气相色谱法测定饮用水及其源水中灭草松和2,4-滴

采用气相色谱ECD检测器同时分离检测水中灭草松和2,4-滴两种农药.水样中灭草松和2,4-滴在酸性条件下经乙酸乙酯萃取,然后用碘甲烷溶液酯化,生成较易挥发的甲基酯类衍生物,用毛细管气相色谱-电子捕获检测器分离测定.对衍生方式、温度和时间进行了优化,分别使用ECD和FPD检测器测定灭草松,而ECD检测灵敏度高.本法的最低检测质量浓度为灭草松0.15 μg/L,2,4-滴0.050 μg/L.方法灵敏度和精密度均满足分析要求.     

阻抑动力学光度法测定痕量间二硝基苯

在盐酸介质中，痕量间二硝基苯能灵敏地阻抑Fe^3 催化高碘酸钾氧化孔雀绿的反应。研究了该阻抑反应的最佳条件及动力学参数，建立了测定痕量间二硝基苯的新方法，间二硝基苯的线性范围为0.0-10.0μg/L，检出限为1.8μg/L。该法灵敏、简便，选择性好，用于环境水样中间二硝基苯的测定，结果准确。     

三正丁基膦参与的二苯联硒与吖啶及环氧化合物的开环反应

Aziridines and epoxides were reacted with diphenyl diselenide in the presence of a stoichiometric amount of （n-Bu）3P, respectively, giving β-amino- or β-hydroxy selenides in moderate to excellent yields under mild conditions. In the reactions the （n-Bu）3P might act as a reductant though it was a nucleophilic catalyst in other similar ring-opening reactions.     

Rare‐Earth Metal Alkyl Complexes with 3‐Arylamido‐Functionalized Indolyl Ligands: Synthesis,Characterization and Reactivity†

A series of dinuclear rare‐earth metal alkyl complexes {[μ‐η²:η¹:η¹‐3‐( L NCH)(CH₂SiMe₃)Ind]RE(CH₂SiMe₃)(THF)}₂ ( L ¹ = 2‐^tBuC₆H₄, RE = Y, Gd, Dy, Er, Yb; L ² = 2,4,6‐Me₃C₆H₂, RE = Dy, Er; Ind = indolyl) and {[μ‐η²:η¹:η¹‐3‐( L NCH₂)Ind]RE(CH₂SiMe₃)(THF)}₂ ( L ¹, RE = Y, Dy, Er, Yb; L ², RE = Er, Yb) bearing 3‐arylamido functionalized indolyl ligands having diverse bonding modes with metal ions were synthesized either by the insertion reaction of the imino group to the RE—C bond or by the alkane elimination reaction. In the preparation of above complexes, rare‐earth metal alkyl complexes [μ‐η⁵:η¹:η¹‐3‐( L ²NCH)(CH₂SiMe₃)Ind]Gd(CH₂SiMe₃)(THF)}₂ with a μ‐η⁵:η¹:η¹ coordination mode to the gadolinium ion and {[μ‐η³:η¹:η¹‐3‐( L ²NCH₂)Ind]Dy(CH₂SiMe₃)(THF)}₂ with a μ‐η³:η¹:η¹ coordination mode to the dysprosium ion were unexpectedly isolated. The reactions of 3‐( L ²N=CH)Ind with Er(CH₂SiMe₃)₃(THF)₂ at room temperature, generated a tetranuclear imino‐indolyl erbium intermediate {[μ‐η¹:η¹‐3‐( L ²N=CH)Ind]Er(CH₂SiMe₃)₂(THF)}₄, which can transform into the amido functionalized indolyl erbium complex in hot toluene. Moreover, the reactivities of the newly synthesized ytterbium complex with N‐heterocyclic compounds were investigated, affording the corresponding products of the mixed pyridyl‐indolyl, imidazolyl‐indolyl, and ortho‐metalated complexes. The yttrium complexes showed a high regioselectivity and steroselectivity for the isoprene polymerization with 1,4‐trans selectivity up to 91.7% and 1,4‐cis selectivity up to 96.1% in the presence of cocatalysts, respectively.     

L-半胱氨酸自组装膜修饰金电极的电化学特性

采用电化学石英晶体微天平（EQCM）和循环伏安法（CV）研究了L-半胱氨酸在金电极表面形成自组装膜的机理及其电化学性质.结果表明, L-半胱氨酸分子在金电极表面有特性吸附，而且在等电点pH附近因静电引力和氢键作用形成分子对，从而自组装形成双层膜.该膜电极在0.2 mol•L－1的醋酸缓冲溶液中，于－0.2～0.5 V(vs SCE)间CV扫描出现了一对稳定的氧化还原峰，并对抗坏血酸的氧化有良好的催化作用.     

一维链状2-氧-1(4H)-吡啶乙酸桥联钙配位聚合物[Ca(2-OPA)2(H2O)2]n的合成、晶体结构及热稳定性研究

A novel coordination polymer of [Ca(2-OPA)₂(H₂O)₂]_n (2-OPA-=2-oxo-1(4H)-pyridineacetate anion) was synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex crystallizes in orthorhombic with space group Pna2₁, a=0.799 96(16) nm, b=0.823 77(16) nm, c=2.415 3(5) nm, V=1.591 6(6) nm³, Z=4, R=0.030 3, wR=0.070 0. The Ca atom is eight-coordinated by six O atoms of four 2-OPA^- ligands and two water molecules, and displays a dodecahedron coordination geometry. Each 2-OPA^- ligand bridges two adjacent Ca atoms, forming a infinite chain along the a direction. The Ca…Ca distance is 0.4102 2(8)nm. A two-dimensional supramolecular framework is further constructed by the hydrogen bonds and the weak π-π interactions. The results of TG analysis show the chain structure of the title complex was stable under 297.5 ℃. CCDC: 251669.     

人尿中合成麻醉镇痛剂的系统分析

采用液－液萃取结合ＧＣ／ＭＳ选择离子的方法，建立了人尿中８种合成麻醉镇痛剂的分析方法，讨论了回收率和检测限问题，并成功地用于实际尿样检测。     

Keggin结构的磷钨钒稀土四元杂多配合物对过氧化氢分解的催化作用

在磷钨钒稀土四元杂多配合物中，由于Ｖ原子的使用，使其对Ｈ２Ｏ２分解的催化活性显著增加。因配合物中心原子稀土元素不同。催化活性也随之变化，其活化能与三阶稀土离子的电离能有密切关系。动力学曲线为Ｓ型。实验证明，在反应过程中有反应活性中间体生成。     

Electrospray and matrix-assisted laser desorption/ionization mass spectral characterization of linear single nylon-6 oligomers

Synthetic nylon-6 single molecular mass oligomers were studied by matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) mass spectrometry. These oligomers, considered as model compounds for the study of nylon-6 polymers, gave good mass spectrometric results using both MALDI and ESI. In spite of the gentle nature of both techniques, the MALDI and ESI spectra showed evidence of end-group cleavage from the oligomer chains. MALDI-MS was found to give similar fragmentation patterns for all of the oligomer samples. An increase in doubly charged ion signals with increasing oligomer mass was observed in the ESI mass spectra, as was end-group fragmentation. Signals from oligomer clusters were observed in ESI-MS for the dimer, tetramer and hexamer, most likely due to non-covalent bonding among the low-mass oligomer molecules.