Photocatalytic degradation of 2,2‐bis(4‐hydroxy‐3‐methylphenyl) propane (BPP) based on molecular recognition interaction

BACKGROUND: Endocrine disruptors in the aquatic environment and their potential adverse effects are currently issues of concern. One of these endocrine disruptors is 2,2‐bis(4‐hydroxy‐3‐methylphenyl)propane (BPP). In this work the molecular recognition interaction of BPP with β‐cyclodextrin (β‐CD) was studied using IR spectroscopy and steady state fluorescence spectroscopy, and the photocatalytic degradation behaviour of BPP based on molecular recognition interaction was investigated in a TiO₂/UV–visible (λ_max = 365 nm) system. This might provide a new method for the treatment of some organic pollutants in wastewater. RESULTS: β‐CD reacts with BPP to form a 1:1 inclusion complex, the formation constant of which is 4.94 × 10³ L mol^?1. The photodegradation rate constant of BPP after molecular recognition by β‐CD showed a 1.42‐fold increase in the TiO₂/UV–visible (λ_max = 365 nm) system. The photodegradation of BPP depended on the concentration of β‐CD, the pH value, the gaseous medium and the initial concentration of BPP. The photodegradation efficiency of BPP with molecular recognition was higher than that without molecular recognition. After 100 min of irradiation the mineralisation efficiency of BPP after molecular recognition by β‐CD reached 94.8%, whereas the mineralisation efficiency of BPP before molecular recognition by β‐CD was only 40.6%. CONCLUSION: The photocatalytic degradation of BPP after molecular recognition by β‐CD can be enhanced in the TiO₂/UV‐visible (λ_max = 365 nm) system. This enhancement is dependent on the enhancement of the adsorption of BPP, the moderate inclusion depth of BPP in the β‐CD cavity and the increase in the frontier electron density of BPP after molecular recognition. Copyright © 2008 Society of Chemical Industry     

控制W9Cr3Mo4V低倍碳化物剥落的工艺改进

针对W9Cr3M04V轧制成品材低倍碳化物剥落的形成原因分析，得出一次碳化物颗粒粗大、在1／4D至中心区域聚集是导致低倍热酸浸试验碳化物剥落的主因；由此进行冶炼过程中注速（锭形）、浇注温度选择对比工艺试验，得出在原有冶炼＋轧制的工艺基础上选用2．2t锭、降低浇注温度（1489℃）能有效改善一次碳化物颗粒大小和聚集程度，进而有效降低低倍碳化物剥落倾向。     

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     

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.     

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.     

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。     

Calculation methods for comparing the performance of pure and mixed working fluids in heat pump applications

Three methods for comparing cycle performance of working fluids, pure as well as non-azeotropic mixtures, are investigated for two applications and for two mixture pairs, HCFC22-CFC114 and HCFC22-HCFC142b, and their pure components. The methods differ in the way of calculating the heat exchange processes. They assume, respectively, equal minimum approach temperatures, equal mean temperature differences and equal heat transfer areas. Changes of coefficient of performance (COP) with composition are explained for all methods. It is shown that transport properties must be taken into account when making rigorous comparisons between working fluids. To predict the relations between fluids with high accuracy, one must use the method with equal heat transfer areas. By the method with equal mean temperature differences, the COP can be estimated with the same accuracy for mixtures as for pure fluids, and can be used for rough estimations of the COP level with different fluids. The method of equal minimum approach temperatures should be avoided for non-azeotropic mixtures.     

Effet de la pression sur la transition ruisselant-pulsé dans les réacteurs catalytiques à lit fixe arrosé

The effect of pressure on transition displacement between trickle and pulsed regimes (TPR: trickle-pulsed transition) in catalytic trickle bed reactors (CTBR) is not properly predicted by existing theoretical models and empirical correlations. Based on high pressure TPR data available to date, a modified Charpentier diagram is proposed to quantify directly the effect of pressure in non-foaming systems.