秦巴山区钮子根茎、叶中微量元素的研究

为研究秦巴山区钮子根茎、叶中微量元素的含量,采用微波消解的方法处理样品,用火焰原子吸收分光光度法分别测定了其K、Na、Mg、Fe、Cu、Mn、Zn、Co、Ni、Pd 10种金属元素的含量,确立了样品消解试剂、微波消解条件,并对样品进行了精密度和回收率试验。结果表明,相对标准偏差在0.772 8%~6.813 7%之间,回收率在94.0%~109.9%之间,钮子根茎、叶中均含有丰富的K、Na、Mg、Fe、Cu、Mn、Zn等金属元素,Co、Ni等有益微量元素的含量次之,Pd的含量最低。     

A new near-infrared fluorescent chemodosimeter for discrimination of sulfide from disulfide

Research on Chemical Intermediates - A new near-infrared fluorescent “turn-on” chemodosimeter (probe 1) based on dicyanomethylene-4H-chromene fluorophore for sulfide was developed....     

MCM-41@Schiff base-Co(OAc)2 as an efficient catalyst for the synthesis of pyran derivatives

Research on Chemical Intermediates - Heterogeneous ordered mesoporous silica materials catalyst, MCM-41@Schiff base-Co(AcO)2, reveals high catalytic performance within the synthesis of pyran...     

Dual Spectroscopic Responses of Pyridinium Hemicyanine Dyes to Anions

The absorption and fluorescence spectroscopic responses of three pyridinium hemicyanine dyes to anions F⁻, Cl⁻, Br⁻, I⁻, H₂PO₄⁻, HSO₄⁻ and OAc⁻ were investigated. At lower concentrations of OAc⁻ (less than 1 equiv.), both the absorption and the fluorescence intensities of 1 – 3 were more effectively changed than F⁻ at identical concentrations. At higher concentrations of OAc⁻ (more than 1 equiv.), the interaction was opposite for each compound. ¹H NMR results indicated the interaction between 1 , 2 or 3 and F⁻ proceeded through hydrogen bonding. The results showed that these dyes are promising to develop dual fluorescence and chromogenic chemosensors toward F⁻ and OAc⁻ according to the subtle difference in the affinity of F⁻ and OAc⁻.     

Further studies of intramolecular Michael reactions of nitrosoalkenes for construction of functionalized bridged ring systems

A wide variety of stabilized carbanions have been found to participate as nucleophiles in intramolecular Michael-type conjugate additions to in situ generated nitrosoalkenes to form bridged carbocyclic systems. The vinylnitroso platforms for these cyclizations have been prepared via two key steps involving ring-closing metathesis of vinyl chlorides and regioselective conversion of vinyl chlorides to α-chloroketones with sodium hypochlorite in glacial acetic acid/acetone. An alternative approach to preparation of some cyclization substrates has involved use of more reactive enol ethers as precursors to the requisite α-chloroketones. A sulfonamide anion has also been found to be an effective nucleophile in this type of reaction, leading to formation of a 6-azabicyclo[3.2.1]octane.     

Solid-state structures and magnetic properties of halide-bridged, face-to-face bis-nickel(II)-macrocyclic ligand complexes: ligand-mediated interchanges of electronic configuration

Dramatic differences are found between the ambient and 100 K X-ray structures of [L(2)Ni2Br2](ClO4)2 (L(2) = alpha,alpha'-bis{(5,7-dimethyl-1,4,8,11-tetraazacyclotetradeca-6-yl)-o-xylene), in which the bromide-bridged, bimetallic, macrocyclic ligand complexes of nickel(II) are held face-to-face and in which each bimetallic complex has a net triplet spin multiplicity. The ambient structure of this complex consists of very highly ordered, infinite chains of alternating R and S isomers in which the identical Ni(II) coordination spheres are near to the average expected for the high- and low-spin Ni(II) coordination sites, and there is appreciable stereochemical strain in the linkage of the macrocyclic ligands to the phenyl ring. In contrast, every other dinickel complex of the 100 K structure is displaced about 40 pm along the infinite chains to form tetrameric repeat units (pairs of dinickel complexes), in which each dinickel complex has well-defined high-spin and low-spin Ni(II) coordination sites; the high-spin sites are adjacent in the tetramers, and the stereochemical strain in the linkage to the phenyl spacer is relaxed. The molecular magnetic moments and structural contrasts are similar for the 100 K structure and the previously reported ambient structure of [L(2)Ni2Br3](ClO4) complex for which the molecular magnetic moments also correspond to a single triplet state per complex. The halide-bridged, monochloro- and monobromo dinickel complexes also have triplet spin multiplicity, and they crystallize with a coordinated perchlorate completing the axial coordination of the high-spin Ni(II) site, while the other Ni(II) site of these halide-bridged complexes has equatorial Ni-N bond lengths typical of low-spin Ni(II) coordination. The bridging halide is sandwiched between the face-to-face macrocyclic ligand Ni(II) moieties and slightly off the Ni-Ni axis in all of the complexes. The temperature dependence of the magnetic moments of the series of complexes indicates that their singlet-triplet energy gaps are small, with zero point energy differences that are generally less than 10(3) cm(-1). The very weak metal-metal electronic coupling, the triplet state spin multiplicity of each dinickel complex, and the averaged high-spin/low-spin coordination environments of the ambient structure implicate a vibronic mechanism for the electronic configurational exchange in the dibromo and tribromo complexes. The single molecular vibrational mode that correlates with the configurational exchange in these complexes includes the concerted motion of the bridging bromide between the Ni(II) centers. Activation of this vibrational mode is sufficient to effect the configurational exchange. These complexes present especially clear examples of the effects of the coupling of nuclear vibrational motions to the interchange of electronic configuration between two different centers.     

A Novel Colorimetric and Fluorescent “Off-On” Chemosensor for Cu2+ Based on a Rhodamine Derivative Bearing Naphthyridine Group

A new rhodamine-based derivative bearing a naphthyridine group (compound 1) was synthesized as a colorimetric and fluorescent “off-on” chemosensor for Cu²⁺ in aqueous solutions. The sensing behaviors of 1 toward various metal ions in neutral aqueous solutions were investigated by absorption and fluorescence spectroscopies. Compound 1 is found to exhibit a significant increase in absorbance at 561 nm and an amplified fluorescence at 590 nm toward Cu²⁺ in a selective, sensitive and rapid manner. The quantification of Cu²⁺ by 1 using an absorption spectroscopy method was satisfactory in the linear working range 0.9–10 μM, with a detection limit of 5.4?×?10^?8?M for Cu²⁺ and good tolerance of other metal ions. Upon addition of Cu²⁺, the spirolactam ring (colorless and nonfluorescent) of 1 was opened to ring-opened amide (red color and fluorescent) and a 1:1 stoichiochemetry for the 1-Cu²⁺ complex was formed with an association constant of 1.57?×?10⁴?M^?1.     

吨染料与反胶束体系中CdS的光敏电子转移

用ＡＯＴ／异辛烷／水反胶束体系制备出了不同尺寸大小的纳米ＣｄＳ,并以曙红（ＥＯ）和孟加拉玫瑰红（ＲＢ）为探针分子,研究了它们与硫化镉微粒间的光致电荷转移相互作用,用光照实验和ＥＳＲ技术研究了这些染料向ＣｄＳ的导带注入电子的过程并讨论了作用机理