Analysis of polynuclear aromatic hydrocarbons by glass capillary gas chromatography using simultaneous flame ionization and electron capture detection

The possibility of simultaneous application of an electron capture (ECD) and a flame ionization detector (FID) connected to a glass capillary column for analyzing polynuclear aromatic hydrocarbons (PNA) has been investigated. The ECD/FID ratio is determined for 46 PNA compounds. The ratios vary from 0.02 to 117 with relative standard deviations better than 20 percent determined from 10 replicate analyses. The results suggest that the method may be used for obtaining additional evidence in identifying PNA in environmental samples. Impurities and transformation products in the standard were identified by computerized glass capillary gas chromatography/mass spectrometry. Quinones and diones are responsible for the high EC-response determined in some trace components in the standard. An application of the method is shown for PNA from particulates in urban atmospheres.     

钐(II)类卡宾CH3SmCH2I与乙烯环丙烷化反应及溶剂化效应的理论研究

用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理. 对钐类卡宾试剂CH₃SmCH₂I和CH₂CH₂反应的反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化, 并计算了THF溶液的溶剂化效应, 用内禀反应坐标(IRC)计算和频率分析方法, 对过渡态进行了验证. 结果表明: CH₃SmCH₂I与CH₂CH₂环丙烷化反应按亚甲基转移机理(通道A)和卡宾金属化机理(通道B)都可以进行, 与锂类卡宾的反应机理相同, 通道A比通道B反应的势垒降低了14.65 kJ/mol. 溶剂化效应使通道B比通道A的反应势垒大幅度提高, 更有利于反应沿通道A进行, 而不利于通道B.     

Dynamics of superionic Rb3H(SeO4)2 single crystals studied by H and Rb spin-lattice relaxation

The ¹H and ⁸⁷Rb spin-lattice relaxation and spin-spin relaxation times in superionic Rb₃H(SeO₄)₂ single crystals grown by the slow evaporation method were measured over the temperature range 160-450 K. The temperature dependencies of the ¹H T₁, T_1ρ, and T₂ are measured. In the ferroelastic phase, T₁ differs from T_1ρ, which is in turn different from T₂, although these three relaxation times converge to similar values near 410 K. This transition seems to occur at temperature which is about 40 K lower than the superionic transition temperature. The observation of liquid-like values of the ¹H T₁, T_1ρ, and T₂ in the high temperature is compatible with the phase being superionic, indicating that the destruction and reconstruction of hydrogen bonds does indeed occur at high temperature. In addition, the ⁸⁷Rb T₁ and T₂ values at high temperature were similar (on the order of milliseconds), a trend that was also observed for ¹H T₁ and T₂. This behavior is expected for most hopping-type ionic conductors, and could be attributed to interactions between the mobile ions and the neighboring group ions within the crystal. The motion giving rise to this liquid-like behavior is related to the superionic motion.     

Recent progress and challenges in carboxylation with CO2

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树脂填充EVAL纤维吸附剂的制备及其吸附性能表征

采用具有亲水性的乙烯-乙烯醇共聚物(EVAL)作为纤维吸附剂基质材料,粉末型Lewatit阳离子交换树脂CNP80ws为功能材料,采用可控相分离方法,制备了不同表面形态结构的树脂填充EVAL吸附剂.当使用外部液体调控相分离过程时,在纤维的表面形成了粗糙的开孔结构,并且随树脂的填充量提高纤维表面的粗糙度与开孔度有所提高.研究结果表明:树脂填充EVAL纤维吸附剂具有较大的吸附容量与较高的脱附率,其吸附容量不低于53.9mg BSA/g吸附剂(树脂填充量50%).     

Experimental and density functional studies on two structurally similar antipyrine derivatives: 4-(2-hydroxy-5-nitrobenzylidene-amino)-1,2-dihydro-1,5-dimethyl-2-phenylpyrazol-3-one and 4-(3-bromo-5-chloro-2-hydroxybenzylideneamino)-1,2-dihydro-1,5-dimethyl-2-phenylpyrazol-3-one

The Schiff base compounds, 4-(2-hydroxy-5-nitr- obenzylideneamino)-1,2-dihydro-1,5-dimethyl-2-phenylpy- razol-3-one and 4-(3-bromo-5-chloro-2-hydroxybenz- ylideneamino)-1,2-dihydro-1,5-dimethyl-2-phenylpyrazol-3-one, have been synthesized and characterized by elemental analysis, IR, and X-ray single crystal determination. Density functional calculations of the structures, natural bond orbitals, and frontier molecular orbitals and Mülliken charge analysis on the compounds were performed at B3LYP/6-31+G(d) level of theory. Vibrational frequencies were also predicted, assigned, and compared with the experimental values, which supported each other.     

A bird nest-like manganese dioxide and its application as electrode in supercapacitors

A novel bird nest-like nanostructured MnO2(BNNS-MnO2) was prepared by a facile and cost-effective strategy. Their structures and morphologies were characterized by field emission scanning electron microscopy, transmission electron microscopy and powder X-ray diffraction. Capacitive behaviors were investigated by cyclic voltammetry and galvanostatic charge-discharge. The obtained nano-MnO2 possesses a well designed loose-assembled hierarchical nanoarchitecture with an appropriate crystallinity which gives rise to excellent performances as an electrode material for supercapacitors. A maximum specific capacitance of 917 F/g has been obtained at a current density of 5 mA/cm2 in 6 mol/L KOH aqueous solution, and a specific capacitance of 210 F/g has been maintained for 500 cycles. As the low cost of MnSO4 and KCr2O7 and the low reaction temperature, the present method avoids the requirements for complicated operations, time/energy-consuming and expensive reagents, and perhaps is ready for the industrialization of nano-MnO2 production.     

化学蒸气发生-电感耦合等离子体原子发射光谱法测定地质样品中痕量金

地质样品经盐酸-硝酸(3+1)混合酸溶解,活性炭分离富集后,于90℃用12g.L-1硼氢化钠溶液(溶于0.5g.L-1氢氧化钠溶液中)作还原剂,用化学蒸气发生-电感耦合等离子体原子发射光谱法测定其中痕量的金。金的质量浓度在1 500μg.L-1以内与其发射强度呈线性关系,方法的检出限(3s)为0.59μg.L-1。方法用于测定2个标准物质(GBW 07289和GBW 07291)中金含量,测定值与认定值相符。     

A cation trap for anodic stripping voltammetry: NH3–plasma treated carbon nanotubes for adsorption and detection of metal ions

NH₃–plasma treated multi-walled carbon nanotubes (pn-MWCNTs) with cation traps for the detection of ultratrace quantities of Zn(II), Cd(II), Cu(II), and Hg(II) using square wave anodic stripping voltammetry (SWASV) is described. The pn-MWCNTs use their adsorption performance to enhance the sensitivity. It is found that under optimized conditions Zn(II), Cd(II), Cu(II) and Hg(II) were individually detected at potentials of −1.16, −0.78, −0.268 and 0.108 V, respectively. The detection limit (3σ method) of 0.314, 0.0272, 0.2263, and 0.1439 nM toward Zn(II), Cd(II), Cu(II), and Hg(II) is achievable, respectively. No interference could be seen during the simultaneous detection of Zn(II), Cd(II), Cu(II), and Hg(II). The pn-MWCNTs exhibit excellent selectivity owing to the different ability of adsorption. A study of the ability of pn-MWCNTs in practical application is carried out using a sample of water collected from Dongpu Reservoir in Hefei City, Anhui, China. It is found that the results were favorable when compared against inductively coupled plasma atomic emission spectrometry (ICP-AES) analysis.