Iodine(III)-Mediated Migratory gem-Difluorinations: Synthesis of β Transformable Functionality Substituted gem-Difluoroalkanes

Geminal-difluoroalkanes featuring intriguing steric and electronic properties are of great significance in medicinal chemistry, and great progresses have been achieved for their synthesis. In recent years, iodine(III) reagent-mediated migratory gem-difluorination of alkenes has proved to be an efficient and powerful strategy to access to diverse gem-difluoroalkanes, especially those bearing a readily transformable functionality (TF), which are important for rapid assembly of complex gem-difluorinated molecules in a modular and diverse manner. In this review, we systematically summarize the recent development of iodine(III)-mediated migratory gem-difluorination reactions for the synthesis of gem-difluoroalkanes bearing a synthetically versatile TF at the β position. The reaction mechanism and the utilities of the products are also discussed. This review is presented and grouped basically according to the types of transformable functionalities within the products.     

催化裂解-金汞齐富集-冷原子吸收光谱仪测定土壤样品中总汞含量

为建立采用催化裂解-金汞齐富集-冷原子吸收光谱仪即直接测汞仪测定土壤样品中汞含量的方法,本研究配制汞总量为0~2 ng、0~15 ng和25~1023 ng的三种不同汞浓度系列的标准工作曲线,选取9个土壤样品,3种国家土壤有证标准物质,同一样品分别进行6组平行测定,并抽取3个土壤样品进行3种不同浓度加标回收试验,以对其方法精密度和准确度进行论证。 结果显示：仪器信号值与Hg总量之间均呈良好的线性关系。根据仪器多次测定空白数据结果,按照称样量0.1 g计算,方法最小检出量为0.09 ng/g;平行测定结果相对标准偏差均小于10%,土壤标准物质测定值与标准物质标准参考值均相符,不同浓度的加标回收率范围为78.4%～92.7%。结果表明催化裂解-金汞齐富集-冷原子吸收光谱仪,可用于批量土壤样品中汞含量的快速测定分析,方法的精密度和准确度可满足测定分析要求,且实验过程中无需前处理消煮,操作方便、快速高效。     

增敏剂改进超级微波消解-电感耦合等离子体质谱(ICP-MS)法测定食品中硒元素

合适比例增敏剂会对超级微波消解-电感耦合等离子体质谱法(ICP-MS)测定食品中硒元素含量具有一定的优化效果。本文采用超级微波消解仪对1.0 g食品样品进行全消解,采用碰撞池模式规避质谱干扰,内标校正非质谱干扰,选择甲醇、乙醇、乙酸、异丙醇、丙三醇作为增敏剂,并调整测试过程中的添加比例,用电感耦合等离子体质谱法测定。结果表明：2%异丙醇存在时硒元素各同位素响应值最高,其中78Se具有低至0.0003 mg·kg-1的方法检出限;用以上方法对食品标准物质（GSB-8、GSB-9、GSB-24、GSB-30）及实际样品进行分析,标准物质测定值均在其认定值及不确定度范围内,相对误差小于-5.4%;实际样品测定值的相对标准偏差（n=7,RSD）为0.3~1.7%,加标回收率为99.2~105%。本方法操作简便,精密度好,准确度高,可以作为各类食品样品中硒含量测试方法。     

Experimental study on synchrotron radiation photoionization of secondary organic aerosol derived from styrene ozonolysis

Secondary organic aerosol (SOA) produced by ozonolysis of styrene and other alkene compounds is a major part of fine particles in urban atmospheres. The atmospheric ozonolysis process of styrene is simulated in a smog chamber, and the formed SOA particles are detected on-line by a synchronous radiation vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) in this study. Through molecular ion peaks in the photonionization mass spectra of SOA and the corresponding photoionization efficiency curve, combined with off-line measurement verification of ultraviolet visible and infrared absorption spectra, it is determined that formaldehyde, formic acid, benzene, phenol, benzaldehyde, and benzoic acid are the main constituents of styrene SOA. These provide new information for studying the atmospheric ozonolysis oxidation mechanism of styrene. VUV-PIMS can get over complicated sample preparation procedures, secondary pollution, and other shortcomings of the off-line method and is a useful instrument to measure constituents and unveil the formation process of SOA particles.     

An insight into the electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction

Journal of Solid State Electrochemistry - The electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction were investigated as a function...     

高效液相色谱串联质谱法测定含藻水氯化消毒后7种亚硝胺物质

采用液相色谱串联质谱法(LC/MS/MS)测定含藻水氯消毒产生7种亚硝胺类(NAms)消毒副产物(NDMA,NMEA,NDEA,NDPA,NDBA,NPyr,NPip).方法检出限分别为5.0,14,8.6,3.6,2.9,6.3和4.9 ng/L,相关系数r＞0.999.除NDBA回收率(60％)较低外,其余6种亚硝胺回收率均在80％～120％之间,相对标准偏差为1.4％～12.6％.分别以藻原液和消毒后藻液配制基质标准曲线,采用其与纯水标准曲线斜率之比评估基质效应.藻原液的基质效应为0.79 ～0.94,藻液消毒后NDMA基质效应为0.36,其他亚硝胺为0.63～0.96.应用此方法检测了自来水、富营养江河水、景观水及藻类悬浮液氯消毒后的亚硝胺含量.     

不同次级结构的硫酸钡多晶体制备研究

以过氧化钡(Ba O2)晶体为母体钡源,利用溶液中碱性条件下过氧化氢电离控制Ba O2分解速度,结合过量SO42-制备了具有Ba O2宏观形貌的Ba SO4多晶体,该多晶体由条形结构单元组成。进一步通过不同聚合物添加剂调节次级结构单元的形貌,在溶液中引入聚苯乙烯磺酸钠制备了由球形次级结构单元组成的Ba SO4多晶体;而在不同浓度的聚丙烯酸添加剂作用下,可制得由纳米颗粒和纳米棒状结构单元组成的Ba SO4多晶体。制备的多晶体材料为具有母体材料统一宏观形貌的大颗粒,其次级结构可通过聚合物添加剂调控,为合成具有特定形貌的功能晶体材料提供了一个新的途径。     

加速溶剂萃取-凝胶色谱净化高效液相色谱法测定动物源性食品中的胆固醇

采用加速溶剂萃取-凝胶色谱净化建立了动物源性食品中胆固醇检测的高效液相色谱方法。结果表明,胆固醇浓度在1.0~40.0mg/L范围内线性关系良好,加标回收率为89.1%~99.8%,相对标准偏差为3.1%~7.8%。该方法准确、灵敏度高,适用于富含脂类的动物源性食品中胆固醇的检测。     

粘塑性薄壁管中复合应力波的传播特性研究

以本构关系一般理论为基础,导出了计及材料功硬化效应和应变率硬化效应的粘塑性薄壁管的本构关系及管中复合应力波的控制方程,应用有限差分方法研究了在压扭复合冲击载荷作用下粘塑性薄壁管中复合应力波的传播特性与演化规律,分析了复合应力波的耦合效应以及薄壁管中粘塑性参数和功硬化效应对复合应力波传播与演化规律的影响,并对有关现象进行了分析和解释。     

Np原子外壳层电子波函数性质的理论研究

利用基于多组态Dirac-Fock(MCDF)方法的原子结构性质计算程序包GRASP 2K,在考虑和不考虑相对论效应的情况下,分别计算了超铀元素镎的外壳层电子轨道波函数和轨道束缚能,分析了相对论效应对轨道波函数以及束缚能的影响,并讨论了相对论效应对锕系元素原子半径收缩的影响.