Network formation and photoluminescence in copper(i) halide complexes with substituted piperazine ligands

The synthesis, X-ray structures and photophysics of ten complexes of CuX (X = I or Br) with bridging N-substituted and N,N'-disubstituted piperazines (Pip) are presented. Depending on the steric demand of the Pip substituents, the complexes fall into four categories: (CuX)(4)(Pip)(2), which are networks of linked Cu(4)X(4) cubane units, (CuX)(2)(Pip), which are chains of linked Cu(2)X(2) rhombs, and (CuX)(2)(Pip)(2) or (CuX)(4)(Pip)(4), which are simple rhomboid dimers and cubane tetramers. A combination of spectroscopic studies and DFT calculations was used to investigate the luminescence of the products. The results suggest that the relatively high energy emission seen in dimers is due to cluster-centred (XMLT/metal-centred) excitations for the aliphatic amines and MLCT (d →π*) for aromatic amines, and low energy emission seen in the tetramers is the result of cluster-centred transitions. The (CuI)(2)(Pip) complexes act as sensor materials, undergoing irreversible reaction with aliphatic and aromatic amines (Nu) in the vapour state, irreversibly producing cubanes (CuI)(4)Nu(4), with corresponding production of long wavelength emission.     

PTCs promoted biphasic oxidation of ethylbenzene catalyzed by NHPI and CoSPc

An easy workup and environmentally friendly method to convert ethylbenzene into the corresponding oxides,catalyzed by a combined catalytic system consisting of NHPI and CoSPc,was developed in a water involved liquid-liquid heterogeneous system.Experimental results showed that the reaction performed well facilitated by PTCs at multigrams material level,under which the conversion rate of ethylbenzene and the selectivity of acetophenone reached 60.6% and 95.2% after 0.5 h of reaction in oxygen atmosphere.An oxidation process was proposed at the end of this paper.     

Subwavelength lithography using metallic grating waveguide heterostructure

We present subwavelength periodic gratings achieved by employing a metallic grating waveguide heterostructure (MGWHS). The mask can be designed to make one of its diffraction order (±mth) waves resonate with the surface plasmon wave supported by the MGWHS. With a finite-difference time-domain method, we numerically demonstrate that one-dimensional periodic structure of about 60 nm feature, which is far beyond the diffraction limit, can be patterned with the interference of the 3rd diffraction order waves of the mask at a wavelength of 546 nm. The technique can also be extended to two-dimensional patterns using circularly polarized incidence and for the incidence with an angle θ.     

Highly efficient removal of allyloxycarbonyl(Alloc)function provides a practical orthogonal protective strategy for carbohydrates

Highly efficient removal of allyloxycarbonyl(Alloc)group was achieved in the presence of CH3COONH4,Pd[P(C6H5)3]4,and NaBH4 in MeOH-THF,within 5 min in almost quantitative yields(90%,isolated yield)without affecting acetyl,benzoyl,isopropylidene,benzylidene,allyl,benzyl,benzyl carbonate,or azido groups.     

反相高效液相色谱同时测定复方降压药中三组分

建立了一种反相高效液相色谱法 ,用于同时测定复方降压药中三组分。采用YWGC1 8柱 ,以甲醇 醋酸 醋酸钠缓冲液 水 ( 60∶2 0∶2 0 )为流动相 ,流速为 0 .8mL·min- 1 ,二极管阵列检测器于检测波长 2 60nm测定。硫酸双肼酞嗪、氢氯噻嗪和氨苯喋啶的线性范围分别为 0 .0 8～ 1 .1mg/mL ,0 .0 1～ 0 .30mg/mL ,0 0 3～ 0 .45mg/mL ,检测限分别为 0 0 0 6mg/mL ,0 0 0 1mg/mL ,0 0 0 1mg/mL ,已用于北京降压0号样品的测定     

广山药中16种元素的分析比较

用原子吸收法和分光光度法测定了5个产地的广山药及怀山药中16种元素的含量,并进行了比较。发现广山药及怀山药中均含有Mn,Fe,Zn,Ca,Cu,Mg,P,Se等元素,5个产地的广山药中的Cu/Zn值均低于正常人血清的Cu/Zn,这些元素可能是怀山药,广山药具有补脾养胃,生津益肺,补肾涩精,治疗糖尿病等功效的物质基础之一;广山药长期作为山药的一个品种同等入药,食用是有科学根据的;广山药,怀山药中含有一定量的As,Hg。     

Triphenylamine Derivatives Containing Nitronyl Nitroxide and Iminyl Nitroxide‐Syntheses,Characterization, Crystal Structures and Magnetic Studies

New triphenylamine derivatives 1, 2, 3, and 4 were synthesized and characterized by IR, FAB‐MS, EPR and EA. All of them displayed similar absorption and fluorescence spectra except compound 1, for which a possible explanation was proposed. Quasi‐reversible oxidation waves at about 0.76 V (vs. SCE) and 1.1 V for nitronyl nitroxide and iminyl nitroxide respectively as well as irreversible one at about 1.5 V for triphenylamine group were detected with cyclic voltammetry for compounds 1, 2, 3 and 4. Crystal structures of 2 and 4 were determined by X‐ray diffraction analysis. Their crystal data are as follows: for 2: monoclinic, C2/c, a = 1.69914 (4), b = 1.37435(5), c = 1.24621(5) ran, β= 106.553(2)°, V = 2.7896(2) nm³ Z = 4; for 4: orthorhombic, Pbca, a = 1.95970(6), b = 1.33096(4), c = 4.84691(14) nm, V = 12.6421(7) nm³, Z = 8. Magnetic studies indicated that all of them showed antiferromagnetic properties in solid state, but with strong intermolecular spin‐spin coupling as indicated by the relatively large values of 6, in particular for 4 (θ = ?12 K). Possible spin‐spin interaction mechanism was suggested based on the crystal structures of 2 and 4.