Trade and infrastructure in the Andean Community

Includes bibliography

Novel metallo-porphyrin based colourimetric amine sensors and their processing via plasma enhanced chemical vapour deposition at atmospheric pressure : synthesis, characterisation and mechanistic studies

Volatile amines are prominent indicators of food freshness, as they are produced during many microbiological food degradation processes. Monitoring and indicating the volatile amine concentration within the food package by intelligent packaging solutions might therefore be a simple yet powerful way to control food safety throughout the distribution chain.rnrnIn this context, this work aims to the formation of colourimetric amine sensing surfaces on different substrates, especially transparent PET packaging foil. The colour change of the deposited layers should ideally be discernible by the human eye to facilitate the determination by the end-user. rnrnDifferent tailored zinc(II) and chromium(III) metalloporphyrins have been used as chromophores for the colourimetric detection of volatile amines. A new concept to increase the porphyrins absorbance change upon exposure to amines is introduced. Moreover, the novel porphyrins’ processability during the deposition process is increased by their enhanced solubility in non-polar solvents.rnrnThe porphyrin chromophores have successfully been incorporated into polysiloxane matrices on different substrates via a dielectric barrier discharge enhanced chemical vapour deposition. This process allows the use of nitrogen as a cheap and abundant plasma gas, produces minor amounts of waste and by-products and can be easily introduced into (existing) roll-to-roll production lines. The formed hybrid sensing layers tightly incorporate the porphyrins and moreover form a porous structure to facilitate the amines diffusion to and interaction with the chromophores.rnrnThe work is completed with the thorough analysis of the porphyrins’ amine sensing performance in solution as well as in the hybrid coatings . To reveal the underlying interaction mechanisms, the experimental results are supported by DFT calculations. The deposited layers could be used for the detection of NEt3 concentrations below 10 ppm in the gas phase. Moreover, the coated foils have been tested in preliminary food storage experiments. rnrnThe mechanistic investigations on the interaction of amines with chromium(III) porphyrins revealed a novel pathway to the formation of chromium(IV) oxido porphyrins. This has been used for electrochemical epoxidation reactions with dioxygen as the formal terminal oxidant.rn

Perspectives esthétique et compositionnelle d’une dialectique entre le son et la musique

Visant à contribuer à la pérennité de la musique d’art instrumentale, cette thèse aborde plusieurs sujets la concernant, autant sur les plans théorique et esthétique que pratique et compositionnel. Les deux principaux contextes observés sont ceux de la modernité et de l’économie de marché. Le premier, par le triomphe de la raison technicienne, aurait conduit à l’autonomie de l’art désormais confronté aux risques de l’autoréférence. Le deuxième, par la pression exercée sur le compositeur à la base de la chaîne création-production-diffusion, compromettrait cette autonomie qu’elle avait pourtant contribuée à rendre possible. Or, l’autonomie de l’art, en tant que conquête sur les plans esthétique, social, politique, économique et intellectuel, représente un enjeu de taille, puisque d’éventuelles compromissions envers des impératifs extérieurs impliquent un recul sur tous ces plans. Pour répondre à cette problématique, la thèse explore des pistes de réflexions et d’opérations pour réaffirmer – en le revendiquant – ce que la musique d’art possède en propre et qui mérite encore d’être entendu, militant ainsi pour la survie de ce qui la rend possible. Plus précisément, la dialectique du son et de la musique que je développe ici me permet, dans un premier temps, d’aborder les médiations successives conduisant des ondes mécaniques à se structurer dans notre conscience jusqu’à se transmettre à nous sous forme de patrimoine; puis, dans un deuxième temps, de décrire ma propre intention de communication par la musique en analysant deux œuvres de ma composition : Musique d’art pour quintette à cordes et Musique d’art pour orchestre de chambre II (partie 1.). Musique d’art pour quintette à cordes est une œuvre-concert de soixante-cinq minutes pour quatuor à cordes et contrebasse, spatialisation, traitement et mise en espace des musiciens. Il s’agit d’un projet de recherche-création de mon initiative que j’ai aussi mené à titre de producteur. Musique d’art pour orchestre de chambre II (partie 1.) est une œuvre de commande de quatorze minutes. Le retour critique portant sur l’ensemble des composantes caractéristiques du média ouvre la voie à une corrélation plus étroite entre son contenu et sa forme privilégiée de présentation, le concert. Cette corrélation peut amener le public à désirer visiter les œuvres et apprécier leur signification, préservant la musique d’art comme mode spécifique de connaissance du monde.

Perspectives esthétique et compositionnelle d’une dialectique entre le son et la musique

Visant à contribuer à la pérennité de la musique d’art instrumentale, cette thèse aborde plusieurs sujets la concernant, autant sur les plans théorique et esthétique que pratique et compositionnel. Les deux principaux contextes observés sont ceux de la modernité et de l’économie de marché. Le premier, par le triomphe de la raison technicienne, aurait conduit à l’autonomie de l’art désormais confronté aux risques de l’autoréférence. Le deuxième, par la pression exercée sur le compositeur à la base de la chaîne création-production-diffusion, compromettrait cette autonomie qu’elle avait pourtant contribuée à rendre possible. Or, l’autonomie de l’art, en tant que conquête sur les plans esthétique, social, politique, économique et intellectuel, représente un enjeu de taille, puisque d’éventuelles compromissions envers des impératifs extérieurs impliquent un recul sur tous ces plans. Pour répondre à cette problématique, la thèse explore des pistes de réflexions et d’opérations pour réaffirmer – en le revendiquant – ce que la musique d’art possède en propre et qui mérite encore d’être entendu, militant ainsi pour la survie de ce qui la rend possible. Plus précisément, la dialectique du son et de la musique que je développe ici me permet, dans un premier temps, d’aborder les médiations successives conduisant des ondes mécaniques à se structurer dans notre conscience jusqu’à se transmettre à nous sous forme de patrimoine; puis, dans un deuxième temps, de décrire ma propre intention de communication par la musique en analysant deux œuvres de ma composition : Musique d’art pour quintette à cordes et Musique d’art pour orchestre de chambre II (partie 1.). Musique d’art pour quintette à cordes est une œuvre-concert de soixante-cinq minutes pour quatuor à cordes et contrebasse, spatialisation, traitement et mise en espace des musiciens. Il s’agit d’un projet de recherche-création de mon initiative que j’ai aussi mené à titre de producteur. Musique d’art pour orchestre de chambre II (partie 1.) est une œuvre de commande de quatorze minutes. Le retour critique portant sur l’ensemble des composantes caractéristiques du média ouvre la voie à une corrélation plus étroite entre son contenu et sa forme privilégiée de présentation, le concert. Cette corrélation peut amener le public à désirer visiter les œuvres et apprécier leur signification, préservant la musique d’art comme mode spécifique de connaissance du monde.

A marketing plan for Lightning Bolt

This project had as main goal to improve the perception of male surfers about the surf brand Lightning Bolt. It was proposed the creation of a collection of wetsuits as well as the “A Pure Source” Project to show the commitment of the brand with the surf community. To promote both several promotional activities are suggested such as the use of magazines, radio, banners and social media. To complement the distribution chain of the brand, a concept store and a mobile store are also recommended. With this project the brand will be able to double the number of current surfers that buy the brand in a profitable and effective way. The project is expected to generate a net profit of 91,294€ in year 1.

Engineering design of an integrated sustainable process system for cassava biobased materials

Cassava contributes significantly to biobased material development. Conventional approaches for its bio-derivative-production and application cause significant wastes, tailored material development challenges, with negative environmental impact and application limitations. Transforming cassava into sustainable value-added resources requires redesigning new approaches. Harnessing unexplored material source, and downstream process innovations can mitigate challenges. The ultimate goal proposed an integrated sustainable process system for cassava biomaterial development and potential application. An improved simultaneous release recovery cyanogenesis (SRRC) methodology, incorporating intact bitter cassava, was developed and standardized. Films were formulated, characterised, their mass transport behaviour, simulating real-distribution-chain conditions quantified, and optimised for desirable properties. Integrated process design system, for sustainable waste-elimination and biomaterial development, was developed. Films and bioderivatives for desired MAP, fast-delivery nutraceutical excipients and antifungal active coating applications were demonstrated. SRRC-processed intact bitter cassava produced significantly higher yield safe bio-derivatives than peeled, guaranteeing 16% waste-elimination. Process standardization transformed entire root into higher yield and clarified colour bio-derivatives and efficient material balance at optimal global desirability. Solvent mass through temperature-humidity-stressed films induced structural changes, and influenced water vapour and oxygen permeability. Sevenunit integrated-process design led to cost-effectiveness, energy-efficient and green cassava processing and biomaterials with zero-environment footprints. Desirable optimised bio-derivatives and films demonstrated application in desirable in-package O2/CO2, mouldgrowth inhibition, faster tablet excipient nutraceutical dissolutions and releases, and thymolencapsulated smooth antifungal coatings. Novel material resources, non-root peeling, zero-waste-elimination, and desirable standardised methodology present promising process integration tools for sustainable cassava biobased system development. Emerging design outcomes have potential applications to mitigate cyanide challenges and provide bio-derivative development pathways. Process system leads to zero-waste, with potential to reshape current style one-way processes into circular designs modelled on nature's effective approaches. Indigenous cassava components as natural material reinforcements, and SRRC processing approach has initiated a process with potential wider deployment in broad product research development. This research contributes to scientific knowledge in material science and engineering process design.

Mass conservative three-dimensional water tracer distribution from Markov chain Monte Carlo inversion of time-lapse ground-penetrating radar data

Time-lapse geophysical measurements are widely used to monitor the movement of water and solutes through the subsurface. Yet commonly used deterministic least squares inversions typically suffer from relatively poor mass recovery, spread overestimation, and limited ability to appropriately estimate nonlinear model uncertainty. We describe herein a novel inversion methodology designed to reconstruct the three-dimensional distribution of a tracer anomaly from geophysical data and provide consistent uncertainty estimates using Markov chain Monte Carlo simulation. Posterior sampling is made tractable by using a lower-dimensional model space related both to the Legendre moments of the plume and to predefined morphological constraints. Benchmark results using cross-hole ground-penetrating radar travel times measurements during two synthetic water tracer application experiments involving increasingly complex plume geometries show that the proposed method not only conserves mass but also provides better estimates of plume morphology and posterior model uncertainty than deterministic inversion results.

Evaluation of Philips and Ziegler-Natta high-density polyethylene degradation during processing in an internal mixer using the chain scission and branching distribution function analysis

The oxidative and thermo-mechanical degradation of HDPE was studied during processing in an internal mixer under two conditions: totally and partially filled chambers, which provides lower and higher concentrations of oxygen, respectively. Two types of HDPEs, Phillips and Ziegler-Natta, having different levels of terminal vinyl unsaturations were analyzed. Materials were processed at 160, 200, and 240 degrees C. Standard rheograrns using a partially filled chamber showed that the torque is much more unstable in comparison to a totally filled chamber which provides an environment depleted of oxygen. Carbonyl and transvinylene group concentrations increased, whereas vinyl group concentration decreased with temperature and oxygen availability. Average number of chain scission and branching (n(s)) was calculated from MWD curves and its plotting versus functional groups' concentration showed that chain scission or branching takes place depending upon oxygen content and vinyl groups' consumption. Chain scission and branching distribution function (CSBDF) values showed that longer chains undergo chain scission easier than shorter ones due to their higher probability of entanglements. This yields macroradicals that react with the vinyl terminal unsaturations of other chains producing chain branching. Shorter chains are more mobile, not suffering scission but instead are used for grafting the macroradicals, increasing the molecular weight. Increase in the oxygen concentration, temperature, and vinyl end groups' content facilitates the thermo-mechanical degradation reducing the amount of both, longer chains via chain scission and shorter chains via chain branching, narrowing the polydispersity. Phillips HDPE produces a higher level of chain branching than the Ziegler-Natta's type at the same processing condition. (c) 2006 Elsevier Ltd. All rights reserved.

Chain-store system of marketing and distribution.

Mode of access: Internet.

Long chain alkyl diol distribution in Arabian Sea surface sediments

Oxygen exposure has a large impact on lipid biomarker preservation in surface sediments and may affect the application of organic proxies used for reconstructing past environmental conditions. To determine its effect on long chain alkyl diol and keto-ol based proxies, the distributions of these lipids was studied in nine surface sediments from the Murray Ridge in the Arabian Sea obtained from varying water depths (900 to 3000 m) but in close lateral proximity and, therefore, likely receiving a similar particle flux. Due to substantial differences in bottom water oxygen concentration (<3 to 77 µmol/L) and sedimentation rate, substantial differences exist in the time the biomarker lipids are exposed to oxygen in the sediment. Long chain alkyl diol and keto-ol concentrations in the surface sediments (0-0.5 cm) decreased progressively with increasing oxygen exposure time, suggesting increased oxic degradation. The 1,15-keto-ol/diol ratio (DOXI) increased slightly with oxygen exposure time as diols had apparently slightly higher degradation rates than keto-ols. The ratio of 1,14- vs. 1,13- or 1,15-diols, used as upwelling proxies, did not show substantial changes. However, the C30 1,15-diol exhibited a slightly higher degradation rate than C28 and C30 1,13-diols, and thus the Long chain Diol Index (LDI), used as sea surface temperature proxy, showed a negative correlation with the maximum residence time in the oxic zone of the sediment, resulting in ca. 2-3.5 °C change, when translated to temperature. The UK'37 index did not show significant changes with increasing oxygen exposure. This suggests that oxic degradation may affect temperature reconstructions using the LDI in oxic settings and where oxygen concentrations have varied substantially over time.

Modeling the molecular weight distribution of block copolymer formation in a reversible addition-fragmentation chain transfer mediated living radical polymerization

Block copolymers have become an integral part of the preparation of complex architectures through self-assembly. The use of reversible addition-fragmentation chain transfer (RAFT) allows blocks ranging from functional to nonfunctional polymers to be made with predictable molecular weight distributions. This article models block formation by varying many of the kinetic parameters. The simulations provide insight into the overall polydispersities (PDIs) that will be obtained when the chain-transfer constants in the main equilibrium steps are varied from 100 to 0.5. When the first dormant block [polymer-S-C(Z)=S] has a PDI of 1 and the second propagating radical has a low reactivity to the RAFT moiety, the overall PDI will be greater than 1 and dependent on the weight fraction of each block. When the first block has a PDI of 2 and the second propagating radical has a low reactivity to the RAFT moiety, the PDI will decrease to around 1.5 because of random coupling of two broad distributions. It is also shown how we can in principle use only one RAFT agent to obtain block copolymers with any desired molecular weight distribution. We can accomplish this by maintaining the monomer concentration at a constant level in the reactor over the course of the reaction. (c) 2005 Wiley Periodicals, Inc.

Exploring the digital supply chain:implications and models for online software distribution

As a discipline, supply chain management (SCM) has traditionally been primarily concerned with the procurement, processing, movement and sale of physical goods. However an important class of products has emerged - digital products - which cannot be described as physical as they do not obey commonly understood physical laws. They do not possess mass or volume, and they require no energy in their manufacture or distribution. With the Internet, they can be distributed at speeds unimaginable in the physical world, and every copy produced is a 100% perfect duplicate of the original version. Furthermore, the ease with which digital products can be replicated has few analogues in the physical world. This paper assesses the effect of non-physicality on one such product – software – in relation to the practice of SCM. It explores the challenges that arise when managing the software supply chain and how practitioners are addressing these challenges. Using a two-pronged exploratory approach that examines the literature around software management as well as direct interviews with software distribution practitioners, a number of key challenges associated with software supply chains are uncovered, along with responses to these challenges. This paper proposes a new model for software supply chains that takes into account the non-physicality of the product being delivered. Central to this model is the replacement of physical flows with flows of intellectual property, the growing importance of innovation over duplication and the increased centrality of the customer in the entire process. Hybrid physical / digital supply chains are discussed and a framework for practitioners concerned with software supply chains is presented.

Fish Biodiversity Of The Vitória-trindade Seamount Chain, Southwestern Atlantic: An Updated Database.

Despite a strong increase in research on seamounts and oceanic islands ecology and biogeography, many basic aspects of their biodiversity are still unknown. In the southwestern Atlantic, the Vitória-Trindade Seamount Chain (VTC) extends ca. 1,200 km offshore the Brazilian continental shelf, from the Vitória seamount to the oceanic islands of Trindade and Martin Vaz. For a long time, most of the biological information available regarded its islands. Our study presents and analyzes an extensive database on the VTC fish biodiversity, built on data compiled from literature and recent scientific expeditions that assessed both shallow to mesophotic environments. A total of 273 species were recorded, 211 of which occur on seamounts and 173 at the islands. New records for seamounts or islands include 191 reef fish species and 64 depth range extensions. The structure of fish assemblages was similar between islands and seamounts, not differing in species geographic distribution, trophic composition, or spawning strategies. Main differences were related to endemism, higher at the islands, and to the number of endangered species, higher at the seamounts. Since unregulated fishing activities are common in the region, and mining activities are expected to drastically increase in the near future (carbonates on seamount summits and metals on slopes), this unique biodiversity needs urgent attention and management.