气相色谱法测定污染空气中恶臭硫化物

应用固相微萃取(SPME)预处理技术,采用脉冲火焰光度检测器(PFPD)-气相色谱法(GC)测定污染空气中硫化氢、二硫化碳、甲硫醇、1,2-乙二硫醇、甲硫醚、羰基硫6种恶臭硫化物.同时探讨了SPME及色谱的最佳条件.所得各物质的校正曲线相关系数在0.998 0～0.999 4之间,检出限在1.9～4.1 pg之间,加标回收率在89%～102%之间,测定结果的RSD值在1.3%～3.1%之间,所建立方法应用于实际样品分析,获得满意结果.     

掺杂Co2+和Sm3+对纳米ZnFe2O4铁氧体的电磁损耗性质的影响

采用NaHCO3与FeCl3?6H2O,ZnSO4?7H2O,Co(NO3)2?6H2O和Sm(NO3)3?6H2O进行室温固相反应制得碱式碳酸盐和氢氧化铁混合前驱物,先微波加热,再热分解分别制得复合氧化物ZnFe2O4,Co0.5Zn0.5Fe2O4和Co0.5Zn0.5Fe1.95-Sm0.05O4.由激光粒度分析仪、XRD和SEM表征:获得了颗粒分布均匀、平均粒度为62nm左右的立方晶系尖晶石结构的纳米铁氧体粉体.并测试样品的相对介电常数和相对磁导率,研究了它们的电磁损耗特性.结果表明:在ZnFe2O4中,掺入Co2 ,Sm3 元素可以在100～1800MHz测试频率范围内不同程度提高材料的电磁损耗特性.     

多环芳烃与不饱和自由基氢提取反应类的动力学研究

对2~6个环的多环芳烃的氢提取反应类进行了系统研究, 提取氢原子的不饱和自由基包括丙炔基自由基（C₃H₃）、 烯丙基自由基（C₃H₅）、 丁二烯基自由基（nC₄H₅, iC₄H₅）、 环戊二烯基自由基（C₅H₅）以及苯基自由基（C₆H₅）. 采用M06-2X/cc-pVTZ方法得到了多环芳烃的电子结构信息, 利用过渡态理论并结合Eckart隧道校正, 计算了所有反应在500~2500 K范围内的反应速率常数.考察了多环芳烃的大小、 结构对反应速率常数的影响, 对比了不同氢提取自由基及不同氢提取反应类型的速率常数. 结果表明, 多环芳烃的大小对反应速率常数影响不大, 但是多环芳烃的环结构对反应速率常数影响较大. 将不同的氢提取反应类简化为发生在五元环上的C₅类和发生在六元环上的C₆类两类, 结果表明, C₆类的反应活性高于C₅类. 研究了nC₄H₅, iC₄H₅以及C₆H₅自由基与多环芳烃的氢提取反应, 它们的氢提取反应活性大小顺序为C₆H₅>nC₄H₅>iC₄H₅. 通过对每类典型反应的速率常数取平均值, 总结出相应类型的速率规则, 可用于构建多环芳烃和碳烟机理.     

“食品中的铁元素检验”教学实验条件的优化*

2019年人教版普通高中化学必修一新增了“检验食品中的铁元素”实验,按照该实验方案检测菠菜中的铁元素,由于色素干扰不能观察到明显的实验现象。鉴于此,采用提取液显色后的色度透过率作为评价指标,以控制变量法为实验方法,对常见含铁食品、铁元素提取方法、提取时间、提取剂中盐酸浓度和提取剂用量等条件进行了研究和优化。优化后的实验结果表明:采用2 g豆筋、20 mL浓度为4 mol/L的盐酸、破壁机搅拌提取5 min后的提取液显色,其色度值为62%,显示很明显的血红色。此实验方案能够有效证明食品中铁元素的存在,具有明显的实验现象,能应用于教师演示实验和学生分组实验。     

基于丝线流动显示技术的内转进气道起动性能实验

采用丝线法流动显示技术,在高超声速冷流暂冲式下吹风洞开展了快速获取内转进气道起动性能的实验研究。实验在中国空气动力研究与发展中心（CARDC）Φ0.5 m高超声速风洞中进行,来流Mach数为5。实验模型为椭圆转圆形内转进气道,总收缩比为5.8,内部收缩比为1.7,喉部为直径50 mm的圆形截面。模型的肩部区域种植了长度与间隔可更换的丝线,为了改善进气道的起动性能,模型进气道的内压缩段开设了可以动态堵塞的泄流孔,在喉道下游设置了可动态节流的节流锥。实验获得了丝线长度、相邻丝线间隔的推荐值,同时表明,丝线流动显示技术能够快速、准确、直观、方便地判断进气道的起动状态,并能定量给出流动分离起始位置与分离结构,所采用的丝线流动显示技术丰富了高超声速风洞实验的流场可视化方法库。研究还表明,采用丝线流动显示技术,所研究的内转进气道在Ma＝5时处于双解区,实验给出了进气道重起动及退出不起动的一种可行方案。      

高超声速再入体表面热解烧蚀效应数值模拟

表面防热材料热解与烧蚀效应研究在高超声速飞行器总体设计中具有重要应用价值。以热解烧蚀效应对飞行器目标特性及通信性能影响的预测评估为背景, 从化学非平衡气体动力学方程及固体热传导方程出发, 建立了气-固交界面上热解烧蚀壁面边界条件的一般形式及热物理化学模型, 发展了高超声速再入体绕流流场与表面材料内部温度场耦合求解的数值模拟方法, 并对计算模型和数值方法的可靠性进行了验证分析。在此基础上针对复杂外形再入体及表面硅基防热材料, 开展了典型再入条件下再入体绕流及尾流流场的数值模拟, 重点分析了表面材料热解烧蚀效应对流场等离子体分布的影响。研究表明: 在表面材料中不含碱金属杂质的情况下, 热解与烧蚀效应对流场中等离子体分布影响较小, 而在含有微量碱金属杂质的情况下, 热解与烧蚀效应对流场中等离子体分布及化学组分分布具有很大影响, 由此对再入目标特性与电磁通信性能带来的影响不容忽视。      

Detonation development in PRF/air mixtures under engine-relevant conditions

The development of advanced boosted internal combustion engines (ICEs) is constrained by super-knock which is closely associated with end gas autoignition and detonation development. The present study numerically investigates the transient autoignition and detonation development processes under engine-relevant conditions for primary reference fuel (PRF) consisting of n-heptane and isooctane. The effects of PRF composition are systematically examined. By considering the transient local sound speed rather than its initial value, a new non-dimensional parameter is proposed to assess the transient chemical-acoustic interaction and to quantify the autoignition modes. Two detonation sub-modes, normal and over-driven detonation, are identified and the corresponding mechanisms are interpreted. For the over-driven detonation, there exist two developing regimes with weak/strong chemical-acoustic coupling and slow/rapid pressure enhancement. It is found that the maximum pressure caused by autoignition decreases with the blending ratio of isooctane, mainly due to the increase in excitation time. Besides, the strongest detonation induced by hot spot usually occurs within the over-driven detonation sub-regime. Its condition can be well quantified by the new non-dimensional parameter proposed in work and its strength is determined by the ratio of hot spot acoustic time to excitation time. The deviation of transient autoignition front propagation from prediction based on homogenous ignition is mainly attributed to the non-uniform compression effect caused by gradually enhanced pressure wave, while the influence of heat conduction and mass diffusion is negligible. The initial expansion stage dominating the induction period of local autoignition is greatly influenced by the compression of pressure wave. Therefore, the continuously enhanced pressure wave non-uniformly changes the local ignition delay (i.e. reduces its spatial gradient) within the hot spot and thereby accelerates the autoignition front propagation. The relationship among the parameters quantifying the detonation propensity is assessed and interpreted. The present study provides helpful understanding of detonation development under engine conditions.     

铁氨基黏土-葡萄糖氧化酶纳米复合催化剂的构筑及多酶级联反应研究

以铁氨基黏土(FeAC)为载体, 通过共价交联固定葡萄糖氧化酶(GO_x), 构筑了铁氨基黏土-葡萄糖氧化酶纳米复合催化剂(FeAC-GO_x). 利用FeAC的过氧化物酶活性, 与GO_x结合进行级联反应, 可催化葡萄糖转化为过氧化氢并产生显色反应; 采用扫描电子显微镜(SEM)、 X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)对FeAC-GO_x进行了形貌和结构表征, 并评价了其酶动力学参数、 催化稳定性和重复使用性等. 结果表明, GO_x的固定化率可达到76.4%, 所构筑的纳米结构酶复合体系具有高效的级联催化能力. 与天然酶体系相比, FeAC-GO_x具有更优异的温度和pH耐受性, 且在重复使用6次后, 酶催化活性无明显降低. 该体系不仅为新型葡萄糖传感器的开发奠定了基础, 还为多酶级联纳米结构酶的构筑提供了新思路.     

Accelerated discovery of novel high-performance zinc-ion battery cathode materials by combining high-throughput screening and experiments

Aqueous zinc ion batteries (AZIBs) have attracted much attention in recent years due to their high safety, low cost, and decent electrochemical performance. However, the traditional electrodes development process requires tedious synthesis and testing procedures, which reduces the efficiency of developing high-performance battery devices. Here, we proposed a high-throughput screening strategy based on first-principles calculations to aid the experimental development of high-performance spinel cathode materials for AZIBs. We obtained 14 spinel materials from 12,047 Mn/Zn-O based materials by examining their structures and whether they satisfy the basic properties of electrodes. Then their band structures and density of states, open circuit voltage and volume expansion rate, ionic diffusion coefficient and energy barrier were further evaluated by first-principles calculations, resulting in five potential candidates. One of the promising candidates identified, Mg₂MnO₄, was experimentally synthesized, characterized and integrated into an AZIB based cell to verify its performance as a cathode. The Mg₂MnO₄ cathode exhibits excellent cycling stability, which is consistent with the theoretically predicted low volume expansion. Moreover, at high current density, the Mg₂MnO₄ cathode still exhibits high reversible capacity and excellent rate performance, indicating that it is an excellent cathode material for AZIBs. Our work provides a new approach to accelerate the development of high-performance cathodes for AZIBs and other ion batteries.     

Rapid detection of pathogenic bacteria based on a universal dual-recognition FRET sensing system constructed with aptamer-quantum dots and lectin-gold nanoparticles

The threat to public health from bacterial infections has led to an urgent need to develop simpler, faster and more reliable bacterial detection methods. In this work, we developed a universal dual-recognition based sandwich fluorescence resonance energy transfer (FRET) sensor by using specific aptamer-modified quantum dots (Aptamer-QDs) as energy donor and lectin concanavalin A (Con A) modified gold nanoparticles (Con A-AuNPs) as energy acceptor to achieve rapid and sensitive detection of Escherichia coli (E. coli) within 0.5 h. In the presence of the target E. coli, the energy donor of Aptamer-QDs and acceptor of Con A-AuNPs were close to each other, causing changes of FRET signals. Based on the constructed FRET sensor, a linear detection range of from 10² cfu/mL to 2 × 10⁸ cfu/mL with the detection limit of 45 cfu/mL for E. coli was achieved. Furthermore, the FRET sensor was applied to detect E. coli in the milk and orange juice with the detection limit of 300 cfu/mL and 200 cfu/mL, respectively and recovery rate from 83.1% to 112.5%. The strategy holds great promise in pathogenic bacteria detection due to its rapid and sensitivity.