SFG and DFG investigation of Au(111), Au(210), polycrystalline Au,Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing KCN and 4-cyanopyridine

We report on potential-dependent in situ SFG and DFG spectroscopy carried out at Au(111), Au(210), polycrystalline Au, Au–Cu and Au–Ag–Cu electrodes in contact with aqueous solutions containing CN⁻ and 4-cyanopyridine (4CP). Spectroelectrochemical work was complemented by cyclic voltammetry. The chief stress has been placed on systematising and quantifying the interaction between 4CP and CN⁻ and the attending effects on the vibrational and electronic structures of the interface. The voltammetric behaviour of the investigated electrodes, modified by the addition of 4CP to the CN⁻ electrolyte, denote changes in the CN⁻ adsorption characteristics and effects of the adsorbed CN⁻ layer on the electrodic reactivity of 4CP. The differences among the investigated electrodes can be explained in terms of their respective degrees of atomic packing or with alloying effects on the stability of adsorbed CN⁻. The potential-dependent spectra have been analysed quantitatively with a model for the second order non linear susceptibility accounting for vibrational and electronic effects. The spectral changes induced by addition of 4CP denote interaction of the aromatic with the electrode through the CN⁻ monolayer. The non-resonant contribution yields information on the effects of 4CP on the fine structure of the bound electron density of states.     

Synthesis,extraction, and adsorption properties of calix[4]arene‐poly(ethylene‐glycol) crosslinked polymer

Novel calix[4]arene‐poly(ethylene glycol) crosslinked polymer (CCP) has been synthesized by the polycondensation reaction between a p‐tert‐butylcalix[4]arene derivative and dihydroxyl capped poly(ethylene glycol) (DHPEG, M_n = 1000) catalyzed by neodymium tosylate. The hydrogel, consisted of 66.9% water and 33.1% CCP, can selectively extract aromatic organic molecules from aqueous solution according to the diameter of the guest molecules, which infers that the diameter of the calix[4]arene cavity is about 5.4 Å and the conformation of calix[4]arene units altered from cone conformation to 1,3‐alternate conformation during the polycondensation reaction. Furthermore, CCP can also adsorb naphthalene from gas phase, showing much higher capacity than active carbon does, which may have some potential applications in the field of separation and environment protection. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

单相负载三相供电功率分配之PLC改造实践

介绍了单相负载一工频感应炉供电的S7-200CPU224改造实践方案.依托原有设备条件,三相功率分配同样设计采用电容、电抗进行调节,起、停及三相电流平衡控制由晶闸管 接触器形式替代原单纯采用接触器控制,有效值测量使用有别于FFT的检测算法.运行实践表明:节能降耗明显,设备故障率大幅降低,具有良好的推广应用价值.     

Mesomorphism of Lanthanide(Ⅲ) 4-Hexyloxybenzoates

The 4-alkoxybenzoic acids are well-known liquid crystals showing several mesophases(nematic,smectic C phase or both)depending on the alkoxy chain length and whereby the rigid core of the mesogen is formed by intermolecular hydrogen bonds.In this paper it is shown that the thermal behaviour of lanthanide salts of 4-hexyloxybenzoic acids depends on the lanthanide ion(Ln=La,Pr,Nd,Sm,Eu).The lanthanum(Ⅲ)and praseodymium(Ⅲ)4-hexyloxybenzoates exhibit a smectic A mesophase.No mesophase is found for the corresponding compounds of heavier lanthanides.The thermal properties of the lanthanide(Ⅲ)4-hexyloxybenzoates were investigated by differential scanning calorimetry(DSC),polarising thermo-optical microscopy and synchrotron X-ray radiation.     

基于S2A6000存储的新闻制播网络安全设计

从分析S2A6000新闻制播网系统特点,拓扑结构入手,完整总结了S2A6000存储的新闻制播网络安全设计与安全措施。     

3-N-丙酰基-2-芳基-5-(3-碘苯基)-1,3,4-(口恶)唑啉类化合物的合成及表征

以3-碘苯甲酸为原料,在浓硫酸作用下与乙醇反应制得3-碘苯甲酸乙酯(1),再以无水乙醇为溶剂,在105℃化合物1与80％的水合肼反应8 h,制得3-碘苯甲酰肼(2)。在无水乙醇中,在90～95℃化合物2分别与4-甲基苯甲醛、2-氯苯甲醛、4-氯苯甲醛、4-羟基苯甲醛、2,4-二氯苯甲醛、4-甲氧基苯甲醛、3-硝基苯甲醛、4-硝基苯甲醛和4-二甲氨基苯甲醛反应得到相应的酰腙[3(a～i)]。最后化合物3(a～i)分别与丙酸酐脱水环化成了3-N-丙酰基-2-芳基-5-(3-碘苯基)-1,3,4-(口恶)唑啉类化合物[4(a～i)],收率分别为86．2％,70．5％, 80．1％,68．2％,62．4％,75．2％,73．2％,70．5％和63．2％。并通过元素分析,IR,1H NMR和MS对化合物4(a～i)的结构进行了表征。     

Oxidation of oleuropein studied by EPR and spectrophotometry

The autoxidation at alkaline pH and enzymatic oxidation by mushroom tyrosinase of oleuropein, the dominant biophenol present in the fruits and leaves of Olea europea, was followed by both electron paramagnetic resonance (EPR) and absorption spectroscopy. For comparison, the same oxidation processes were applied to 4‐methylcatechol, a simple polyphenol present in olive mill wastewaters. EPR spectra of stable o‐semiquinone radicals produced during autoxidation at pH 12 and short‐lived o‐semiquinone free radicals produced during autoxidation at pH 9.0 or tyrosinase action and stabilized by chelation with a diamagnetic metal ion (Mg²⁺) were recorded for both polyphenols, and the corresponding hyperfine splitting constants were determined. The UV‐Vis spectral characteristics of the oxidation of polyphenols were highly dependent on the type of polyphenol, oxidant type and the pH of the reaction. The kinetic behavior of tyrosinase in the presence of oleuropein and 4‐methylcatechol was followed by recording spectral changes at 400 nm (absorption maximum) over time. The tysosinase activity with oleuropein showed a pronounced pH optimum at pH 6.5 and a minor one around pH 8. From the data analysis of the initial rate at pH 6.5, the kinetic parameters K_m = 0.34 ± 0.03 mM and V_max = 0.029 ± 0.002 ΔA₄₀₀ min^–1 were determined for oleuropein.     

Direct synthesis and catalytic performance of ultralarge pore GaSBA-15 mesoporous molecular sieves with high gallium content

Mesoporous GaSBA-15 molecular sieves with different n_Si/n_Ga ratios have been directly synthesized using Pluronic 123 triblock polymer as a structure-directing agent by pH-adjusting method. The mesoporous materials have been characterized using ICP-AES, XRD, N₂ adsorption, ⁷¹Ga-MAS NMR, SEM and TEM. ICP-AES studies show a high amount of gallium incorporation on the silica pore walls. The structural and textural properties of calcined GaSBA-15 are characterized by XRD and N₂ adsorption. ⁷¹Ga MAS NMR results demonstrate that a high amount of tetrahedral-gallium could be substituted for Si in the framework of SBA-15. TEM and FE-SEM images show the uniform pore diameter and rope-like hexagonal mesoporous structure of GaSBA-15. These GaSBA-15 materials have been used as catalysts for vapour-phase t-butylation of 1,2-dihydroxybenzene (DHB) for selective synthesis of 4-t-butylcatechol (4-TBC) under different reaction conditions. GaSBA-15(10) gave the highest 93.2% conversion of DHB and 95.7% selectivity of 4-TBC as compared with other GaSBA-15 catalysts.     

固体超强酸S_2O_8~(2-)/SnO_2-SiO_2催化合成环己酮1,2-丙二醇缩酮

采用沉淀-浸渍法制备了固体超强酸S2O28-/SnO2-SiO2,以它为催化剂催化环己酮和1,2-丙二醇合成了环己酮1,2-丙二醇缩酮;考察了带水剂种类及用量、酮醇摩尔比、催化剂用量、反应时间对产品收率的影响,并用正交实验对反应条件进行了优化。实验结果表明,适宜的反应条件为:n(环己酮)∶n(1,2-丙二醇)=1∶1.6、催化剂用量为反应物料总质量的2.0%、带水剂环己烷用量5.0mL、反应时间50min。在此条件下,环己酮1,2-丙二醇缩酮收率达到91.47%;催化剂的稳定性良好,在重复使用5次后环己酮1,2-丙二醇缩酮收率为82.20%,活性下降的主要原因为催化剂表面积碳和吸附了有机物;经傅里叶变换红外光谱和气相色谱质谱分析表明,产物为环己酮1,2-丙二醇缩酮,纯度为100%。     

甲状腺素T4免疫传感器的研究

报道以甲基丙烯酸羟乙酯与甲基丙烯酸甲酯的共聚物为载体膜材料，研制成非酶标记的Ｔ４免疫传感器，并对载体膜材料的共聚方法及共聚物共聚比与传感器灵敏度的关系进行了探讨。