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     

A Simple Experimental Technique to Measure Tortuosity in Packed Beds

In this article, a simple and inexpensive experimental technique easy to build in laboratory, for the measurement of tortuosity of a packed bed of inert particles, is described. Experimental values of the tortuosity were obtained with four different packed beds of sand. The experimental results obtained are in good agreement with the theoretical values of tortuosity in a porous media; and the data reported showed the tortuosity to increase with decrease in the void fraction of the packed bed as expected.     

Preparation and characterization of metal-complex imprinted PVDF hollow fiber membranes

Using nickel-2,2′-dipyridyl complex as a template, N-vinyl-2-pyrrolidone as the metal coordination functional monomer, and ethylene glycol dimethacrylate as the crosslinker, polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration membrane as the supported membrane, metal complex imprinted polymeric membranes were prepared. The association constant of template-monomer interaction in the prepolymerization solution was estimated to be 4.38 × 10⁴ (L/mol)² by spectrophotometric titration analysis. The attenuated total reflection Fourier transform infrared spectroscopy and scanning electron micrograph characterization indicated that the surface of the support PVDF membrane was completely coated by the imprinted polymer layer after modification. The imprinted membranes exhibited the selective permeability for the template in certain nickel acetate solution. The molecularly imprinted membranes gave higher permeation separation factors at about pH 6, whereas increasing pressure would lower the separation ability. The effects of ion concentration, cations and counterions, ligand selectivity, pH, and trans-membrane pressure were investigated and the permeation performances of the imprinted membranes could be regarded as facilitated transport mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Intercalated clays from pentaerythritol stearate for use in polymer nanocomposites

Smectite clays treated with quaternary ammonium salts have been utilized for decades in paints, greases, cosmetics, and personal care products as rheological modifiers. They have also been used in industrial wastewater treatment extensively. In more recent times these surface modified clays have demonstrated benefits in polymer/clay nanocomposites. The use of quaternary ammonium modifiers limits the usefulness of these composites in food packaging because they are not approved for direct food contact. It would be advantageous to have surface modifying chemicals acceptable for direct food contact in these composites. This article reports research conducted on a promising surface modifier pentaerythritol stearate (PS), which is approved by the FDA for inclusion in food as a preservative. The surface modification of montmorillonite with PS is reported in detail as well as the production of nanocomposites with selected polymers made with the modified clay. Molecular modeling and purification of commercial PS samples indicate that the mono‐ and diesters are the critical surface modifiers, although the as received commercial material works well in forming intercalated clay complexes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

钛硅分子筛催化环己酮氨肟化反应过程--本征动力学

对钛硅分子筛(HTS)催化环己酮氨肟化反应本征动力学进行了研究。利用经验方程拟合了试验数据，并采用Marquardt算法对经验方程的参数进行确定，获得了不同试验条件下的反应初速率，然后再用高斯-牛顿法对本征动力学模型进行了参数估计，得出了氨肟化反应以及该反应体系中H2O2分解的本征动力学。并对该模型进行了残差分析和F检验，对氨肟化反应和H2O2分解的动力学模型的计算值与试验值进行了比较，获得相对误差绝对值的平均值分别为5．21％和6．25％。表明该模型能真实反映HTS催化环己酮氨肟化的反应特性，是合理可靠的，能为进一步的过程开发与工程设计提供一些理论上的指导和设计上的依据；而H2O2分解副反应动力学模型仅适用于该反应体系。     

Heavy arsenic doping of silicon grown by atmospheric pressure selective epitaxial chemical vapor deposition

Selective epitaxial Si with a high arsenic concentration of 2.2×10¹⁹ atoms/cm³ was deposited at a high growth rate of 3.3 nm/min under atmospheric pressure. It was confirmed that this method had excellent selectivity and produced films having good crystalline quality, abrupt dopant profiles at the interfaces, and smooth surfaces. The growth mechanism is discussed in terms of the relationship between the effects of arsenic surface segregation and etching by hydrogen chloride.     

最大重迭对称性分子轨道和分子几何参数计算

建立了AMl级别的最大重迭对称性分子轨道计算方案(MOSMO)。采用通常的半经验分子轨道方法AMl级别中完全相同的参数，计算了各种分子的几何参数等。所得计算结果与实验值及HF／6-31G*从头算方法计算结果相符，说明提出的计算方案是可行的。同时，由于提出的计算方案过程简单，更易推广使用到从头算方法难以解决的大分子体系和超分子体系的结构和性质研究。     

La3+掺杂对纳米TiO2微观结构及光催化性能的影响

以钛酸丁酯和氯化镧为原料,采用溶胶-凝胶法制备了La3+掺杂TiO2纳米粉体,讨论了不同掺杂浓度、不同热处理温度的样品催化降解刚果红染料实验中的光催化活性,并通过X射线衍射(XRD)、透射电镜(TEM)分析了La3+掺杂TiO2样品的相组成、晶胞参数和晶粒大小对光催化活性的影响.结果表明:La3+掺杂能够显著提高TiO2粒子的光催化活性,最佳掺杂浓度为100∶3 0,最佳热处理温度为600℃;La3+掺杂的TiO2的相组成是影响光催化活性的决定性因素;晶格膨胀程度及晶粒大小对光催化活性的影响,主要是在相组成相同或相近时才体现得比较明显.     

Effect of functionalization and boron and nitrogen substitution on some properties of carbon nanotubes

Molecular orbital calculations of the ionization potential of single wall carbon nanotubes having donor NH₂ and acceptor NO₂ groups bonded to the side walls and ends and boron and nitrogen substituted for carbon show substantial increases in ionization potential compared to carbon nanotubes with no functional groups and no carbon substitutions. The presence of a carbon vacancy on the side wall also causes a substantial increase in the ionization potential. The effect of tube length on the ionization energy is also calculated. The calculations also suggest that at appropriate levels of boron and nitrogen doping the armchair carbon nanotubes could be high temperature organic ferromagnetic materials.