Formation of aluminosilicate-bearing quartz veins in the Simano nappe (Central Alps): structural, thermobarometric and oxygen isotope constraints

We combined structural analysis, thermobarometry and oxygen isotope geochemistry to constrain the evolution of kyanite and/or andalusite-bearing quartz veins from the amphibolite facies metapelites of the Simano nappe, in the Central Alps of Switzerland. The Simano nappe records a complex polyphase tectonic evolution associated with nappe stacking during Tertiary Alpine collision (D1). The second regional deformation phase (132) is responsible for the main penetrative schistosity and mineral lineation, and formed during top-to-the-north thrusting. During the next stage of deformation (D3) the aluminosilicate-bearing veins formed by crystallization in tension gashes, in tectonic shadows of boudins, as well as along shear bands associated with top-to-the-north shearing. D2 and D3 are coeval with the Early Miocene metamorphic peak, characterised by kyanite + staurolite + garnet + biotite assemblages in metapelites. The peak pressure (P) and temperature (T) conditions recorded are constrained by multiple-equilibrium thermobarometry at 630 +/- 20 degrees C and 8.5 +/- 1 kbar (similar to 27 km depth), which is in agreement with oxygen isotope thermometry indicating isotopic equilibration of quartz-kyanite pairs at 670 +/- 50 degrees C. Quartz-kyanite pairs from the aluminosilicate-bearing quartz veins yield equilibration temperatures of 645 +/- 20 degrees C, confirming that the veins formed under conditions near metamorphic peak. Quartz and kyanite from veins and the surrounding metapelites have comparable isotopic compositions. Local intergranular diffusion in the border of the veins controls the mass-transfer and the growth of the product assemblage, inducing local mobilization of SiO2 and Al2O3. Andalusite is absent from the host rocks, but it is common in quartz veins, where it often pseudomorphs kyanite. For andalusite to be stable at T-max, the pressure in the veins must have been substantially lower than lithostatic. An alternative explanation consistent with structural observations would be inheritance by andalusite of the kyanite isotopic signature during polymorphic transformation after the metamorphic peak.

Protein-protein interactions between adenovirus DNA polymerase and nuclear factor I mediate formation of the DNA replication preinitiation complex.

The in vitro adenovirus (Ad) DNA replication system provides an assay to study the interaction of viral and host replication proteins with the DNA template in the formation of the preinitiation complex. This initiation system requires in addition to the origin DNA sequences 1) Ad DNA polymerase (Pol), 2) Ad preterminal protein (pTP), the covalent acceptor for protein-primed DNA replication, and 3) nuclear factor I (NFI), a host cell protein identical to the CCAAT box-binding transcription factor. The interactions of these proteins were studied by coimmunoprecipitation and Ad origin DNA binding assays. The Ad Pol can bind to origin sequences only in the presence of another protein which can be either pTP or NFI. While NFI alone can bind to its origin recognition sequence, pTP does not specifically recognize DNA unless Ad Pol is present. Thus, protein-protein interactions are necessary for the targetting of either Ad Pol or pTP to the preinitiation complex. DNA footprinting demonstrated that the Ad DNA site recognized by the pTP.Pol complex was within the first 18 bases at the end of the template which constitutes the minimal origin of replication. Mutagenesis studies have defined the Ad Pol interaction site on NFI between amino acids 68-150, which overlaps the DNA binding and replication activation domain of this factor. A putative zinc finger on the Ad Pol has been mutated to a product that fails to bind the Ad origin sequences but still interacts with pTP. These results indicate that both protein-protein and protein-DNA interactions mediate specific recognition of the replication origin by Ad DNA polymerase.

The Schizosaccharomyces pombe cdc14 gene is required for septum formation and can also inhibit nuclear division.

A conditional heat-sensitive mutation in the cdc14 gene of the fission yeast Schizosaccharomyces pombe results in failure to form a septum. Cells become highly elongated and multinucleate as growth and nuclear division continue in the absence of cell division. This article describes the cloning of the cdc14 gene and the identification of its product, a protein of 240 amino acids, p28cdc14. A null allele of the cdc14 gene shows that the gene is essential for septum formation and completion of the cell-division cycle. Overexpression of the gene product, p28cdc14, causes cell-cycle arrest in late G2 before mitosis. Cells leaking past the block activate p34cdc2 kinase and show condensed chromosomes, but the normal rearrangements of the microtubules and microfilaments that are associated with the transition from interphase to mitosis do not occur. Overexpression of p28cdc14 in mutants, in which the timing of mitosis is altered, suggests that these effects may be mediated upstream of the mitotic inhibitor wee1. These data are consistent with the idea that p28cdc14 may play a role in both the initiation of mitosis and septum formation and, by doing so, be part of the mechanism that coordinates these two cell-cycle events.

Offering planning process development: Bridging the Offering Gaps and Consolidating Top Priority Needs in Product Offering

The aim of this Thesis is to study how to manage the front-end of the offering planning process. This includes actual process development and methods to gather and analyze information to achieve the best outcome in customer oriented product offering. Study is carried out in two parts: theoretical part and company related part. Theoretical framework is created introducing different types of approaches to manage product planning processes. Products are seen as platforms and they are broken down to subsystems to show different parts of the development. With the help of the matrix-based approaches product platform related information is gathered and analyzed. In this kind of analysis business/market drivers and cus-tomer/competitor information are connected with product subsystems. This gives possibilities to study product gaps/needs and possible future ideas/scenarios in different customer segments. Company related part consists of offering planning process development in real company environment. Process formation includes documents and tools that guide planning from the information gathering to the prioritization and decision making.

Development of Collaborative Product Structure Management

The purpose of this thesis is to develop an environment or network that enables effective collaborative product structure management among stakeholders in each unit, throughout the entire product lifecycle and product data management. This thesis uses framework models as an approach to the problem. Framework model methods for development of collaborative product structure management are proposed in this study, there are three unique models depicted to support collaborative product structure management: organization model, process model and product model. In the organization model, the formation of product data management system (eDSTAT) key user network is specified. In the process model, development is based on the case company’s product development matrix. In the product model framework, product model management, product knowledge management and design knowledge management are defined as development tools and collaboration is based on web-based product structure management. Collaborative management is executed using all these approaches. A case study from an actual project at the case company is presented as an implementation; this is to verify the models’ applicability. A computer assisted design tool and the web-based product structure manager, have been used as tools of this collaboration with the support of the key user. The current PDM system, eDSTAT, is used as a piloting case for key user role. The result of this development is that the role of key user as a collaboration channel is defined and established. The key user is able to provide one on one support for the elevator projects. Also the management activities are improved through the application of process workflow by following criteria for each project milestone. The development shows effectiveness of product structure management in product lifecycle, improved production process by eliminating barriers (e.g. improvement of two-way communication) during design phase and production phase. The key user role is applicable on a global scale in the company.

Examining the Role of Rebranding in Perceived Image of a Product Line

The main objective for this study was to explore certain organization’s product line rebranding process and its impact on product line’s perceived image. The case company is a global paper, packaging and forest products company, business segment paper board. The audience explored is one of the company’s major customers, merchant in Germany. The research was performed as a descriptive case study with a purpose to provide longitudinal insight into the product line image and its eventual alteration as a result of the case company’s rebranding process. Mainly qualitative methods were used for conducting the research. The data for the empirical part was collected with a web-based survey at two different points of time; before the rebranded products entered the market and after they had been available approximately six months. The results of this study reveal that the case company has performed well in its attempt to improve product line’s brand image through rebranding. It was found that between the two brand image measurements the product brand image seems to have improved in all of the areas which according to theoretical framework of this study contribute to formation of brand image; brand associations, marketing communications and interpersonal relationships, not forgetting the original platform that initiated the change; technical quality modifications. In other words it may be concluded that as technical quality was brought to a new level, also assessments about the brand image improved respectively.

Recovery and refining of manganese as by-product from hydrometallurgical processes

The consumption of manganese is increasing, but huge amounts of manganese still end up in waste in hydrometallurgical processes. The recovery of manganese from multi-metal solutions at low concentrations may not be economical. In addition, poor iron control typically prevents the production of high purity manganese. Separation of iron from manganese can be done with chemical precipitation or solvent extraction methods. Combined carbonate precipitation with air oxidation is a feasible method to separate iron and manganese due to the fast kinetics, good controllability and economical reagents. In addition the leaching of manganese carbonate is easier and less acid consuming than that of hydroxide or sulfide precipitates. Selective iron removal with great efficiency from MnSO4 solution is achieved by combined oxygen or air oxidation and CaCO3 precipitation at pH > 5.8 and at a redox potential of > 200 mV. In order to avoid gypsum formation, soda ash should be used instead of limestone. In such case, however, extra attention needs to be paid on the reagents mole ratios in order to avoid manganese coprecipitation. After iron removal, pure MnSO4 solution was obtained by solvent extraction using organophosphorus reagents, di-(2-ethylhexyl)phosphoric acid (D2EHPA) and bis(2,4,4- trimethylpentyl)phosphinic acid (CYANEX 272). The Mn/Ca and Mn/Mg selectivities can be increased by decreasing the temperature from the commonly used temperatures (40 –60oC) to 5oC. The extraction order of D2EHPA (Ca before Mn) at low temperature remains unchanged but the lowering of temperature causes an increase in viscosity and slower phase separation. Of these regents, CYANEX 272 is selective for Mn over Ca and, therefore, it would be the better choice if there is Ca present in solution. A three-stage Mn extraction followed by a two-stage scrubbing and two-stage sulfuric acid stripping is an effective method of producing a very pure MnSO4 intermediate solution for further processing. From the intermediate MnSO4 some special Mn- products for ion exchange applications were synthesized and studied. Three types of octahedrally coordinated manganese oxide materials as an alternative final product for manganese were chosen for synthesis: layer structured Nabirnessite, tunnel structured Mg-todorokite and K-kryptomelane. As an alternative source of pure MnSO4 intermediate, kryptomelane was synthesized by using a synthetic hydrometallurgical tailings. The results show that the studied OMS materials adsorb selectively Cu, Ni, Cd and K in the presence of Ca and Mg. It was also found that the exchange rates were reasonably high due to the small particle dimensions. Materials are stable in the studied conditions and their maximum Cu uptake capacity was 1.3 mmol/g. Competitive uptake of metals and acid was studied using equilibrium, batch kinetic and fixed-bed measurements. The experimental data was correlated with a dynamic model, which also accounts for the dissolution of the framework manganese. Manganese oxide micro-crystals were also bound onto silica to prepare a composite material having a particle size large enough to be used in column separation experiments. The MnOx/SiO2 ratio was found to affect significantly the properties of the composite. The higher the ratio, the lower is the specific surface area, the pore volume and the pore size. On the other hand, higher amount of silica binder gives composites better mechanical properties. Birnesite and todorokite can be aggregated successfully with colloidal silica at pH 4 and with MnO2/SiO2 weight ratio of 0.7. The best gelation and drying temperature was 110oC and sufficiently strong composites were obtained by additional heat-treatment at 250oC for 2 h. The results show that silica–supported MnO2 materials can be utilized to separate copper from nickel and cadmium. The behavior of the composites can be explained reasonably well with the presented model and the parameters estimated from the data of the unsupported oxides. The metal uptake capacities of the prepared materials were quite small. For example, the final copper loading was 0.14 mmol/gMnO2. According to the results the special MnO2 materials are potential for a specific environmental application to uptake harmful metal ions.

Behavior of black liquor nitrogen in combustion : formation of cyanate

The Kraft pulping process is the dominant chemical pulping process in the world. Roughly 195 million metric tons of black liquor are produced annually as a by-product from the Kraft pulping process. Black liquor consists of spent cooking chemicals and dissolved organics from the wood and can contain up to 0.15 wt% nitrogen on dry solids basis. The cooking chemicals from black liquor are recovered in a chemical recovery cycle. Water is evaporated in the first stage of the chemical recovery cycle, so the black liquor has a dry solids content of 65-85% prior to combustion. During combustion of black liquor, a portion of the black liquor nitrogen is volatilized, finally forming N2 or NO. The rest of the nitrogen remains in the char as char nitrogen. During char conversion, fixed carbon is burned off leaving the pulping chemicals as smelt, and the char nitrogen forms mostly smelt nitrogen (cyanate, OCN-). Smelt exits the recovery boiler and is dissolved in water. The cyanate from smelt decomposes in the presence of water, forming NH3, which causes nitrogen emissions from the rest of the chemical recovery cycle. This thesis had two focuses: firstly, to determine how the nitrogen chemistry in the recovery boiler is affected by modification of black liquor; and secondly, to find out what causes cyanate formation during thermal conversion, and which parameters affect cyanate formation and decomposition during thermal conversion of black liquor. The fate of added biosludge nitrogen in chemical recovery was determined in Paper I. The added biosludge increased the nitrogen content of black liquor. At the pulp mill, the added biosludge did not increase the NO formation in the recovery boiler, but instead increased the amount of cyanate in green liquor. The increased cyanate caused more NH3 formation, which increased the NCG boiler’s NO emissions. Laboratory-scale experiments showed an increase in both NO and cyanate formation after biosludge addition. Black liquor can be modified, for example by addition of a solid biomass to increase the energy density of black liquor, or by separation of lignin from black liquor by precipitation. The precipitated lignin can be utilized in the production of green chemicals or as a fuel. In Papers II and III, laboratory-scale experiments were conducted to determine the impact of black liquor modification on NO and cyanate formation. Removal of lignin from black liquor reduced the nitrogen content of the black liquor. In most cases NO and cyanate formation decreased with increasing lignin removal; the exception was NO formation from lignin lean soda liquors. The addition of biomass to black liquor resulted in a higher nitrogen content fuel mixture, due to the higher nitrogen content of biomass compared to black liquor. More NO and cyanate were formed from the fuel mixtures than from pure black liquor. The increased amount of formed cyanate led to the hypothesis that black liquor is catalytically active and converts a portion of the nitrogen in the mixed fuel to cyanate. The mechanism behind cyanate formation during thermal conversion of black liquor was not clear before this thesis. Paper IV studies the cyanate formation of alkali metal loaded fuels during gasification in a CO2 atmosphere. The salts K2CO3, Na2CO3, and K2SO4 all promoted char nitrogen to cyanate conversion during gasification, while KCl and CaCO3 did not. It is now assumed that cyanate is formed when alkali metal carbonate or an active intermediate of alkali metal carbonate (e.g. -CO2K) reacts with the char nitrogen forming cyanate. By testing different fuels (bark, peat, and coal), each of which had a different form of organic nitrogen, it was concluded that the form of organic nitrogen in char also has an impact on cyanate formation. Cyanate can be formed during pyrolysis of black liquor, but at temperatures 900°C or above, the formed cyanate will decompose. Cyanate formation in gasifying conditions with different levels of CO2 in the atmosphere was also studied. Most of the char nitrogen was converted to cyanate during gasification at 800-900°C in 13-50% CO2 in N2, and only 5% of the initial fuel nitrogen was converted to NO during char conversion. The formed smelt cyanate was stable at 800°C 13% CO2, while it decomposed at 900°C 13% CO2. The cyanate decomposition was faster at higher temperatures and in oxygen-containing atmospheres than in an inert atmosphere. The presence of CO2 in oxygencontaining atmospheres slowed down the decomposition of cyanate. This work will provide new information on how modification of black liquor affects the nitrogen chemistry during thermal conversion of black liquor and what causes cyanate formation during thermal conversion of black liquor. The formation and decomposition of cyanate was studied in order to provide new data, which would be useful in modeling of nitrogen chemistry in the recovery boiler.

Microfacies analysis of the lower paleocene beda formation in Western Concession 59 and Block 59F, Sirte Basin, Libya /

The rock sequence of the Tertiary Beda Formation of S. W. concession 59 and 59F block in Sirte Basin of Libya has been subdivided into twelve platformal carbonate microfacies. These microfacies are dominated by muddy carbonates, such as skeletal mudstones, wackestones, and packstones with dolomites and anhydrite. Rock textures, faunal assemblages and sedimentary structures suggest shallow, clear, warm waters and low to moderate energy conditions within the depositional shelf environment. The Beda Formation represents a shallowing-upward sequence typical of lagoonal and tidal flat environments marked at the top by sabkha and brackish-water sediments. Microfossils include benthonic foraminifera, such as miliolids, Nummulites, - oerculina and other smaller benthonics, in addition to dasycladacean algae, ostracods, molluscs, echinoderms, bryozoans and charophytes. Fecal pellets and pelloids, along with the biotic allochems, contributed greatly to the composition of the various microfacies. Dolomite, where present, is finely crystalline and an early replacement product. Anhydrite occurs as nodular, chickenwire and massive textures indicating supratidal sabkha deposition. Compaction, micr it i zat ion , dolomit izat ion , recrystallization, cementation, and dissolution resulted in alteration and obliteration of primary sedimentary structures of the Beda Formation microfacies. The study area is located in the Gerad Trough which developed as a NE-SW trending extensional graben. The Gerad trough was characterized by deep-shallow water conditions throughout the deposition of the Beda Formation sediments. The study area is marked by several horsts and grabens; as a result of extent ional tectonism. The area was tectonically active throughout the Tertiary period. Primary porosity is intergranular and intragranular, and secondary processes are characterized by dissolution, intercrystalline, fracture and fenestral features. Diagenesis, through solution leaching and dolomitization, contributed greatly to porosity development. Reservoir traps of the Beda Formation are characterized by normal fault blocks and the general reservoir characteristics/properties appear to be facies controlled.

Kinetic and product studies for the oxidtion of organic sulfides and sulfoxides in the presence of transition metal complexes

Rates and products of the oxidation of diphenyl sulfide, phenyl methyl sulfide, p-chlorophenyl methyl sulfide and diphenyl sulfoxide have been determined. Oxidants included t-Bu02H alone, t-Bu02H plus molybdenum or vanadium catalysts and the molybdenum peroxo complex Mo0(02)2*HMPT. Reactions were chiefly carried out in ethanol at temperatures ranging from 20° to 65°C. Oxidation of diphenyl sulfide by t-Bu02H in absolute ethanol at 65°C followed second-order kinetics with k2 = 5.61 x 10 G M~1s"1, and yielded only diphenyl sulfoxide. The Mo(C0)g-catalyzed reaction gave both the sulfoxide and the sulfone with consecutive third-order kinetics. Rate = k3[Mo][t-Bu02H][Ph2S] + k^[Mo][t-Bu02H][Ph2S0], where log k3 = 12.62 - 18500/RT, and log k^ = 10.73 - 17400/RT. In the absence of diphenyl sulfide, diphenyl sulfoxide did not react with t-Bu02H plus molybdenum catalysts, but was oxidized by t-Bu02H-V0(acac)2. The uncatalyzed oxidation of phenyl methyl sulfide by t-Bu02H in absolute ethanol at 65°C gave a second-order rate constant, k = 3.48 x 10~"5 M^s""1. With added Mo(C0)g, the product was mainly phenyl methyl sulfoxide; Rate = k3[Mo][t-Bu02H][PhSCH3] where log k3 = 22.0 - 44500/RT. Both diphenyl sulfide and diphenyl sulfoxide react readily with the molybdenum peroxy complex, Mo0(02)2'HMPT in absolute ethanol at 35°C, yielding diphenyl sulfone. The observed features are mainly in agreement with the literature on metal ion-catalyzed oxidations of organic compounds by hydroperoxides. These indicate the formation of an active catalyst and the complexation of t-Bu02H with the catalyst. However, the relatively large difference between the activation energies for diphenyl sulfide and phenyl methyl sulfide, and the non-reactivity of diphenyl sulfoxide suggest the involvement of sulfide in the production of an active species.

L’influence du développement durable à travers la formation universitaire en design industriel

Aujourd’hui, nous savons qu’environ 75 à 80% des impacts environnementaux des produits sont déterminés lors de la conception. Le rôle du designer industriel est donc crucial pour arriver à une forme de développement plus viable. Cette recherche tente de cibler les champs de connaissances qui devraient faire partie de la formation des professionnels du développement de produits pour y intégrer les aspects environnementaux. Après une recension de la littérature en design industriel, en pédagogie et en environnement, l’étude de terrain a été conduite en deux temps. Selon des critères prédéfinis, des programmes universitaires « spécialisés » en environnement/développement durable, au Québec, ainsi que des formations en éco-conception, offerts en France, ont été analysés. L’étude de terrain a été complétée par un entretien en profondeur semi-dirigé avec un consultant, qui aide des entreprises québécoises à intégrer l’environnement en développement de produits. L’analyse des informations recueillies met en évidence la nécessité de transformer rapidement les formations universitaires en conception de produits. Le nouveau cursus de design industriel devrait; 1. Intégrer les connaissances relatives aux impacts environnementaux; 2. Encourager le travail en équipes multidisciplinaires pour enrichir la collecte d’informations relative aux projets de développement; 3. Établir une collaboration étroite entre les établissements d’enseignement et les industries, ce qui est essentiel à la compréhension des enjeux de développement de produits et services (culture de l’entreprise, coût, délais, logistique, réglementation, etc.).

Analysis of psychological aspects of Lovemarks formation

El presente trabajo es una revisión de literatura que busca contribuir al entendimiento de los procesos psicológicos subyacentes en la Teoría de Roberts sobre Lovemarks que, dentro del campo del marketing, ha buscado reemplazar la idea que se tiene sobre las marcas. La primera parte proporciona una introducción de lo que ha sido la evolución de las marcas desde una perspectiva psicológica y de mercadeo. En la segunda parte se explica la teoría de Lovemarks haciendo énfasis en sus componentes: el eje amor/respeto, las características de misterio, sensualidad e intimidad. Adicionalmente, se soporta esta teoría a través de literatura complementaria y casos de aplicación exitosos. La tercera parte, corresponde a la identificación y análisis de los procesos y aspectos psicológicos que explican la formación de un Lovemark: percepción, memoria, motivación individual y social y emoción. La cuarta y última parte contiene las conclusiones e implicaciones en la formación de la relación entre el consumidor y una marca.

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.

Formation of organic acids from the gas-phase ozonolysis of terpinolene

Gas-phase ozonolysis of terpinolene was studied in static chamber experiments using gas chromatography coupled to mass spectrometric and flame ionisation detection to separate and detect products. Two isomers of C-7-diacids and three isomers of C-7-aldehydic acids were identified in the condensed phase after derivatisation. Possible mechanisms of formation of these acids were investigated using different OH radical scavengers and relative humidities, and were compared to those reported earlier for the ozonolysis of beta-pinene. In addition, branching ratios for some of the individual reaction steps, e. g. the branching ratio between the two hydroperoxide channels of the C-7-CI, were deduced from the quantitative product yield data. Branching ratios for POZ decomposition and the stabilisation/decomposition of the C-7-CI were also obtained from measurements of the C-7 primary carbonyl product.

Pressure-dependent product distribution of citral hydrogenation over micelle-hosted Pd and Ru nanoparticles in supercritical carbon dioxide

In situ synthesis and testing of Ru and Pd nanoparticles as catalysts in the presence of ammonium perfluorohydrocarbo-carboxylate surfactant in supercritical carbon dioxide were carried out in a stainless steel batch reactor at 40 degrees C over a pressure range of 80-150 bar CO2/H-2. Direct Visualization of the formation of a supercritical phase at above 80 bar, followed by the formation of homogeneous microemulsions containing dispersed Ru nanoparticles and Pd nanoparticles in scCO(2) at above 95-100 bar, were conducted through a sapphire window reactor using a W-0 (molar water to surfactant ratio) of 30. The synthesised RU and Pd nanoparticles showed interesting product distributions in the selective hydrogenation of organic molecules, depending critically oil the density and polarity of the fluid (which ill turn depends on the pressure applied). Thus, selective hydrogenation of the citral molecule, which contains three reducible groups (aldehydes and double bonds at the 23 and 6,7 positions), is feasible Lis a chemical probe. (c) 2005 Elsevier Inc. All rights reserved.