exhibited different photophysical and redox properties to those of octahydrobelt[8]arene analogues.