Pastoral Livelihoods in South Ethiopia - Value Chain Assessment of Gum & Resins in Moyale Area

This research assessed the value chain of gum and resins, which are available in four woreda in the southern lowlands of Ethiopia. They are Moyale Somali, Moyale Oromia, Dhas and Dire woreda. The output of this research is the elaboration of three value chains. The first is a general one for all the woreda, while the other two concern the Moyale and Dubluk markets. The assessed products are the gum arabic from Acacia trees and the resin exuded by the dunkhal tree - Boswellia family. The aim of this study was not only to understand the way in which resins and gum gain value through the chain and the profit each stakeholder gains, but more importantly how pastoralists use resin and gum collection to diversify their income. The first chapter analyses what it means to be a pastoralist in the Moyale area and its challenges. The second chapter describes how the policies of the central state influenced the pastoral access to rangelands and water and the way in which this contributed to the increase of conflict among the different groups. A particular focus is on the settlement. The third chapter describes the different ethnic groups living in the studied area and their management system to preserve resources and cope with the dry season. This chapter considers the dynamic evolution of the relations among the various groups in terms of negotiating access to resources while facing political and climatic challenges. The fourth chapter illustrates the physical context and the environment, and the way in which it has been managed in order to preserve the pastoral lifestyle. The fifth chapter describes the characteristics of gum and resins in the studied area. Finally, the sixth chapter describes how the value chain methodology was applied in this specific study and its outputs.

Evaluation of fluid transport processes in dental enamel. Methods to assess the relevance of enamel permeability in caries prevention and etching treatments.

This thesis evaluated in vivo and in vitro enamel permeability in different physiological and clinical conditions by means of SEM inspection of replicas of enamel surface obtained from polyvinyl siloxane impressions subsequently later cast in polyether impression ma-terial. This technique, not invasive and risk-free, allows the evaluation of fluid outflow from enamel surface and is able to detect the presence of small quantities of fluid, visu-alized as droplets. Fluid outflow on enamel surface represents enamel permeability. This property has a paramount importance in enamel physiolgy and pathology although its ef-fective role in adhesion, caries pathogenesis and prevention today is still not fully under-stood. The aim of the studies proposed was to evaluate enamel permeability changes in differ-ent conditions and to correlate the findings with the actual knowledge about enamel physiology, caries pathogenesis, fluoride and etchinhg treatments. To obtain confirmed data the replica technique has been supported by others specific techniques such as Ra-man and IR spectroscopy and EDX analysis. The first study carried out visualized fluid movement through dental enamel in vivo con-firmed that enamel is a permeable substrate and demonstrated that age and enamel per-meability are closely related. Examined samples from subjects of different ages showed a decreasing number and size of droplets with increasing age: freshly erupted permanent teeth showed many droplets covering the entire enamel surface. Droplets in permanent teeth were prominent along enamel perikymata. These results obtained through SEM inspection of replicas allowed innovative remarks in enamel physiology. An analogous testing has been developed for evaluation of enamel permeability in primary enamel. The results of this second study showed that primary enamel revealed a substantive permeability with droplets covering the entire enamel sur-face without any specific localization accordingly with histological features, without changes during aging signs of post-eruptive maturation. These results confirmed clinical data that showed a higher caries susceptibility for primary enamel and suggested a strong relationship between this one and enamel permeability. Topical fluoride application represents the gold standard for caries prevention although the mechanism of cariostatic effect of fluoride still needs to be clarified. The effects of topical fluoride application on enamel permeability were evaluated. Particularly two dif-ferent treatments (NaF and APF), with different pH, were examined. The major product of topical fluoride application was the deposition of CaF2-like globules. Replicas inspec-tion before and after both treatments at different times intervals and after specific addi-tional clinical interventions showed that such globule formed in vivo could be removed by professional toothbrushing, sonically and chemically by KOH. The results obtained in relation to enamel permeability showed that fluoride treatments temporarily reduced enamel water permeability when CaF2-like globules were removed. The in vivo perma-nence of decreased enamel permeability after CaF2 globules removal has been demon-strated for 1 h for NaF treated teeth and for at least 7 days for APF treated teeth. Important clinical consideration moved from these results. In fact the caries-preventing action of fluoride application may be due, in part, to its ability to decrease enamel water permeability and CaF2 like-globules seem to be indirectly involved in enamel protection over time maintaining low permeability. Others results obtained by metallographic microscope and SEM/EDX analyses of or-thodontic resins fluoride releasing and not demonstrated the relevance of topical fluo-ride application in decreasing the demineralization marks and modifying the chemical composition of the enamel in the treated area. These data obtained in both the experiments confirmed the efficacy of fluoride in caries prevention and contribute to clarify its mechanism of action. Adhesive dentistry is the gold standard for caries treatment and tooth rehabilitation and is founded on important chemical and physical principles involving both enamel and dentine substrates. Particularly acid etching of dental enamel enamel has usually employed in bonding pro-cedures increasing microscopic roughness. Different acids have been tested in the litera-ture suggesting several etching procedures. The acid-induced structural transformations in enamel after different etching treatments by means of Raman and IR spectroscopy analysis were evaluated and these findings were correlated with enamel permeability. Conventional etching with 37% phosphoric acid gel (H3PO4) for 30 s and etching with 15 % HCl for 120 s were investigated. Raman and IR spectroscopy showed that the treatment with both hydrochloric and phosphoric acids induced a decrease in the carbonate content of the enamel apatite. At the same time, both acids induced the formation of HPO42- ions. After H3PO4 treatment the bands due to the organic component of enamel decreased in intensity, while in-creased after HCl treatment. Replicas of H3PO4 treated enamel showed a strongly reduced permeability while replicas of HCl 15% treated samples showed a maintained permeability. A decrease of the enamel organic component, as resulted after H3PO4 treatment, involves a decrease in enamel permeability, while the increase of the organic matter (achieved by HCl treat-ment) still maintains enamel permeability. These results suggested a correlation between the amount of the organic matter, enamel permeability and caries. The results of the different studies carried out in this thesis contributed to clarify and improve the knowledge about enamel properties with important rebounds in theoretical and clinical aspects of Dentistry.

A study of new and more sustainable catalytic routes for the synthesis of adipic acid

The aim of my PhD research project was to investigate new and more sustainable routes, compared to those currently used, for the production of adipic acid (AA). AA is a very important chemical intermediate. The main use of AA is the production of Nylon-6,6 fibers, resins, polyesters, plasticizers. My project was divided into two parts: 1. The two-step oxidation of cyclohexene, where the latter is first oxidized into trans-1,2-cyclohexanediol (CHD) with aqueous hydrogen peroxide, and then the glycol is transformed into AA by reaction with molecular oxygen. Various catalysts were investigated in this process, both heterogeneous (alumina-supported Ru(OH)x and Au nanoparticles supported on TiO2, MgO and Mg(OH)2) and homogeneous (polyoxometalates). We also studied the mechanism of CHD oxidation with oxygen in the presence of these catalysts. 2. Baeyer-Villiger oxidation of cyclohexanone with aqueous hydrogen peroxide into ɛ-caprolactone, as a first step on the way to produce AA. Study on the mechanism of the uncatalyzed (thermal) oxidation of cyclohexanone were also carried out. Investigation on how the different heterogeneous catalysts affect the formation of the reaction products and their distribution was done.

Fully bio-based epoxy resins

Epoxy resins are mainly produced by reacting bisphenol A with epichlorohydrin. Growing concerns about the negative health effects of bisphenol A are urging researchers to find alternatives. In this work diphenolic acid is suggested, as it derives from levulinic acid, obtained from renewable resources. Nevertheless, it is also synthesized from phenol, from fossil resources, which, in the current paper has been substituted by plant-based phenols. Two interesting derivatives were identified: diphenolic acid from catechol and from resorcinol. Epichlorohydrin on the other hand, is highly carcinogenic and volatile, leading to a tremendous risk of exposure. Thus, two approaches have been investigated and compared with epichlorohydrin. The resulting resins have been characterized to find an appropriate application, as epoxy are commonly used for a wide range of products, ranging from composite materials for boats to films for food cans. Self-curing capacity was observed for the resin deriving from diphenolic acid from catechol. The glycidyl ether of the diphenolic acid from resorcinol, a fully renewable compound, was cured in isothermal and non-isothermal tests tracked by DSC. Two aliphatic amines were used, namely 1,4-butanediamine and 1,6-hexamethylendiamine, in order to determine the effect of chain length on the curing of an epoxy-amine system and determine the kinetic parameters. The latter are crucial to plan any industrial application. Both diamines demonstrated superior properties compared to traditional bisphenol A-amine systems.