Phase separation, porous structure, and cure kinetics in aliphatic epoxy resin containing hyperbranched polyester

Thermosetting blends of an aliphatic epoxy resin and a hydroxyl-functionalized hyperbranched polymer (HBP), aliphatic hyperbranched polyester Boltorn H40, were prepared using 4,4'-diaminodiphenylmethane (DDM) as the curing agent. The phase behavior and morphology of the DDM-cured epoxy/HBP blends with HBP content up to 40 wt% were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The cured epoxy/HBP blends are immiscible and exhibit two separate glass transitions, as revealed by DMA. The SEM observation showed that there exist two phases in the cured blends, which is an epoxy-rich phase and an HBP-rich phase, which is responsible for the two separate glass transitions. The phase morphology was observed to be dependent on the blend composition. For the blends with HBP content up to 10 wt%, discrete HBP domains are dispersed in the continuous cured epoxy matrix, whereas the cured blend with 40 wt% HBP exhibits a combined morphology of connected globules and bicominuous phase structure. Porous epoxy thermosets with continuous open structures on the order of 100-300 nm were formed after the HBP-rich phase was extracted with solvent from the cured blend with 40 wt% HBP. The DSC study showed that the curing rate is not obviously affected in the epoxy/HBP blends with HBP content up to 40 wt %. The activation energy values obtained are not remarkably changed in the blends; the addition of HBP to epoxy resin thus does not change the mechanism of cure reaction of epoxy resin with DDM. (c) 2006 Wiley Periodicals, Inc.

Nanocomposite Polymer Electrolyte Membranes: Methanol Crossover and Conductivity

Commercial Nafion® 117 membranes were successfully modified by in-situ reactions (sol-gel of TEOS and/or polymerization of aniline) within Nafion structures. Water-methanol permeability and proton conductivity were investigated in order to determine the potential performance of these membranes for DMFC systems. Silica-polyaniline modification resulted in 84% methanol crossover reduction, from 2.45x10^-5 cm2.s^-1 for conventional Nafion membranes to 3.71x10^-6 cm2.s^-1 for the modified silica-polyaniline composite membrane at 75 degrees C. In addition, conductivity was not hindered, as the polyaniline-Nafion membrane increased from 12.2 to 15 mS.cm^-1 as compared to Nafion, while a reduction of 11% was observed for silica-polyaniline-Nafion composite membrane. The results in this work strongly suggest the potential of polyaniline nanocomposites to enhance the performance of DMFCs.

Opposite roles of O-2 in NO- and N2O-carbon reactions: An ab initio study

Previous experimental studies showed that the presence of O-2 greatly enhances NO-carbon reaction while it depresses N2O-carbon reaction on carbon surfaces. A popular explanation for the rate increase is that the addition of O-2 results in a large number of reactive carbon-oxygen complexes, and decomposition of these complexes produces many more active sites. The explanation for the latter is that excess O-2 simply blocks the active sites, thus reducing the rate of N2O-carbon reaction. The contradiction is that O-2 can also occupy active sites in NO-carbon reaction and produce active sites in N2O-carbon reduction. By using ab initio calculation, we find that the opposite roles of O-2 are caused by the different manners of N2O and NO adsorption on the carbon surface. In the presence of excess O-2, most Of the active sites are occupied by oxygen groups. In the competition for the remaining active sites, NO is more likely to chemisorb in the form of NO2 and NO chemisorption is mon thermodynamically favorable than O-2 chemisorption. By contrast, the presence of excess O-2 makes N2O chemisorption much less thermally stable either on the consecutive edge sites or edge sites isolated by semiquinone oxygen. A detailed analysis and discussion of the reaction mechanism of N-2 formation from NO- and N2O-carbon reaction in the presence of O-2 is presented in this paper.

Effects of oxide promoters on metal dispersion and metal-support interactions in Ni catalysts supported on activated carbon

Various oxide-promoted Ni catalysts supported on activated carbon were prepared, and the effect of promoters on the surface structure and properties of Ni catalysts was studied. Physical adsorption (Na adsorption), thermogravimetric analysis (TGA), temperature-programmed desorption (TPD), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts. It is found that nickel is fairly uniformly distributed in the pores of the carbon support. Addition of promoters produces a more homogeneous distribution of nickel ion in carbon. However, distributions of promoters in the pores are varying. Addition of promoters increases the dispersion of nickel in carbon. Promoters also change the interaction between the carbon and Ni, resulting in significantly different behaviors of catalysts under various environments. CaO and MgO promoters improve the reactivity of nickel catalysts with O-2 but retard the interaction between nickel oxide and carbon. La2O3 shows some inhibiting effect on the interactions between nickel oxide and oxygen as well as carbon.

Multi-fluorescent silica colloids for encoding large combinatorial libraries

Large chemical libraries can be synthesized on solid-support beads by the combinatorial split-and-mix method. A major challenge associated with this type of library synthesis is distinguishing between the beads and their attached compounds. A new method of encoding these solid-support beads, 'colloidal bar-coding', involves attaching fluorescent silica colloids ('reporters') to the beads as they pass through the compound synthesis, thereby creating a fluorescent bar code on each bead. In order to obtain sufficient reporter varieties to bar code extremely large libraries, many of the reporters must contain multiple fluorescent dyes. We describe here the synthesis and spectroscopic analysis of various mono- and multi-fluorescent silica particles for this purpose. It was found that by increasing the amount of a single dye introduced into the particle reaction mixture, mono- fluorescent silica particles of increasing intensities could be prepared. This increase was highly reproducible and was observed for six different fluorescent dyes. Multi-fluorescent silica particles containing up to six fluorescent dyes were also prepared. The resultant emission intensity of each dye in the multi-fluorescent particles was found to be dependent upon a number of factors; the hydrolysis rate of each silane-dye conjugate, the magnitude of the inherent emission intensity of each dye within the silica matrix, and energy transfer effects between dyes. We show that by varying the relative concentration of each silane-dye conjugate in the synthesis of multi-fluorescent particles, it is possible to change and optimize the resultant emission intensity of each dye to enable viewing in a fluorescence detection instrument.

Characterization of micro-mesoporous carbon media

A simple method to characterize the micro and mesoporous carbon media is discussed. In this method, the overall adsorption quantity is the sum of capacities of all pores (slit shape is assumed), in each of which the process of adsorption occurs in two sequential steps: the multi-layering followed by pore filling steps. The critical factor in these two steps is the enhancement of the pressure of occluded 'free' molecules in the pore as well as the enhancement of the adsorption layer thickness. Both of these enhancements are due to the overlapping of the potential fields contributed by the two opposite walls. The classical BET and modified Kelvin equations are assumed to be applicable for the two steps mentioned above, with the allowance for the enhanced pore pressure, the enhanced adsorption energy and the enhanced BET constant,all of which vary with pore width. The method is then applied to data of many carbon samples of different sources to derive their respective pore size distributions, which are compared with those obtained from DFT analysis. Similar pore size distributions (PSDs) are observed although our method gives sharper distribution. Furthermore, we use our theory to analyze adsorption data of nitrogen at 77 K and that of benzene at 303 K (ambient temperature). The PSDs derived from these two different probe molecules are similar, with some small differences that could be attributed to the molecular properties, such as the collision diameter. Permeation characteristics of sub-critical fluids are also discussed in this paper. (C) 2001 Elsevier Science B.V. All rights reserved.

Olfaction in the Queensland fruit fly, Bactrocera tryoni. II: Response spectra and temporal encoding characteristics of the carbon dioxide receptors

Single-unit electrophysiology was used to record the nerve impulses from the carbon dioxide receptors of female Queensland fruit flies, Bactrocera tryoni. The receptors responded to stimulation in a phasic-tonic manner and also had a period of inhibition of the nerve impulses after the end of stimulation, at high stimulus intensities. The cell responding to carbon dioxide was presented with a range of environmental odorants and found to respond to methyl butyrate and 2-butanone. The coding characteristics of the carbon dioxide cell and the ability to detect other odorants are discussed, with particular reference to the known behavior of the fly.

Study on diffusion and flow of benzene, n-hexane and CCl4 in activated carbon by a differential permeation method

In this paper the diffusion and flow of carbon tetrachloride, benzene and n-hexane through a commercial activated carbon is studied by a differential permeation method. The range of pressure is covered from very low pressure to a pressure range where significant capillary condensation occurs. Helium as a non-adsorbing gas is used to determine the characteristics of the porous medium. For adsorbing gases and vapors, the motion of adsorbed molecules in small pores gives rise to a sharp increase in permeability at very low pressures. The interplay between a decreasing behavior in permeability due to the saturation of small pores with adsorbed molecules and an increasing behavior due to viscous flow in larger pores with pressure could lead to a minimum in the plot of total permeability versus pressure. This phenomenon is observed for n-hexane at 30degreesC. At relative pressure of 0.1-0.8 where the gaseous viscous flow dominates, the permeability is a linear function of pressure. Since activated carbon has a wide pore size distribution, the mobility mechanism of these adsorbed molecules is different from pore to pore. In very small pores where adsorbate molecules fill the pore the permeability decreases with an increase in pressure, while in intermediate pores the permeability of such transport increases with pressure due to the increasing build-up of layers of adsorbed molecules. For even larger pores, the transport is mostly due to diffusion and flow of free molecules, which gives rise to linear permeability with respect to pressure. (C) 2002 Elsevier Science Ltd. All rights reserved.

Purification and characterisation of functional early pregnancy factor expressed in Sf9 insect cells and in Escherichia coli

Early pregnancy factor (EPF) is a secreted protein with growth regulatory and immunomodulatory properties. It is an extracellular form of the mitochondrial matrix protein chaperonin 10 (Cpn10), a molecular chaperone. An understanding of the mechanism of action of EPF and an exploration of therapeutic potential has been limited by availability of purified material. The present study was undertaken to develop a simple high-yielding procedure for preparation of material for structure/function studies, which could be scaled up for therapeutic application. Human EPF was expressed in Sf9 insect cells by baculovirus infection and in Escherichia coli using a heat inducible vector. A modified molecule with an additional N-terminal alanine was also expressed in E coli. The soluble protein was purified from cell lysates via anion exchange (negative-binding mode), cation exchange, and hydrophobic interaction chromatography, yielding similar to42 and 36 mg EPF from 300 ml bacterial and I L Sf9 cultures, respectively. The preparations were highly purified ( greater than or equal to99% purity on SDS-PAGE for the bacterial products and greater than or equal to97% for that of insect cells) and had the expected mass and heptameric structure under native conditions, as determined by mass spectrometry and gel permeation chromatography, respectively. All recombinant preparations exhibited activity in the EPF bioassay, the rosette inhibition test, with similar potency both to each other and to the native molecule. In two in vivo assays of immuno suppressive activity, the delayed-type hypersensitivity reaction and experimental autoimmune encephalomyelitis, the insect cell and modified bacterial products, both with N-terminal additions (acetylation or amino acid), exhibited similar levels of suppressive activity, but the bacterial product with no N-terminal modification had no effect in either assay. Studies by others have shown that N-terminal addition is not necessary for Cpn10 activity. By defining techniques for facile production of molecules with and without immunosuppressive properties, the present studies make it possible to explore mechanisms underlying the distinction between EPF and Cpn10 activity. (C) 2003 Elsevier Inc. All rights reserved.

Matrix metalloproteinase-2 and-9 involvement in canine tumors

Matrix metalloproteinases (MMPs) are a family of enzymes implicated in the degradation and remodeling of extracellular matrix and in vascularization. They are also involved in pathologic processes such as tumor invasion and metastasis in experimental cancer models and in human malignancies. We used gelatin zymography and inummohistochemistry to determine whether MMP-2 and MMP-9 are present in canine tumors and normal tissues and whether MMP production correlates with clinicopathologic parameters of prognostic importance. High levels of pro-MMP-9, pro-MMP-2, and active MMP-2 were detected in most canine tumors. Significantly higher MMP levels were measured in canine tumors than in nontumors, malignancies had higher MMP levels than benign tumors, and sarcomas had higher active MMP-2 than carcinomas. Cartilaginous tumors produced higher MMP levels than did nonsarcomatous malignancies, benign tumors, and normal tissues, and significantly greater MMP-2 than osteosarcomas and fibrosarcomas. Pro-MMP-9 production correlated with the histologic grade of osteosarcomas. The 62-kd form of active MMP-2 was detected only in high-grade, p53-positive, metastatic malignancies. Zymography proved to be a sensitive and quantitative technique for the assessment of MMP presence but has the limitation of requiring fresh tissue; inummohistochemistry is qualitative and comparatively insensitive but could be of value in archival studies. MMP presence was shown in a range of canine tumors, and their link to tumor type and grade was demonstrated for the first time. This study will allow a substantially improved evaluation of veterinary cancer patients and provides baseline information necessary for the design of clinical trials targeting MMPs.