基态Hse分子及Hsex(x=+1,-1) 离子的量子力学计算

用原子-分子反应静力学原理推导出了HSe分子、HSe^x（x=＋1，-1）离子的基态电子状态及其离解极限．在cc—pVDZ水平基础上，用B3LYP方法计算了它们的平衡核间距Re和离解能De．并在计算出来的一系列单点势能基础上，用正规方程组拟合Murrell—Sorbie（M—S）势能函数，得到相应态的解析势能函数，由此计算对应的光谱参数（Be，αe，ωe，ωe，χe）和力学性质，计算结果表明HSe分子、HSe^x（x=＋1，-1）离子可稳定存在．     

导数-同步荧光法同时测定苯甲酸和水杨酸

本文建立了一种同时测定苯甲酸、水杨酸的新方法.苯甲酸、水杨酸的检测限分别为 0.026 μg/mL,0.083 μg/mL;相对标准偏差分别为 1.8％和 3.1％.将该方法用于商品杀菌防腐剂中苯甲酸及水杨酸的同时测定,结果满意.     

[Co(HOC10H6COO)2(H2O)4]配合物的合成、晶体结构和性质研究

Complex [Co(HOC₁₀H₆COO)₂(H₂O)₄] was synthesized by reaction of hydroxy-2-naphthoic acid with CoCl₂·6H₂O. The compound was characterized by elemental analysis, IR and the structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P2₁/n with a=0.675 8(2) nm, b=0.518 15(14) nm, c=2.962 9(9) nm, β=94.925(8)°. V=1.033 6(5) nm³, Z=2, D=1.624 Mg·m^-3, F(000)=522. The Co atom has an octahedron coordination geometry and was six-coordinated with two oxygen atoms from two carboxylate ligands and four oxygen atoms from four water molecules. The complex molecules were linked by different hydrogen bonds to form a 2D network. The complex has thermal stability and shows a strong fluorescent emission at 421 nm (λ_ex=342 nm). CCDC: 250903.     

催化荧光法测定痕量Mn(Ⅱ)的研究

利用Mn(Ⅱ)对高碘酸钾氧化还原型罗丹明B的催化作用,建立了荧光增强测定痕量锰的新方法,用初始速率法研究了最佳反应条件。在此条件下,方法的线性范围为0.08～2.0ng·ml~(-1),检出限为0.028ng·ml~(-1),方法直接用于化学试剂硫酸钾中锰的测定,结果满意。     

胶束溶液中同步荧光法测定苯半[a]芘的研究

在不同胶束溶液中考察了苯并［ａ］芘（Ｂ［ａ］Ｐ）的同步荧光光谱。结果表明，在十二烷基苯磺酸钠胶束溶液中，Ｂ［ａ］Ｐ的检测限可达０．００９３ｎｇ／ｍＬ，方法相对标准偏差为１．７％。用于实际水样的测定，结果满意。     

甲基叔丁基醚光催化降解的反应历程

以自制的TiO2为催化剂,在间歇式光催化反应装置中考察了水中甲基叔丁基醚的光催化降解反应.结果表明,水中MTBE在TiO2催化剂、氧气和紫外光照射的条件下能被光催化转化成无毒产物并最终被矿化.MTBE光催化降解过程中产生的主要中间产物有甲酸叔丁酯、叔丁醇和丙酮,尽管降解速率不同,它们也都能被光催化降解.通过对反应物、中间物及产物的追踪分析,认为MTBE的光催化降解首先是通过羟基化过程来进行,进而提出MTBE光催化降解的可能反应历程.     

Synthesis and Structural Characterization of Alkali Metal Guanidinates

Reactions of 1,3-diisopropylcarbodiimide with alkali metal amides, MN（SiMe3）2 （M=Li or Na） in hexane or THF produced the alkali metal guanidinates { （i-PrN）2C [N（SiMe3）2]Li }2 （1） and { （i-PrN）2C[N（SiMe3）2]Na（THF） } 2 （2） in nearly quantitative yields. Both complexes 1 and 2 were well characterized by elemental analysis, IR spectra, ^1H and ^13C NMR spectra, and X-ray diffraction. It was found that the guanidinates adopt different coordination modes in these complexes.     

配合物(ArO)2Yb(NPh2)2K(THF)4(Ar=C6H2-t-Bu3-2,4,6)的合成、分子结构和催化行为

Reaction of anhydrous YbC13 with 2 equiv, of sodium 2,4,6-tri-tert-butylphenoxide (ArONa, Ar=C6H2-t-Bu3-2,4,6) and 2 equiv, of potassium diphenyl amide in THF afforded the first bis(aryloxo) amido-lanthanide complex of (ArO)2Yb(NPh2)2K(THF)4 (1). In 1, the ytterbium and potassium were bridged via diphenyl amido ligands.The ytterbium metal center was coordinated to two oxygen atoms of aryloxide ligands and two nitrogen atoms of diphenyl amido ligands in a conventional distorted tetrahedral fashion, while the potassium interacted in η^2-fashion with two phenyl rings of the diphenyl amido ligands besides four THF molecules. 1 displayed moderate catalytic activities for the polymerization of methyl methacrylate and acrylonitrile.     

N,N',N",N"'-四对甲苯碘酰-1，4，7，10-四氮杂环十二烷的微小常压快速水解

N,N',N",N"'-四对甲苯磺酰-1,4,7,10-四氮杂环十二烷是Atkins法合成1, 4,7,10-四氮杂环十二烷的关键中间体,但其水解脱磺酰基比较困难,常规水解 一般需要采用96%-98%硫酸在140 ℃左右加热2-3d。报道了一种微波促进快速水解 法,即在稍加改装或未改装的家用微波炉中,采用95%-98%硫酸,控制火力2-5档, 全对甲苯碘酰化全氮冠醚仅需50-120 s即可完成水解,比常规加热水解所需时间缩 短约3000-8000倍,浓硫酸用量也比常规加热水解少,收率较常规水解高。     

Cooperative C-H…O H-bonds in ''Bay Area'' and Crystal Structure of 1-(4-Methylphenyl)- 3-(4-methoxyphenyl)-2-propene-1-one

The title compound (C17H16O2, Mr = 252.30) crystallizes in the monoclinic system, space group P21/c with a = 11.5763(14), b = 11.0321(11), c = 11.5094(13) (A),β = 114.581(3)°, V= 1336.7(3) (A)3, Z = 4, Dc = 1.254 g/cm3, μ(MoKa) = 0.081 cm-1 and F(000) = 536.00. The final R and wR are 0.0527 and 0.1285, respectively for 3058 observed reflections (I ＞ 2σ(I)). In the title molecule, two phenyl rings are rotated oppositely with respect to the central part C(1)-C(2)=C(3)- C(4) (plane 3) and the dihedral angle between them is 14.8°. The phenone O(1) atom deviates from plane 3 by 0.291(A). In the crystal the molecules form H-bond chains of R21(6) and R21 (5) types similar crystals are also presented.