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。     

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。     

助模板剂对MCM—41分子筛孔结构和性能的影响

在硅酸钠－硫酸铝－十六烷基三甲基氯化铵－水体系中，加入不同类型，如正庚烷、三甲基苯和十二胺的有机助模板剂（简称助剂）进行ＭＣＭ－４１分子筛的合成试验，并用ＸＲＤ、ＩＲ及Ｎ２吸附等方法考察了助剂对ＭＣＭ－４１分子筛孔径、热稳定性及酸性的影响。结果表明，十二胺助剂对ＭＣＭ－４１分子筛的孔径影响最大，但热稳定性较差，相比之下，三甲基苯助剂合成的ＭＣＭ－４１分子筛具有孔径大、热稳定性好和酸性特征较好的特点。     

SAPO-34/SiO_2催化甲醇制烯烃

采用水热法合成了SAPO-34分子筛,并用X射线粉末衍射仪和扫描电子显微镜对SAPO-34分子筛的结构进行了表征,同时探讨了黏合剂种类、甲醇分压、催化剂粒径和硅源等对SAPO-34分子筛催化甲醇制烯烃(MTO)反应性能的影响。实验结果表明,在MTO反应中,三烯(乙烯、丙烯和丁烯)选择性在反应初期存在明显的诱导期;以S iO2为黏合剂合成的SAPO-34/S iO2催化剂不但可缩短MTO反应的诱导期,三烯选择性也较未添加黏合剂或以A l2O3为黏合剂时高1~2个百分点;且当催化剂活性明显下降时,三烯选择性下降的幅度较小。催化剂粒径、甲醇分压及硅源对催化剂的诱导期也有明显的作用。在甲醇分压低于19kPa、催化剂粒径0.25~0.38mm、S iO2为黏合剂、硅酸四乙酯为硅源时,SAPO-34/S iO2催化剂的MTO性能明显提高。     

DX centers in AlxGa1-xAs bulk alloy,AlAs/GaAs ordered,and disordered superlattices

Properties of theDX centers in Al_0.5Ga_0.5As bulk alloy (b-AL), (AlAs)₂ (GaSa)₂ ordered superlattice (o-SL) and (AlAs) _m (GaAs) _n disordered superlattice (d-SL) (m = 1, 2, 3,n = 1, 2, 3) with the same macroscopic composition were measured and compared. By deconvolution of deep level transient spectroscopy (DLTS) spectrum due to theDX center, we have found a decrease in the number of separate peaks in DLTS spectrum in an intentionally atomic ordered arrangement. Visiting Scholar of the Japan Society for the Promotion of Science. On leave from Department of Electrical Engineering, San Jose State University, San Jose, California 95192-0084, USA.     

Influence of washing and of heat-treatment conditions on the thermal stability of VPI-5

Thorough washing of a VPI-5 synthesized with n-dipropylamine as template improves greatly its thermal stability while no major change is observed in the template content. A detailed study of the influence of the pretreatment conditions shows that in order to obtain a high thermal stability (up to at least 960 °C) two parameters are of importance. The removal of both the template and the adsorbed water requires either a low heating rate at atmospheric pressure or a low pressure (less than 3 Torr) when the heating rate is 300 ° per hour.