聚苯胺复合材料研究进展

综述了聚苯胺/无机物复合材料和聚苯胺/有机高聚物复合材料的合成方法，性能特征，并展望了聚苯胺复合材料的研究，应用前景。     

Electrochemical Determination of Ascorbic Acid in Room Temperature Ionic Liquid BPPF6 Modified Carbon Paste Electrode

A room temperature ionic liquid N‐butylpyridinium hexafluorophosphate (BPPF₆) was used as a binder to make an ionic liquid modified carbon paste electrode (IL‐CPE), which showed good characteristics such as simple preparation procedure, fast electrochemical response and good conductivity. The electrochemical oxidation of ascorbic acid (AA) on the new IL‐CPE was carefully studied. The oxidation peak potential of AA on the IL‐CPE appeared at 109 mV (vs. SCE), which was about 338 mV decrease of the overpotential compared to that obtained on the traditional carbon paste electrode (CPE) and the oxidation peak current was increased for about four times. The electrochemical parameters of AA on the IL‐CPE were calculated with the charge transfer coefficient (α) and the electrode reaction rate constant (k_s) as 0.87 and 0.800 s^?1, respectively. Based on the relationship of the oxidation peak current and the concentration of AA a sensitive analytical method was established with cyclic voltammetry. The linear range for AA determination was in the range from 1.0×10^?5 to 3.0×10^?3 mol/L with the linear regression equation as I_p (μA)=?2.52–0.064C (μmol/L) (n=13, γ=0.9942) and the detection limit was calculated as 8.0×10^?6 mol/L (3σ). The proposed method was free of the interferences of coexisting substances such as dopamine (DA) and amino acids etc., and successfully applied to the vitamin C tablets determination.     

Three‐Component Reactions with (S)‐Methyl Pyroglutamate: An Efficient Way to Diversely Substituted Asymmetric Amidocyclohexenes

Chiral N‐dienyl lactams are crucial building blocks for the synthesis of complex organic compounds. However, their generation is rather challenging. This paper reports the novel one‐pot reaction of (S)‐methyl pyroglutamate as the a mide component with different a ldehydes and d ienophiles (AAD reaction) to give novel chiral 1‐amido‐2‐cyclohexenes. The corresponding N‐dienyl lactams generated in situ undergo subsequent Diels–Alder reactions in good yield and diastereoselectivity. The scope and limitations of the three‐component protocol were investigated. X‐ray and NMR spectroscopic analysis of the products as well as DFT calculations of the intermediates were also performed to explain the observed stereoselectivity and structural features.     

A SAPO-11 Silicoaluminophosphate Molecular Sieve with Stable Crystal Structure

A SAPO-11 silicoaluminophosphate molecular sieve with stable crystal structure was synthesized for the first time. After removing template by calcination, its crystal space group still retains Icm2 which the as-synthesized has. The catalyst deriving from the present SAPO-I 1 materials shows higher isomerization selectivity and higher paraffin hydroisomerization yield than those reported elsewhere.     

Long‐range π‐type hydrogen bond in dimers CH2?HF,CH2O?H2O,and CH2O?NH3

Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH₂O? HF, CH₂O? H₂O, CH₂O? NH₃, and CH₂O? CH₄. The structures of CH₂O? HF, CH₂O? H₂O, and CH₂O? NH₃ are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH₂O and lone pair(s) on the F atom in HF, the O atom in H₂O, or the N atom in NH₃. In contrast with the above three dimers, for CH₂O? CH₄, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH₂O? CH₄ is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Structure and stability of endohedral X@Si20H20 complexes (X = Li, Na, K, Be, Mg, Ca)

The structure and stability of endohedral X@Si₂₀H₂₀ complexes (X = Li^0/+, Na^0/+, K^0/+, Be^0/2+, Mg^0/2+, Ca^0/2+) have been studied at the B3LYP/6-31G* level of density functional theory. It is found that complexes with X = Na^0/+, K^0/+, Mg and Ca^0/2+ are energy minimum structures with X at the cage center in I_h symmetry, while those with X = Li^0/+, Be^0/2+, Mg²⁺ have off-centered structures with X towards one pentagon face in C_5v symmetry. Large electron or charge transfer between the Si₂₀H₂₀ cage and the encapsulated X has been observed.     

Thermokinetics on the reaction of formation of Dy[(C<Subscript>5</Subscript>H<Subscript>8</Subscript>NS<Subscript>2</Subscript>)<Subscript>3</Subscript>(C<Subscript>12</Subscript>H<Subscript>8</Subscript>N<Subscript>2</Subscript>)]

The enthalpy change of formation of the reaction of hydrous dysprosium chloride with ammonium pyrrolidinedithiocarbamate (APDC) and 1,10-phenanthroline (o-phen?H₂O) in absolute ethanol at 298.15 K has been determined as (-16.12 ± 0.05) kJ?mol^-1 by a microcalormeter. Thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), rate constant and kinetics parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of the reaction have also been calculated. The enthalpy change of the solid-phase reaction at 298.15 K has been obtained as (53.59 ± 0.29) kJ?mol^t-1 by a thermochemistry cycle. The values of the enthalpy change of formation both in liquid-phase and solid-phase reaction indicated that the complex could only be synthesized in liquid-phase reaction.     

Detection of TMV with ODA-H(2)O(2)-HRP voltammetric enzyme-linked immunoassay system

o-Dianisidine (ODA)-H₂O₂-horseradish peroxidase (HRP) voltammetric enzyme-linked immunoassay system has firstly been used for the detection of tobacco mosaic virus (TMV). HRP catalyzes strongly the oxidation reaction of ODA by H₂O₂, the product of which produces a sensitive second order derivative linear sweep voltammetric peak at potential of −0.56 V (versus SCE) in Britton–Robinson (BR) buffer. HRP activity has been measured with this voltammetric peak and TMV detected through immunoreaction. The detection limit for HRP is 9.25×10^-7 mU l⁻¹ and the linear range is 2.5×10⁻⁶–5.0×10⁻⁴ mU l⁻¹. The detection limit for the clarified TMV is 0.25 ng ml⁻¹ and the highest dilution ratio detected for the infected leaf sap is 1:8×10⁵. The sensitivity for TMV detection with this method is higher than that with the enzyme-linked immunosorbent spectrophotometric assay (ELISA) using ODA-H₂O₂-HRP system. The processes of the enzyme-catalyzed reaction and the electro-reduction of the product of the enzyme-catalyzed reaction have been described.     

Preparation of nanometer FeCuP alloy and its application in decomposition of PH3

A new ternary Fe-based alloy catalyst FeCuP applied to decompose PH_3 was prepared with low-cost material by chemical reduction deposition method.The properties of it were characterized by XRD,ICP and SEM.Its catalytic activity on the decomposition of PH_3 and the decomposition conditions were studied.FeCuP alloy exhibits high thermal stabilities and high catalytic activity.Using it as catalyst,the decomposition temperature of phosphine decreases from over 800℃to 400-500℃.The decomposition rate of phosphine achieved 100%.     

Cyanex301的纯化及其特性

研究了用Ｃｙａｎｅｘ３０１［ＴＭ］铵盐在苯中重结晶以纯化Ｃｙａｎｅｘ３０１的方法，该法收率６２．４％，产品纯度＞９９％。测定了经纯化后产品的红外光谱，研究了纯化产品在－水正庚烷体系中的分配平衡及其在正庚烷中的缔合，浓度在０．２～１．０ｍｏ１／Ｌ范围，Ｃｙａｎｅｘ３０１主要以二聚形式存在。