New reactions of 1-alkynes catalyzed by transition metal complexes

Recently discovered catalytic reactions with ruthenium and lanthanide metal complexes have extended the scope of 1-alkynes as useful reagents. The specific formation of aryl-substituted (Z)-1,3-enzymes via the dimerization of HC(triple bond) CR(1) (R(1) = aryl) has been attained using dimeric lanthanide complexes, the catalytic activity of which appears to be unaffected by time. The dimerization of HC(triple bond) CR(2) (R(2) = t-Bu, SiMe(3)) catalyzed by Ru(cod)(cot)/PR(3) or RuH(2)(PPh(3))(3) produces a good yield of butatrienes (Z)R(2)CH=C=C=CHR(2) with a high degree of selectivity. Under certain conditions, HC(triple bond) C=SiMe(3) dimerizes to yield exclusively (Z)-M(3)Si-C(triple bond) C-CH=CH-SiMe(3). The hydration of HC(triple bond)CR(3) (R(3) = alkyl, aryl) catalyzed by RuCl(2)/PR'(3) or CpRuCl(PR"(3))(2) has realized the first example of anti-Markovnikov regioselectivity in an addition reaction of water that produces aldehydes R(3)CH(2)bond;CHO. The application of this reaction to propargylic alcohols has lead to their formal isomerization to alpha,beta-unsaturated aldehydes. In contrast, the addition of amines R(4)bond;NH(2) (R(4) = aryl) to HCtbond;CR(5) (R(5) = alkyl, aryl) conforms to Markovnikov's rule to produce ketimines R(5)bond;(C=NR(4))bond;CH(3) when catalyzed by a Ru(3)(CO)(12)/additive. Since the reaction can be performed in air without the need for any solvents, it enables the practical synthesis of aromatic ketimines, which are difficult to prepare by conventional methods. The synthesis of indoles using deactivated anilines is one practical application of this reaction. The mechanisms of some of these reactions have been analyzed in detail with the aid of theoretical calculations.     

Theoretical investigations on the SO2 + HO2 reaction and the SO2–HO2 radical complex

The mechanism of the SO₂ + HO₂ reaction was studied theoretically for the first time. Three product channels were revealed, namely, O₂ + HOSO, O₂ + HSO₂, and OH + SO₃. The O₂ + HOSO channel dominates the reaction under combustion conditions. A five-member-ring complex [SO₂–HO₂] exists at the entrance of the reaction. The structure and binding energy (D_e and D₀) of the SO₂–HO₂ complex have been calculated. In view of D₀ = 21.2 ± 2.0 kJ mol⁻¹, the SO₂–HO₂ complex should be stable at low temperature. The infrared spectra and frequency shifts were calculated for both SO₂–HO₂ and SO₂–DO₂, and compared with the available experimental data.     

Structure-direct assembly of hexagonal pencil-like ZnO group whiskers

Hexagonal ZnO group whiskers synthesized from Zn(NH₃)₄²⁺ precursor at 145°C in a structure-directing template solvent (2.5% v/v alcohol) show strong photoluminescence at 409 and 420 nm. FE-SEM and TEM observation reveals that the ZnO group whiskers consist of uniform pencil-like whiskers with the diameter of around 1.5 μm and the length of up to 6 μm.     

手性高效液相色谱法测定1—（6‘—甲氧基萘）乙醇不对称氢酯基化反应

在自制的硅基纤维素－三（３，５－二甲基苯基氨基甲酸酯）高效液相色谱手性固定相上（ＨＰＬＣ－ＣＳＰ），优化了１－（６＇－甲氧基萘）乙醇氢酯基化反应产物－萘普生甲酯手性分离的条件，测定了相应的一系列不对称氢酯基化反应产物的对映体过剩值（ｅ．ｅ．值）。结果表明，在ＣＤＭＰＣ－ＣＳＰ手性柱上用ＨＰＬＣ测定此类不对称催化反应的光学产率，评价催化剂体系的手性选择是一种非常理想的方法。     

主链含硅聚芳酯的合成及气体透过性能的研究

以双［对－酰氯苯基］二甲基硅烷和酚酞、四溴酚酞以及双酚Ａ为原料，合成了三种主链含硅聚芳酯，并对聚合物相关的物理性质进行了表征，制成了均质透明的薄膜．采用低真空法测定这些聚合物对Ｈ２、Ｏ２、Ｎ２、ＣＯ２、ＣＨ４的气体透过速率，并计算出气体透过系数、扩散系数、溶解系数、分离系数．从气体透过性能与聚合物分子结构关系的角度，按照气体透过的溶解－扩散机制，对聚合物的气体透过性能进行了研究，而且着重讨论了聚合物的堆积密度对气体扩散系数的影响，以及聚合物主链中极性链段的百分含量对气体溶解系数和溶解选择性的影响。     

Inorganic electrides

Inorganic electrides are a novel kind of ionic compounds in which the anions are electrons confined in a complex array of cavities or channels and the cations are nanoscale arrays of alkali metal ions that provide charge balance. In electrides the donated electron behaves like a low-density correlated electron gas, whereby the dimensionality of the electron gas and its electronic and magnetic properties are determined by the topology of the cavities in the host matrix. Unlike traditional electrides, in which alkali cations are encapsulated within an organic cage, inorganic electrides are thermally stable. The current inorganic electrides based on alkali metal loaded zeolites can be designed as useful reduced-dimensionality materials. Inorganic electrides are powerful reducing agents, and they are able to reduce small aromatic molecules to the radical anions within the channels of the zeolite.     

Hydrogen adsorption on zigzag (8,0) boron nitride nanotubes

The chemical adsorption of H atoms on an (8,0) zigzag boron nitride nanotube is studied using the density functional theory with the supercell method. One to four H atoms per 32 B and 32 N are considered. The results show that H atoms prefer to adsorb on the top sites of adjacent B and N atoms to form an armchair chain along the tube axis. An even-odd oscillation behavior of the adsorption energy of H atoms on the tube is found, and the average adsorption energy of even H atoms is obviously bigger than that of odd H atoms. The results can be understood with the frontier orbital theory. Based on this adsorption behavior, several high-symmetric structures of H adsorbed boron nitride nanotubes with 50% and 100% coverages are studied. The pairs of lines' pattern with 50% coverage has the biggest average adsorption energy per H(2) among the chosen configurations, corresponding to approximately 4 wt % hydrogen storage.     

2-(苯并噻唑-2-基)-5-(N,N-二乙基氨基)苯酚衍生物的合成及其对H2S的识别

以4-N,N-二乙基氨基水杨醛为原料,制备了2-(苯并噻唑-2-基)-5-(N,N-二乙基氨基)苯酚衍生物(探针L),并对其结构进行了表征。在DMSO/PBS(体积比3∶7,pH=7.4)溶液中,探针L具有高选择性并可荧光"关-开"识别H_2S,在365nm紫外灯照射下,由无荧光变成蓝色荧光。实验表明,探针L识别H_2S的检测限为2.05×10~(-6)mol/L,pH适用范围为6～9,可用于检测实际水样中的H_2S。     

新显色剂二溴硝基苯基重氮氨基偶氮苯的合成及与镉的显色反应的研究

作者合成了新显色剂2,6-二溴-4-硝基苯基重氮氨基偶氮苯(DBNDAA)。在pH8.5的硼砂-盐酸缓冲介质中,在Tween 80-SDBS存在下,该试剂与镉(Ⅱ)生成络合比为3:1的红色络合物,λ_(max)=500nm,ε_(500)=1.52×10~5L·mol~(-1)·cm~(-1)。镉量在0～28μg/25ml范围内遵守比耳定律。并测定了试剂的表观离解常数和络合物的表观不稳定常数。方法有良好的选择性。用该试剂测定了铝合金标样、环境水样及废水中的痕量镉,结果满意。