Effect and mechanism in compatibilization of poly(styrene-b-2-ethyl-2-oxazoline) diblock copolymer in poly(2,6-dimethyl-1,4-phenylene oxide) poly(ethylene-ran-acrylic acid) blends

The compatibilization effect of poly(styrene-b-2-ethyl-2-oxazoline) diblock copolymer, P(S-b-EOx), on immiscible blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and poly(ethylene-co-acrylic acid) (EAA) is examined in terms of phase structure and thermal, rheological and mechanical properties, and its compatibilizing mechanism is investigated by Fourier-transform infrared spectroscopy. The block copolymer, synthesized by a mechanism transformation copolymerization, is used in solution blending of PPO/EAA. Scanning electron micrographs show that the blends exhibit a more regular and finer dispersion on addition of a small amount of P(S-b-EOx). Thermal analysis indicates that the grass transition of PPO and the lower endothermic peal; of EAA components become closer on adding P(S-b-EOx), and the added diblock copolymer is mainly located at the interface between the PPO and EAA phases. The interfacial tension estimated by theological measurement is significantly reduced on addition of a small amount of P(S-b-EOx). The tensile strength and elongation at break increase with the addition of the diblock copolymer for PPO-rich blends, whereas the tensile strength increases but the elongation at break decreases for EAA-rich blends. This effect is interpreted in terms of interfacial activity and the reinforcing effect of the diblock copolymer, and it is concluded that the diblock copolymer plays a role as an effective compatibilizer for PPO/EAA blends. The specific interaction between EAA and polar parts of P(S-b-EOx) is mainly hydrogen bonding. (C) 1998 Elsevier Science Ltd. All rights reserved.

MORPHOLOGY AND DYNAMIC MECHANICAL-PROPERTIES OF AB CROSS-LINKED POLYMERS BASED ON POLYURETHANES

Polyoxypropylene glycol (PPG) (or castor oil) and toluene diisocyanate (TDI) were mixed, and the prepolymer polyurethane (PU) (I) was formed. Vinyl-terminated polyurethane (II) was prepared from (I), and hydroxyethyl acrylate, AB crosslinked polymers (ABCPs) were synthesized from (II) and vinyl monomers such as styrene, methyl methacrylate, vinyl acetate, etc. The dynamic mechanical properties and morphology of ABCPs were measured. The ABCPs based on PPG have double glass transition temperatures (T(g)) on the sigma-vs. temperature curves. They display a two-phase morphology with plastic components forming the continous phase and PU-rich domains forming the separated phase on the electron micrographs. Irregular shapes and a highly polydisperse distribution of PU-rich domain sizes were observed. The crosslink density of ABCPs has a notable effect on the morphology and properties. The average diameter of the PU-rich domains depends on the molecular weight of prepolymer PPG. The highly crosslinked structures will produce large numbers of very small domains. ABCPs based on castor oil show a single T(g) relaxation on the dynamic mechanical spectra. The compatibility between the two components is much better in ABCPs based on castor oil than in those based on PPG, because there is a high crosslink density in the former. Comparison of the dynamic mechanical spectra of ABCP and interpenetrating networks (IPN) based on castor oil with similar crosslink density and composition imply that the two components in ABCP are compatible whereas microphase separation occurs in IPN. An improvement in the compatibility is achieved by the crosslinking between the two networks.

Preparation of lanthanide hydrides of nanometric size by the catalytic method

Rare-earth metals were hydrogenated in the presence of TiCl4 catalyst in tetrahydrofuran (THF) at 45 degreesC under normal pressure. Transmission electron micrographs showed that the re. sulting lanthanide hydrides were in the form of nanoparticles. The rate of hydrogenation decreased with increasing atomic number of the rare-earth elements.

A remarkable synergic effect of water-soluble bimetallic catalyst in the hydrogenation of aromatic nitrocompounds

Hydrogenation of nitrobenzene can be catalyzed by the water-soluble catalyst PdCl2(TPPTS)(2) (TPPTS = tris(m-sulfonatophenyl)phosphine trisodium salt) under normal pressure at 65 degrees C in H2O/toluene biphasic solvent system. The exhibits higher catalytic activity and selectivity for the hydrogenation of aromatic nitrocompounds, compared with PdCl2(TPPTS)(2) or H2PtCl6 alone. The transmission electron micrographs demonstrate that the monometallic catalyst is composed of ultrafine palladium particles of almost uniform size while the particles of bimetallic catalyst are more widely distributed in size than those of the monometallic ones. (C) 1999 Elsevier Science B.V. All rights reserved.

Investigation of platinum utilization and morphology in catalyst layer of polymer electrolyte fuel cells

Platinum utilization in the gas-diffusion catalyst layer and thin-film catalyst layer is investigated. The morphology of PTFE and Nafion in a simulated catalyst layer is examined by scanning electronmicroscopy (SEM) and transmission electron microscopy (TEM). The results show that the platinum utilization of the thin-film catalyst layer containing only Pt/C and Nafion is 45.4%. The low utilization is attributed to the fact that the electron conduction of many catalyst particles is impaired by some thick Nafion layers or clumps. For the gas-diffusion (E-TEK) electrode, the platinum utilization is mainly affected by the proton conduction provided by Nafion. The blocking effect of PTFE on the active sites is not serious. When the electrode is sufficiently impregnated with Nafion by an immersion method, the platinum utilization can reach 77.8%. Transmission electron micrographs reveal that although some thick Nafion layers and clumps are observed in the Pt/C + Nafion layer, the distribution of Nafion in the catalyst layer is basically uniform. The melted PTFE disperses in the catalyst layer very uniformly. No large PTFE clumps or wide net-like structure is observed. The reactant gas may have to diffuse evenly in the catalyst layer. (C) 1999 Elsevier Science S.A. All rights reserved.

An efficient approach to modify the catalyst activity for the hydrogenation of nitrobenzene

The addition of a suitable amount of PPh3 to PdCl2 or PdCl2(PhCN)(2) in situ can considerably increase the catalytic activity in the hydrogenation of nitrobenzene, while the catalytic activities of PdCl2 (reduced)+PPh3, PdCl2(PPh3)(2) and Pd(PPh3)(4) are very poor. The poisoning of catalyst by mercury indicates that the catalytically active species are composed of Pd(0) colloidal particles. Transmission electron micrographs show that the size of nanometric Pd(0) particles of PdCl2 with PPh3 added in situ is smaller than that of PhCl2(PPh3) or PdCl2 (reduced)+PPh3. A synergic effect of bimetallic catalysts such as PdCl2+nPPh(3)+NiCl2 (n= 0.5, 1) and PdCl2(PhCN)(2)+PPh3+FeCl3 gives rise to a further increase in the catalytic activity.

Physicochemical properties of silk fibroin after solubilization using calcium chloride with or without ethanol

To elucidate the physicochemical properties of silk protein, we studied the effects of calcium chloride and ethanol on the gelation of fibroin. Fibroin was treated with 5.0 M calcium chloride in water (Ca/W) or 5.0 M calcium chloride in 20% (v/v) ethanol (Ca/Et) and the rheological properties of colloidal fibroin were investigated. The Ca/W-treatment promoted an increased rate of gelation and gave higher gel strength than the Ca/Et-treatment. The maximum gel strengths of Ca/W- and Ca/Et-treated fibroins were obtained at pH 7.0 and pH 5.5, respectively. Scanning electron micrographs showed that the Ca/W-treated fibroin gel had a more developed three-dimensional molecular network than the Ca/Et-treated gel. Further, FT-IR spectra suggested that Ca/W-treated fibroin has more of a beta-structure than Ca/Et-treated one in colloidal conditions. This study indicated that the use of calcium chloride alone was more beneficial to the gelation of fibroin than combined use with ethanol.

Dental microwear in live, wild-trapped Alouatta palliata from Costa Rica.

One problem with dental microwear analyses of museum material is that investigators can never be sure of the diets of the animals in question. An obvious solution to this problem is to work with live animals. Recent work with laboratory primates has shown that high resolution dental impressions can be obtained from live animals. The purpose of this study was to use similar methods to begin to document rates and patterns of dental microwear for primates in the wild. Thirty-three Alouatta palliata were captured during the wet season at Hacienda La Pacifica near Canas, Costa Rica. Dental impressions were taken and epoxy casts of the teeth were prepared using the methods of Teaford and Oyen (1989a). Scanning electron micrographs were taken of the left mandibular second molars at magnifications of 200x and 500x. Lower magnification images were used to calculate rates of wear, and higher magnification images were used to measure the size and shape of microwear features. Results indicate that, while basic patterns of dental microwear are similar in museum samples and samples of live, wild-trapped animals of the same species, ecological differences between collection locales may lead to significant intraspecific differences in dental microwear. More importantly, rates of microwear provide the first direct evidence of differences in molar use between monkeys and humans.

The bactericidal effect of dendritic copper microparticles, contained in an alginate matrix, on Escherichia coli

Although the bactericidal effect of copper has been known for centuries, there is a current resurgence of interest in the use of this element as an antimicrobial agent. During this study the use of dendritic copper microparticles embedded in an alginate matrix as a rapid method for the deactivation of Escherichia coli ATCC 11775 was investigated. The copper/alginate produced a decrease in the minimum inhibitory concentration from free copper powder dispersed in the media from 0.25 to 0.065 mg/ml. Beads loaded with 4% Cu deactivated 99.97% of bacteria after 90 minutes, compared to a 44.2% reduction in viability in the equivalent free copper powder treatment. There was no observed loss in the efficacy of this method with increasing bacterial loading up to 10(6) cells/ml, however only 88.2% of E. coli were deactivated after 90 minutes at a loading of 10(8) cells/ml. The efficacy of this method was highly dependent on the oxygen content of the media, with a 4.01% increase in viable bacteria observed under anoxic conditions compared to a >99% reduction in bacterial viability in oxygen tensions above 50% of saturation. Scanning electron micrographs (SEM) of the beads indicated that the dendritic copper particles sit as discrete clusters within a layered alginate matrix, and that the external surface of the beads has a scale-like appearance with dendritic copper particles extruding. E. coli cells visualised using SEM indicated a loss of cellular integrity upon Cu bead treatment with obvious visible blebbing. This study indicates the use of microscale dendritic particles of Cu embedded in an alginate matrix to effectively deactivate E. coli cells and opens the possibility of their application within effective water treatment processes, especially in high particulate waste streams where conventional methods, such as UV treatment or chlorination, are ineffective or inappropriate.

IN SITU AND IN VITRO IMMUNOLOCALIZATION OF OVIDUCTIN BINDING SITES ON HAMSTER UTERINE EPITHELIAL CELLS AND DETECTION OF A HAMSTER OVIDUCTIN HOMOLOGUE IN THE FEMALE RAT REPRODUCTIVE TRACT

Oviductin is an oviduct-specific and high-molecular-weight glycoprotein that has been suggested to play important roles in the early events of reproduction. The present study was undertaken to localize the oviductin binding sites in the uterine epithelial cells of the golden hamster (Mesocricetus auratus) both in situ and in vitro, and to detect a hamster oviductin homologue in the female rat reproductive tract. Immunohistochemical localization of oviductin in the hamster uterus revealed certain uterine epithelial cells reactive to the monoclonal anti-hamster oviductin antibody. In order to study the interaction between hamster oviductin and the endometrium in vitro, a method for culturing primary hamster uterine epithelial cells has been established and optimized. Study with confocal microscopy of the cell culture system showed a labeling pattern similar to what was observed using immunohistochemistry. Pre-embedding immunolabeling of cultured uterine epithelial cells also showed gold particles associated with the plasma membrane and microvilli. These results demonstrated that hamster oviductin can bind to the plasma membrane of certain hamster uterine epithelial cells, suggesting the presence of a putative oviductin receptor on the uterine epithelial cell surface. In the second part of the present study, using the monoclonal anti-hamster oviductin antibody that cross-reacts with the rat tissue, we have been able to detect an oviduct-specific glycoprotein, with a molecular weight of 180~300kDa, in the female rat reproductive tract. Immunohistochemical labeling of the female rat reproductive tract revealed a strong immunolabeling in the non-ciliated oviductal epithelial cells and a faint immunoreaction on the cell surface of some uterine epithelial cells. Ultrastructurally, immunogold labeling was restricted to the secretory granules, Golgi apparatus, and microvilli of the non-ciliated secretory cells of the oviduct. In the uterus, immunogold labeling was observed on the cell surface of some uterine epithelial cells. Furthermore, electron micrographs of ovulated oocytes showed an intense immunolabeling for rat oviductin within the perivitelline space surrounding the ovulated oocytes. The findings of the present study demonstrated that oviductin is present in the rat oviduct and uterus, and it appears that, in the rat, oviductin is secreted by the non-ciliated secretory cells of the oviduct.

A low molecular weight hydro and organogelator derived from an isohexide and sol-gel transcription of the alcogel

Heating 2,5-di-O-methanesulfonyl-1,4:3,6-dianhydro-D-sorbitol (1) in a range of solvents led to the formation of a gel state at low concentrations. 1 was found to gel aromatics, alcohols and water. The structure of 1 in the solid state was solved by single crystal X-ray crystallography; no strong hydrogen bonds or associated solvents were found in the crystal. Electron micrographs revealed the morphology of the gels to be predominantly rod-like. The ethanol alcogel was used to template silica by sol-gel transcription.

Textural properties of whey based edible films

The objective of this work was to study the textural properties of edible films made from sour (acid) whey for food wrapping application. Acid whey is often regarded as a waste product, obtained as a watery effluent in the manufacturing of cottage cheese. In general, owing to its high nutritional value, whey has gained importance as an additive in food manufacturing processes and in health drink formulations. In this work, fresh sour whey was used to make edible films. The proteins in the whey were concentrated by ultrafiltration to reduce the water content. Only natural ingredients such as acid whey and agar were used to form the film under controlled heating (650 W) in a microwave oven. The structural and surface characteristics of the films were tested by a texture analyser and scanning electron micrographs.

Verification of McCabe's Delta L Law for Growth of Lysozyme Crystals by Hanging Drop Method

Lysozyme is a naturally occurring enzyme in egg white and has high commercial importance due to its antimicrobial properties. The main objective of this work was to study the growth rate of lysozyme crystals isolated from egg for the first 72 hours and verify the results with McCabe’s constant crystal growth theory. Hanging drop crystallization method was used to form high purity lysozyme crystals from the embryonic stage. To this end, this work differs from an earlier work of Forsythe et al., who used seed crystals in the size range of 10 µm - 40 µm for face growth measurements at different pH values. The maximum crystal size recorded in the present work was 392.86 µm, which is within the typical size range of 50 µm - 500 µm for which constant crystal growth is expected to hold according to McCabe’s ?L law. Electron micrographs (SEM) revealed the structure and dimensions of the crystals while SDS-Page was used to measure the purity of the crystals. The SEM results showed that that lysozyme growth rate was linear and agreed with McCabe’s constant growth theory, producing a growth rate of 1.77 x 10-3 µm .s-1

Morphology and compression behaviour of biodegradable scaffolds produced by the sintering process

Porous poly(L-lactic acid) (PLA) scaffolds of 85 per cent and 90 per cent porosity are prepared using polymer sintering and porogen leaching method. Different weight fractions of 10 per cent, 30 per cent, and 50 per cent of hydroxyapatite (HA) are added to the PLA to control the acidity and degradation rate. The three-dimensional (3D) morphology and surface porosity are tested using micro-computer tomography (micro-CT), optical microscopy, and scanning electron microscopy (SEM). Results indicate that the surface porosity does not change on the addition of HA. The micro-CT examinations show a slight decrease in the pore size and increase in the wall thickness accompanied by reduced anisotropy for the scaffolds containing HA. Scanning electron micrographs show detectable interconnected pores for the scaffold with pure PLA. Addition of the HA results in agglomeration of the HA particles and reduced leaching of the porogen. Compression tests of the scaffold identify three stages in the stress-strain curve. The addition of HA results in a reduction in the modulus of the scaffold at the first stage of elastic bending of the wall, but this is reversed for the second and third stages of collapse of the wall and densification in the compression tests. In the scaffolds with 85 per cent porosity, the addition of a high percentage of HA could result in 70 per cent decrease in stiffness in the first stage, 200 per cent increase in stiffness in the second stage, and 20 per cent increase in stiffness in the third stage. The results of these tests are compared with the Gibson cellular material model that is proposed for prediction of the behaviour of cellular material under compression. The pH and molecular weight changes are tracked for the scaffolds within a period of 35 days. The addition of HA keeps the pH in the alkaline region, which results in higher rate of degradation at an early period of observation, followed by a reduced rate of degradation later in the process. The final molecular weight is higher for the scaffolds with HA than for scaffolds of pure PLA. The manufactured scaffolds offer acceptable properties in terms of the pore size range and interconnectivity of the pores and porosity for non-load-bearing bone graft substitute; however, improvement to the mixing of the phases of PLA and HA is required to achieve better integrity of the composite scaffolds. © 2008 IMechE.

Biochemical and histological investigations of viral localisation in the hypersensitive reaction of Phaselous vulgaris L. var Pinto to tobacco mosaic virus infection

STOBBS, Lorne,W ABSTRACT Biochemical and Histological Investigations of viral localisation in the hypersensitive reaction of Phaseolus vulgaris L. var Pinto to tobacco mosaic virus infection. The infection of Phaseolus vulgaris L. var Pinto with tobacco mosaic virus (TMV) results in the production of distinct necrotic lesions confining the virus to restricted areas of the leaf surface. Biochemical and histological changes in the leaf tissue as a result of infection have been described. Trace accumulations of fluorescent metabolites, detected prior to lesion expression represent metabolites produced, by the cell in response to virus infection. These substances, are considered to undergo oxidation and in diffusing into adjacent cells, react with cellular constituents causing the death of these cells. Such cellular necrosis in advance of infection effectively limits virus spread. Chromatographic studies on extracts from TMV infected Pinto bean leaf tissue suggests that a number of extra-fluorescent metabolites produced on lesion'expression represent end products of phenolic oxidation r,eactionsoccurring earlier in these cells. Inhibition of phenolic oxidation by ascorbate infiltration or elevated temperature treatment resulted in the absence of extra-fluorescent metabolites and the continued movement of virus in the absence of necrosis. Further studies with i ascorbate infiltration indicated that irreversible necrotic events were determined as early as 12 tci 18 hrs after viral inoculation. Histochemical tests indicated that callose formation was initiated at this time, and occurred in response to necrotisation. Inhibition of necrosis by either ascorbate infiltration or elevated temp8rature treatment resulted in the absence of callose deposition. Scanning electron'micrographs of infected tissue revealed severe epidermal and palisade cell damage. Histochemical tests indicated extensive callose formation in cells bordering the lesion, and suggested the role of callose iTh the blockage of intercellular connections limiting virus movement. The significance of these cellular changes is discussed. ii