The influence of calcium and magnesium on the growth of the lichens Parmelia saxatilis and Xanthoria parietina on slate substrates

In South Gwynedd, Wales, U.K., the calcicole lichen Xanthoria parietina occurs not only on alkaline substrates at inland sites but also on siliceous rock at coastal martimie sites while the calcifuge species Parmelia saxatilis occurs only at inland sites and on slate rocks. Samples of maritime and inland slate did not differ significantly in their calcium or magnesium content. Thalli of X. parietina on pieces of slate did not survive when transplanted from maritime rocks to a site inland. Thalli of maritime X. parietina and P. saxatilis on slate were then transplanted to a site inland and were treated at intervals during 1 year either with calcium carbonate applied as a thick paste or a 0.25 mM solution of calcium chloride. Treatment of X. parietina with calcium carbonate enabled the thalli to survive and grow. However, addition of calcium carbonate to P. saxatilis resulted in low growth rates and fragmentation of the centres of the thalli. The calcium chloride solution had no statistically significant effects on the growth of either species. In addition, thalli of both species were treated with calcium or magnesium carbonates or wetted with an alkaline buffer at intervals over 12-14 months. Thalli of X. parietina survived and grew rapidly when treated with either carbonate but the growth of the buffer-treated thalli gradually declined over the experimental period. Thalli of P. saxatilis fragmented and disappeared after 8-10 months after treatment with either carbonate but normal growth occurred in the buffer treatment. Xanthoria parietina may occur on siliceous maritime rocks at the site because of the presence of calcium or magnesium in sea spray combined with the spray’s alkaline pH. By contrast, P. saxatilis may be confined to siliceous rocks inland because the thalli grow poorly in the presence of calcium and magnesium.

Iron in the substrates and sporophores of Agaricus bisporus (Lange) Pilat during growth and development

The changes of the concentration of iron in the growth substrates and the sporophores of Agaricus bisporus (Lange) Pilat that occurred during culture under standard commercial conditions, were observed using atomic absorption spectrophotometry and iron-59 radiotracing techniques. The routes of translocation and sites of iron accumulation within the sporophore were shovn to alter during development and by the use of novel, pelletised substrates the concentration of iron in the mycelium of the substrates and in developing sporophores was observed during culture. Findings indicated that the compost was the major source of iron and that the concentration of iron in the compost mycelium varied cyclically in relation to the periodic appearance of sporophores. In the casing layer the mycelium is organised into strands which are responsible for the movement of iron from the compost into developing sporophores. A photographic technique for estimating sporophore growth rates showed that the accumulation of iron was not concomitant with sporophore growth and this was attributable to a declining quantity of available iron in the compost mycelium during sporophore growth. Variations in the quantity of iron in sporophores resulted primarily from differences in the quantity of water soluble iron in the compost but, the productivity of the crop, the type of casing layer and differences in watering also influenced sporophore composition. Changes in the concentration of extractable iron in the compost and casing layer throughout culture were related to mycelial activity and to a lesser extent were influenced by watering and the bacterial populations of the casing layer. Thus, the findings of this study give some indication of the relative importance that different cultural conditions exert over sporophore composition together with demonstrations of the movement of a single material within the sporophores and substrates during the cultivation of Agaricus bisporus.

Influence of pretreatment on corrosion behaviour of duplex zinc/polymer coatings on steel substrates

An investigation has been undertaken to determine the major factors influencing the corrosion resistance of duplex-zinc coatings on steel substrates.Premature failure of these systems has been attributed to the presence of defects such as craters and pinholes in the polymer film and debonding of the polymer film from the zinc substrate.Defects found on commercially produced samples have been carefully characterised using metallographic and scanning electron microscopy techniques. The influence of zinc substrate surface roughness, polymer film thickness and degassing of conversion coatings films on the incidence of defects has been determined.Pretreatments of the chromate, chromate-phosphate, non chromate, and alkali-oxide types were applied and the conversion coatings produced characterised with respect to their nature and composition. The effect of degassing on the properties of the films was also investigated. Electrochemical investigations were carried out to determine the effect of the presence of the eta or zeta phase as the outermost layer of the galvanized coating.Flow characteristics of polyester on zinc electroplated hot-dip continuous and batch galvanized and zinc sprayed samples were investigated using hot-stage microscopy. The effects of different pretreatments and degassing after conversion coating formation on flow characteristics were determined.Duplex coatings were subjected to the acetic acid salt spray test. The effect on adhesion was determined using an indentation debonding test and the results compared with those obtained using cross-cut/peel and pull-off tests. The locus of failure was determined using scanning electron microscopy and X-ray photoelectron spectroscopy techniques.

Microstructural study of aluminide surface coatings on single crystal nickel base superalloy substrates

Aluminide diffusion coatings are frequently employed to enhance the oxidation resistance of nickel base superalloys. However, there is a concern that the presence of an aluminide coating could influence the properties of the coated superalloy, especially in respect of fatigue behaviour. To understand the nature of the effects of surface coatings on the fatigue properties of superalloys, an understanding of microstructural development within both the coating and the coating/substrate interfacial zone during high temperature fatigue testing is necessary. This paper is concerned with microstructural changes in aluminide diffusion coatings on single crystal γ′ strengthened superalloy substrates during the course of high temperature fatigue testing. The 'edge on' transmission electron microscopy technique is employed to study cross-sections of two stage (aluminization plus diffusion treatment) coated superalloy samples. The paper examines the degradation of the coating produced by phase transformations induced by loss of aluminum from the coating and/or aging of the coating. Aluminum removal both by interdiffusion with the substrate and by oxidation of the coating surface is considered. Microstructural development in the portion of the substrate influenced by interdiffusion with the coating is also discussed.

An investigation of support effects on the Pt-catalysed selective transformation of α,β-unsaturated substrates

Pt catalyst series were prepared on mesoporous SBA-15, SBA-16, KIT-6, true liquidcrystal-templated meso-macroporous SBA-15 and a commercial, low surface area silicasupport. Support structure can be easily fabricated using surfactant templating as a mode ofstringent control on porosity, surface area and internal structure. The impact of varying Pt-support physicochemical properties was systematically studied for the selective transformation of allylic substrates under chemoselective oxidation and hydrogenation regimes, a class of reactions highly applicable to industry. Pt-based heterogeneous catalysts are well-known for their utilisation in the hydrogenation of α,β-unsaturated aldehydes,although the mode of action and lack of systematic studies in the literature fuels continuing debate into the role of Pt nanoparticles and support choice for this area. This project attempts to shed some light on several frequently asked questions in this field. Successful support synthesis and stability after Pt impregnation is confirmed through HRTEM, XRD and N2 porosimetry. Decreasing metal loading promoted dispersion values,regardless of support choice, with surface PtO2 content also showing visible enhancement.Increasing support surface area and mesoporosity exhibited the following trend on Pt dispersion augmentation; low surface area commercial silica < true liquid crystal-templated SBA-15 < SBA-15 < SBA-16 ~ KIT-6. For the selective oxidation of cinnamyl alcohol,increasing PtO2 surface population confers substantial rate enhancements, with turnover frequencies evidencing PtO2 to be the active species .In the Pt-catalysed hydrogenation of cinnamaldehyde, strong support insensitivity was observed towards catalytic activity; as turnover frequencies normalised to Pt metal reveal constant values. However, structure sensitivity to the desired unsaturated alcohol arose,evidencing the requirement of flat, extended Pt (111) facets for C=O hydrogenation. Pt/SBA-15 proved the most selective, reflecting suppressed cinnamyl alcohol hydrogenation, with DRIFTS and in-situ ATR-IR evidencing the key role of support polarity in re-orientation of cinnamaldehyde to favour di-σCO adsorption and C=O versus C=C hydrogenation. High pressures increased activity, whilst a dramatic shift in selectivity from dominant C=C (1 bar)to C=O hydrogenation (10 bar) was also observed, attributed to surface crowding and suppression of di-σCC and η4 di-σCO+πC=C cinnamaldehyde binding modes.

Embedded heat pipes in cofired ceramic substrates for enhanced thermal management of electronics

A novel and new thermal management technology for advanced ceramic microelectronic packages has been developed incorporating miniature heat pipes embedded in the ceramic substrate. The heat pipes use an axially grooved wick structure and water as the working fluid. Prototype substrate/heat pipe systems were fabricated using high temperature co-fired ceramic (alumina). The heat pipes were nominally 81 mm in length, 10 mm in width, and 4 mm in height, and were charged with approximately 50–80 μL of water. Platinum thick film heaters were fabricated on the surface of the substrate to simulate heat dissipating electronic components. Several thermocouples were affixed to the substrate to monitor temperature. One end of the substrate was affixed to a heat sink maintained at constant temperature. The prototypes were tested and shown to successful and reliably operate with thermal loads over 20 Watts, with thermal input from single and multiple sources along the surface of the substrate. Temperature distributions are discussed for the various configurations and the effective thermal resistance of the substrate/heat pipe system is calculated. Finite element analysis was used to support the experimental findings and better understand the sources of the system's thermal resistance. ^

New organogermanium substrates for palladium-catalyzed cross-coupling reactions. Application of organogermanes towards the synthesis of carbon-5 modified uridine analogues

The diverse biological properties exhibited by uridine analogues modified at carbon-5 of the uracil base have attracted special interest to the development of efficient methodologies for their synthesis. This study aimed to evaluate the possible application of vinyl tris(trimethylsilyl)germanes in the synthesis of conjugated 5-modified uridine analogues via Pd-catalyzed cross-coupling reactions. The stereoselective synthesis of 5-[(2-tris(trimethylsilyl)germyl)ethenyl]uridine derivatives was achieved by the radical-mediated hydrogermylation of the protected 5-alkynyluridine precursors with tris(trimethylsilyl)germane [(TMS)3GeH]. The hydrogermylation with Ph3GeH afforded in addition to the expected 5-vinylgermane, novel 5-(2-triphenylgermyl)acetyl derivatives. Also, the treatment with Me3GeH provided access to 5-vinylgermane uridine analogues with potential biological applications. Since the Pd-catalyzed cross-coupling of organogermanes has received much less attention than the couplings involving organostannanes and organosilanes, we were prompted to develop novel organogermane precursors suitable for transfer of aryl and/or alkenyl groups. The allyl(phenyl)germanes were found to transfer allyl groups to aryl iodides in the presence of sodium hydroxide or tetrabutylammonium fluoride (TBAF) via a Heck arylation mechanism. On the other hand, the treatment of allyl(phenyl)germanes with tetracyanoethylene (TCNE) effectively cleaved the Ge-C(allyl) bonds and promoted the transfer of the phenyl groups upon fluoride activation in toluene. It was discovered that the trichlorophenyl,- dichlorodiphenyl,- and chlorotriphenylgermanes undergo Pd-catalyzed cross-couplings with aryl bromides and iodides in the presence of TBAF in toluene with addition of the measured amount of water. One chloride ligand on the Ge center allows efficient activation by fluoride to promote transfer of one, two or three phenyl groups from the organogermane precursors. The methodology shows that organogermanes can render a coupling efficiency comparable to the more established stannane and silane counterparts. Our coupling methodology (TBAF/moist toluene) was also found to promote the transfer of multiple phenyl groups from analogous chloro(phenyl)silanes and stannanes.

Embedded Heat Pipes in Cofired Ceramic Substrates for Enhanced Thermal Management of Electronics

A novel and new thermal management technology for advanced ceramic microelectronic packages has been developed incorporating miniature heat pipes embedded in the ceramic substrate. The heat pipes use an axially grooved wick structure and water as the working fluid. Prototype substrate/heat pipe systems were fabricated using high temperature co-fired ceramic (alumina). The heat pipes were nominally 81 mm in length, 10 mm in width, and 4 mm in height, and were charged with approximately 50-80 mL of water. Platinum thick film heaters were fabricated on the surface of the substrate to simulate heat dissipating electronic components. Several thermocouples were affixed to the substrate to monitor temperature. One end of the substrate was affixed to a heat sink maintained at constant temperature. The prototypes were tested and shown to successful and reliably operate with thermal loads over 20 Watts, with thermal input from single and multiple sources along the surface of the substrate. Temperature distributions are discussed for the various configurations and the effective thermal resistance of the substrate/heat pipe system is calculated. Finite element analysis was used to support the experimental findings and better understand the sources of the system's thermal resistance.

New Organogermanium Substrates for Palladium-Catalyzed Cross-Coupling Reactions. Application of Organogermanes towards the Synthesis of Carbon-5 Modified Uridine Analogues

The diverse biological properties exhibited by uridine analogues modified at carbon-5 of the uracil base have attracted special interest to the development of efficient methodologies for their synthesis. This study aimed to evaluate the possible application of vinyl tris(trimethylsilyl)germanes in the synthesis of conjugated 5-modified uridine analogues via Pd-catalyzed cross-coupling reactions. The stereoselective synthesis of 5-[(2-tris(trimethylsilyl)germyl)ethenyl]uridine derivatives was achieved by the radical-mediated hydrogermylation of the protected 5-alkynyluridine precursors with tris(trimethylsilyl)germane [(TMS)3GeH]. The hydrogermylation with Ph3GeH afforded in addition to the expected 5-vinylgermane, novel 5-(2-triphenylgermyl)acetyl derivatives. Also, the treatment with Me3GeH provided access to 5-vinylgermane uridine analogues with potential biological applications. Since the Pd-catalyzed cross-coupling of organogermanes has received much less attention than the couplings involving organostannanes and organosilanes, we were prompted to develop novel organogermane precursors suitable for transfer of aryl and/or alkenyl groups. The allyl(phenyl)germanes were found to transfer allyl groups to aryl iodides in the presence of sodium hydroxide or tetrabutylammonium fluoride (TBAF) via a Heck arylation mechanism. On the other hand, the treatment of allyl(phenyl)germanes with tetracyanoethylene (TCNE) effectively cleaved the Ge-C(allyl) bonds and promoted the transfer of the phenyl groups upon fluoride activation in toluene. It was discovered that the trichlorophenyl,- dichlorodiphenyl,- and chlorotriphenylgermanes undergo Pd-catalyzed cross-couplings with aryl bromides and iodides in the presence of TBAF in toluene with addition of the measured amount of water. One chloride ligand on the Ge center allows efficient activation by fluoride to promote transfer of one, two or three phenyl groups from the organogermane precursors. The methodology shows that organogermanes can render a coupling efficiency comparable to the more established stannane and silane counterparts. Our coupling methodology (TBAF/moist toluene) was also found to promote the transfer of multiple phenyl groups from analogous chloro(phenyl)silanes and stannanes.

Kinase C substrates and synaptic plasticity in Aplysia

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Writing self-assembled monolayers with Cs: Optimization of atomic nanolithography imaging using self-assembled monolayers on gold substrates

We report the results of a study into the factors controlling the quality of nanolithographic imaging. Self-assembled monolayer (SAM) coverage, subsequent postetch pattern definition, and minimum feature size all depend on the quality of the Au substrate used in material mask atomic nanolithographic experiments. We find that sputtered Au substrates yield much smoother surfaces and a higher density of {111}-oriented grains than evaporated Au surfaces. Phase imaging with an atomic force microscope shows that the quality and percentage coverage of SAM adsorption are much greater for sputtered Au surfaces. Exposure of the self-assembled monolayer to an optically cooled atomic Cs beam traversing a two-dimensional array of submicron material masks mounted a few microns above the self-assembled monolayer surface allowed determination of the minimum average Cs dose (2 Cs atoms per self-assembled monolayer molecule) to write the monolayer. Suitable wet etching, with etch rates of 2.2 nm min-1, results in optimized pattern definition. Utilizing these optimizations, material mask features as small as 230 nm in diameter with a fractional depth gradient of 0.820 nm were realized.