PREPARATION AND STUDY ON SILICONE ACRYLATE MICRO-EMULSION OF MULTIPOLYMER

A silicone acr3,1ate micro-emulsion of multipolymer was prepared by seed emulsion polymeri.Tation. The effects of polymerization process, emulsifier rate and amount, initiator rate and amounl, polymerization temperalure, functional monomers, titration time on performances of emulsion have been discussed in detail.     

Planar and tubular perovskite-type membrane reactors for the partial oxidation of methane to syngas

Dense planar and tubular oxygen separation membranes of La_0.6Ca_0.4Fe_0.75Co_0.25O_3– were investigated as reactors for the partial oxidation (POX) of methane to syngas. Their permeation properties were measured in an air/argon pO₂ gradient as a function of temperature. At 900 °C, the oxygen flux through a 1.26-mm-thick membrane was 0.075 mol/cm²·s and through a 0.25-mm-thick tube, 0.24 mol/cm²·s.For the POX measurements, a catalyst was added to the membrane and methane was introduced on the argon side. This resulted in a gradual increase of the oxygen flux with increasing concentration of methane, reaching 2 mol/cm²·s at 900 °C with pure methane. For the planar reactor, the CO selectivity reached 99% and the CH₄ conversion 75% at 918 °C with pure methane. For the tubular reactor, the CO selectivity and CH₄ conversion were 83 and 99%, respectively, under the same conditions. After 1,400 h of operation in a tubular POX reactor, the membrane was examined revealing phase demixing and local decomposition.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003     

Chemoenzymatic synthesis of (2S,3S,4S)-form, the physiologically active stereoisomer of dehydroxymethylepoxyquinomicin (DHMEQ), a potent inhibitor on NF-κB

A new route for (2S,3S,4S)-form, the physiologically active stereoisomer of dehydroxymethylepoxyquinomicin (DHMEQ), a potent NF-κB inhibitor, was established by chemoenzymatic approach. Elaboration on the asymmetric epoxidation of a p-benzoquinone monoketal with benzylcinchonidinium tert-butylhydroperoxide yielded an epoxyenone, in 79.8% ee and 57% yield in reproducible manner. By way of the transformation of this key intermediate to enantiomerically pure (2S,3S,4S)-DHMEQ, the contaminating undesired enantiomer could be effectively removed by applying Burkholderia cepacia lipase-catalyzed hydrolysis of diacylated precursor. The above integrated combination of chemical asymmetric synthesis and enzyme-catalyzed kinetic resolution enabled us to prepare active DHMEQ in a large-scale.     

Comparative study of new shell-type,sub-2 μm fully porous and monolith stationary phases,focusing on mass-transfer resistance

Today sub-2 μm packed columns are very popular to conduct fast chromatographic separations. The mass-transfer resistance depends on the particle size but some practical limits exist not to reach the theoretically expected plate height and mass-transfer resistance. Another approach applies particles with shortened diffusion path to enhance the efficiency of separations. In this study a systematical evaluation of the possibilities of the separations obtained with 5 cm long narrow bore columns packed with new 2.6 μm shell particles (1.9 μm nonporous core surrounded by a 0.35 μm porous shell, Kinetex™, Core-Shell), packed with other shell-type particles (Ascentis Express™, Fused-Core), totally porous sub-2 μm particles and a 5 cm long narrow bore monolith column is presented. The different commercially available columns were compared by using van Deemter, Knox and kinetic plots. Theoretical Poppe plots were constructed for each column to compare their kinetic performance. Data are presented on polar neutral real-life analytes. Comparison of a low molecular weight compounds (MW = 270–430) and a high molecular weight one (MW ∼ 900) was conducted. This study proves that the Kinetex column packed with 2.6 μm shell particles is worthy of rivaling to sub-2 μm columns and other commercially available shell-type packings (Ascentis Express or Halo), both for small and large molecule separation. The Kinetex column offers a very flat C term. Utilizing this feature, high flow rates can be applied to accomplish very fast separations without significant loss in efficiency.     

Lipase-catalyzed resolution of 5-acetoxy-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene. Application to the synthesis of (+)-(3R,4S)-cis-4-hydroxy-6-deoxyscytalone, a metabolite isolated from Colletotrichum acutatum

(+)-cis-4-Hydroxy-6-deoxyscytalone, a natural product bio-synthesized by Colletotrichum sp., has been prepared and its absolute configuration confirmed as 3R,4S, the key step being a kinetic racemic resolution of a cis-diol easily obtained from commercial 1,2,3,4-tetrahydronaphthalen-1,5-diol. Four lipases and different reaction conditions were tested in order to obtain the best yield and enantiomeric excess. Confirmation of absolute configuration was made by NMR using a single-derivatization low-temperature procedure and MPA as the auxiliary reagent.     

不同体系下根霉脂肪酶失活动力学模型研究

对根霉脂肪酶储存稳定性(干燥状态)及在水中,甘油微量水中等不同体系的热失活机理进行了研究,并求出了动力学参数.结果表明该酶在不同的外部环境中热失活机理并不一致:干燥酶粉符合一级失活模型,酶水溶液和酶甘油微水溶液却符合两步串联失活机理,而且证实甘油对该脂肪酶的热稳定性有促进作用.     

Kinetic and Stoichiometric Parameters in the Production of Carotenoids by <Emphasis Type="Italic">Sporidiobolus salmonicolor</Emphasis> (CBS 2636) in Synthetic and Agroindustrial Media

With the objective of determining the kinetic behavior (growth, substrate, pH, and carotenoid production) and obtain the stoichiometric parameters of the fermentative process by Sporidiobolus salmonicolor in synthetic and agroindustrial media, fermentations were carried out in shaken flasks at 25°C, 180 rpm, and initial pH of 4.0 for 120 h in the dark, sampling every 6 h. The maximum concentrations of total carotenoids in synthetic (913 μg/L) and agroindustrial (502 μg/L) media were attained approximately 100 h after the start of the fermentative process. Carotenoid bioproduction is associated with cell growth and the ratio between carotenoid production and cell growth (Y _P/X) is 176 and 163 μg/g in the synthetic and agroindustrial media, respectively. The pH of the agroindustrial fermentation medium varied from 4.2 to 8.5 during the fermentation. The specific growth rate (μ _X) for S. salmonicolor in synthetic and agroindustrial media was 0.07 and 0.04 h⁻¹, respectively. The synthetic medium allowed for greater productivity, obtaining maximum cell productivity (P _x) of 0.08 g L⁻¹ h⁻¹ and maximum total carotenoid productivity (P _car) of 14.2 μg L⁻¹ h⁻¹. Knowledge of the kinetics of a fermentative process is of extreme importance when transposing a laboratory experiment to an industrial scale, as well as making a quantitative comparison between different culture conditions.     

Preparation of diatomite–TiO<Subscript>2</Subscript> composite for photodegradation of bisphenol-A in water

To enhance the photodegradation performance of pure titanium dioxide (TiO₂), diatomite was used as a porous carrier to immobilize TiO₂ powders using calcination method. The photodegradation of bisphenol-A (BPA; 4,4′-isopropylidenediphenol), which has been listed as one of endocrine disrupting chemicals, was carried out in a batch suspension reactor using pure TiO₂ powders and diatomite–TiO₂ composites, respectively. Under the controlled conditions, the photocatalytic efficiencies of the BPA degradation by the diatomite–TiO₂ composites can be found to be higher than those by pure TiO₂ powders. This result should be attributable to the accessibility of the BPA molecules to the surface of TiO₂ particle in the modified photocatalysts, showing that the enrichment of the organic solute enhanced the rate of photodegradation on the diatomite–TiO₂ composite. However, the photodegradation efficiency was not dependent on the pore properties of these TiO₂ photocatalysts. The experimental results further indicated that the photodegradation kinetics for the destruction of BPA in water followed the first-order model well. The apparent first-order reaction constants (k _obs), thus obtained from the fittings of the model, were in line with the destruction-removal efficiencies of BPA in all the photocatalytic experiments.     

阻抑茜素红S褪色动力学光度法测定痕量汞

在HAc—NaAc介质中,以邻菲啰啉作活化剂,痕量Cr（Ⅵ）对H2O2氧化茜素红S褪色反应存在强烈的催化作用,而Hg（Ⅱ）对此褪色反应具有明显的阻抑作用,由此建立了测定痕量Hg（Ⅱ）的新阻抑动力学光度法。该方法线性范围为0～1．6μg／mL,检出限为2．6&#215;10^-8g／mL,应用于污水中Hg（Ⅱ）的测定,结果满意。     

Decomposition in HTPB bonded HMX followed by heat generation rate and chemiluminescence

The decomposition in HTPB bonded HMX was characterized with two highly sensitive methods: heat flow microcalorimetry (HFMC) and Chemiluminescence (CL). The material is stabilized with a phenolic antioxidant. The heat generation (HFMC) rate was determined from 120 to 150 °C using a TAM™ microcalorimeter and the oxidation of the substance was followed by the CL emission between 100 and 140 °C directly from the solid state sample. The end of antioxidant activity results in both measurements sets in characteristic changes in the curves. Kinetic parameters were calculated applying Arrhenius parameterization for the times to the end of antioxidant activity and by applying modelling with an autocatalytic model extended by a side reaction, which is assigned to the antioxidant consumption. The evaluation with the characteristic times gives good agreement between the two methods; the modelling represents the different but supplementing probing of the two measurement methods. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.