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     

Recovery of pyruvic acid with weakly basic polymeric sorbents

BACKGROUND: Carboxylic acids are among the most important substances that can be manufactured from biomass. However, the recovery of carboxylic acids from fermentation broths presents a challenging separation problem. To avoid the production of waste salts and net consumption of chemicals in the calcium carboxylate salt process, the use of reversible chemical complexation with polymeric sorbents and extractants is attractive for carboxylic acid recovery. Pyruvic acid is widely used in the manufacture of medicines, pesticides and foodstuffs and can be produced by fermentation. Since the acidity of pyruvic acid (pK_a = 2.49) is stronger than that of normal carboxylic acids, and as few reports on the recovery of pyruvic acid are available, the sorption of pyruvic acid from aqueous solution on two types of weakly basic polymeric sorbent, tertiary amine D301R and primary amine D392, was investigated over a wide pH range and at various salt (MgSO₄) concentrations. RESULTS: Overloading adsorption of pyruvic acid on both weakly basic polymeric sorbents occurred, with the overloading of D392 being greater than that of D301R. The adsorption of pyruvic acid on both sorbents was greatly affected by the solution pH and the salt concentration in the aqueous phase. An overloading model was able to predict the experimental uptake data very well. CONCLUSION: Solution pH is one of the most important operating conditions, and both polymeric sorbents D392 and D301R can be used to recover pyruvic acid from dilute aqueous solution with high efficiency at a solution pH around 2. The uptake by D392 is greater than that by D301R owing to steric hindrance of the tertiary amine. Copyright © 2008 Society of Chemical Industry     

Growth and morphology of nanometer LiMn2O4 powder

The growth of Li_1+xMn₂O₄ via detonation reaction was investigated with respect to the presence of an energetic precursor, such as the metallic nitrate and the degree of confinement of the explosive charge. The detonation products were characterized by scanning electron microscopy. Powder X-ray diffraction and transmission electron microscopy were used to characterize the products. Li_1+xMn₂O₄ with 1-2 μm spherical morphology and more uniform secondary particles, but with smaller primary particles of diameters from 20 to 60 nm and a variety of morphologies were found. The oxides produced by this cheap method affirmed the validity of detonation synthesis of nano-size powders.     

浅谈集成电路的废气处理

集成电路的工业废气有含氟化物、硫酸雾的酸性废气,含氨的碱性废气,含异丙醇、光刻胶的有机废气,含SiO_2的含尘废气,以及含硅烷、磷烷的工艺尾气等,这些工业废气中大部分成分是有毒有害的,必须进行有效的处理才能排入大气中。主要讨论上述工业废气的分类、处理方式、应用范围及应用实例等。     

Negative effect of [bmim][PF6] on the catalytic activity of alcohol dehydrogenase: mechanism and prevention

BACKGROUND: [bmim][PF₆] is a hydrophobic ionic liquid which could be considered as an environmentally friendly solvent for biocatalysis. In pure [bmim][PF₆], however, alcohol dehydrogenase from yeast (YADH) has no catalytic activity. The aim of the present work was (1) to quantitatively study the negative effect of [bmim][PF₆] on the catalytic activity of YADH and the related mechanism and (2) to made an attempt to lessen the negative effect of [bmim][PF₆] on YADH by microemulsifying [bmim][PF₆]. RESULTS: The activity of YADH in the homogeneous solution formed by H₂O, CH₃CH₂OH and [bmim][PF₆] decreased rapidly with the increase of the molar fraction of [bmim][PF₆]. The inhibitory effect of [bmim][PF₆] on YADH was probably caused by the competition of the imidazole group of [bmim][PF₆] with the coenzyme NAD⁺ for the binding sites on YADH. In a water‐in‐[bmim][PF₆] microemulsion, YADH was catalytically active due to the formation of the interfacial membrane of the nonionic surfactant TritonX‐100, which separated YADH from [bmim][PF₆] and avoided the direct inactivation of [bmim][PF₆] on YADH. Under optimal conditions, the activity of YADH was as high as 51 µmol L^?1 min^?1. CONCLUSION: [bmim][PF₆] was an inhibitor of YADH and its negative effect on YADH could be lessened by its microemulsification. Copyright © 2008 Society of Chemical Industry     

Organic‐acid‐catalyzed sol–gel route for preparing poly(methyl methacrylate)–silica hybrid materials

In this study, a series of organic–inorganic hybrid sol–gel materials consisting of a poly(methyl methacrylate) (PMMA) matrix and dispersed silica (SiO₂) particles were successfully prepared through an organic‐acid‐catalyzed sol–gel route with N‐methyl‐2‐pyrrolidone as the mixing solvent. The as‐synthesized PMMA–SiO₂ nanocomposites were subsequently characterized with Fourier transform infrared spectroscopy and transmission electron microscopy. The solid phase of organic camphor sulfonic acid was employed to catalyze the hydrolysis and condensation (i.e., sol–gel reactions) of tetraethyl orthosilicate in the PMMA matrix. The formation of the hybrid membranes was beneficial for the physical properties at low SiO₂ loadings, especially for enhanced mechanical strength and gas barrier properties, in comparison with the neat PMMA. The effects of material composition on the thermal stability, thermal conductivity, mechanical strength, molecular permeability, optical clarity, and surface morphology of the as‐prepared hybrid PMMA–SiO₂ nanocomposites in the form of membranes were investigated with thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, gas permeability analysis, ultraviolet–visible transmission spectroscopy, and atomic force microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Epoxidation of high trans‐1,4‐polyisoprene and its properties

A new organic‐solvent‐free water‐phase suspension method was used to synthesize partially epoxidized high trans‐1,4‐polyisoprene (TPI) to improve its properties, including oil resistance and wet‐skid resistance. The epoxidation was conducted in an aqueous peracetic acid solution and on the TPI granules prepared by a bulk precipitation method with supported titanium catalyst. The effects of the synthesis conditions, including reaction temperature, reaction time, and pH value, on the epoxy content were investigated. Epoxidized trans‐1,4‐polyisoprene (ETPI) with epoxy contents between 10 and 80% were obtained within 4 h. Both the amorphous and crystalline regions of TPI were epoxidized. The crystallization properties decreased with increasing epoxy content. ETPIs possessed lower mechanical properties than TPI but could be enhanced by vulcanization. The oil resistance and wet‐skid resistance were significantly improved after epoxidation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of a novel proton‐exchange membrane for fuel cells operating at high temperatures and low humidities

The synthesis of a p‐toluidine/formaldehyde (PTF) resin was performed, and the effects of the molar ratio of the individual monomers and the polymerization conditions on the structure of the PTF resin were studied. Fourier transform infrared and ¹³C‐NMR spectra were used to characterize the PTF. Wide‐angle X‐ray diffraction patterns revealed the crystalline structures of various PTFs. Polarized optical microscopy revealed that the molar ratio of the monomers had a strong effect on the crystalline morphologies. A longer polymerization time turned out a polymer with a higher intrinsic viscosity and molecular weight, which led to differences in the proton conductivity. All of the PTFs showed a higher proton conductivity than a commercial Nafion membrane at 90–100°C and 0% relative humidity. The proton conductivity of the PTF series could be improved by sulfonation with sulfuric acid and could be maintained after blending with polyurethane. Pure methanol could be used as a fuel source because of the insolubility and nonwetting properties of PTF in methanol to increase the output current density for a PTF membrane electrode assembly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Shear-induced crystallization of poly(phenylene sulfide)

The crystalline morphology of poly(phenylene sulfide) (PPS) isothermally crystallized from the melt under shear has been observed by polarized optical microscope (POM) equipped with a CSS450 hot-stage. The shish–kebab-like fibrillar crystal structure is formed at a higher shear rate or for a longer shear time, which is ascribed to the tight aggregation of numerous oriented nuclei in the direction of shear. The crystallization induction time of PPS decreases with the shear time, indicating that the shear accelerates the formation of stable crystal nuclei. Under shear, the increase of spherulite growth rate results from highly oriented chains. The melting behavior of shear-induced crystallized PPS performed by differential scanning calorimetry (DSC) shows multiple melting peaks. The lower melting peak corresponds to melting of imperfect crystal, and the degree of crystal perfection decreases as the shear rate increases. The higher melting peak is related to the orientation of molecular chains. These oriented molecular chains form the orientation nuclei which have higher thermal stability than the kebab-like lamellae that are developed later. A new model based on the above observation has been proposed to explain the mechanism of shish–kebab-like fibrillar crystal formation under shear flow.     

Accelerated wear testing with a microfabricated surface to evaluate the lubrication ability of biomolecules on polyethylene

Wear of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and wear‐particle‐induced osteolysis and bone resorption are the major factors causing the failure of total joint replacements. It is feasible to improve the lubrication and reduce the wear of artificial joints. We need further understanding of the lubrication mechanism of the synovial fluid. The objective of this study is to evaluate the lubricating ability of three major components in the synovial fluid: albumin, globulin, and phospholipids. An accelerated wear testing procedure in which UHMWPE is rubbed against a microfabricated surface with controlled asperities has been developed to evaluate the lubrication behavior. An analysis of the wear particle dimensions and wear amount of the tests has provided insights for comparing their lubrication performance. It is concluded that the presence of biomolecules at the articulating interface may reduce friction. A higher concentration of a biological lubricant leads to a decrease in the wear particle width. In addition, in combination with the wear results and mechanical analysis, the roles of individual biomolecules contributing to friction and wear at the articulating interface are discussed. These results can help us to identify the role of the biomolecules in the boundary lubrication of artificial joints, and further development of lubricating additives for artificial joints may be feasible. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008