8 resultados para Resins of ionic exchange
em AMS Tesi di Dottorato - Alm@DL - Università di Bologna
Resumo:
My aim is to develop a theory of cooperation within the organization and empirically test it. Drawing upon social exchange theory, social identity theory, the idea of collective intentions, and social constructivism, the main assumption of my work implies that both cooperation and the organization itself are continually shaped and restructured by actions, judgments, and symbolic interpretations of the parties involved. Therefore, I propose that the decision to cooperate, expressed say as an intention to cooperate, reflects and depends on a three step social process shaped by the interpretations of the actors involved. The first step entails an instrumental evaluation of cooperation in terms of social exchange. In the second step, this social calculus is translated into cognitive, emotional and evaluative reactions directed toward the organization. Finally, once the identification process is completed and membership awareness is established, I propose that individuals will start to think largely in terms of We instead of I. Self-goals are redefined at the collective level, and the outcomes for self, others, and the organization become practically interchangeable. I decided to apply my theory to an important cooperative problem in management research: knowledge exchange within organizations. Hence, I conducted a quantitative survey among the members of the virtual community, www.borse.it (n=108). Within this community, members freely decide to exchange their knowledge about the stock market among themselves. Because of the confirmatory requirements and the structural complexity of the theory proposed (i.e., the proposal that instrumental evaluations will induce social identity and this in turn will causes collective intentions), I use Structural Equation Modeling to test all hypotheses in this dissertation. The empirical survey-based study found support for the theory of cooperation proposed in this dissertation. The findings suggest that an appropriate conceptualization of the decision to exchange knowledge is one where collective intentions depend proximally on social identity (i.e., cognitive identification, affective commitment, and evaluative engagement) with the organization, and this identity depends on instrumental evaluations of cooperators (i.e., perceived value of the knowledge received, assessment of past reciprocity, expected reciprocity, and expected social outcomes of the exchange). Furthermore, I find that social identity fully mediates the effects of instrumental motives on collective intentions.
Resumo:
The present Thesis studies three alternative solvent groups as sustainable replacement of traditional organic solvents. Some aspects of fluorinated solvents, supercritical fluids and ionic liquids, have been analysed with a critical approach and their effective greenness has been evaluated from the points of view of the synthesis, the properties and the applications. In particular, the attention has been put on the environmental and human health issues, evaluating the eco-toxicity, the toxicity and the persistence, to underline that applicability and sustainability are subjects with equal importance. The green features of fluorous solvents and supercritical fluids are almost well-established; in particular supercritical carbon dioxide (scCO2) is probably the greenest solvent among the alternative solvent systems developed in the last years, enabling to combine numerous advantages both from the point of view of industrial/technological applications and eco-compatibility. In the Thesis the analysis of these two classes of alternative solvents has been mainly focused on their applicability, rather than the evaluation of their environmental impact. Specifically they have been evaluated as alternative media for non-aqueous biocatalysis. For this purpose, the hydrophobic ion pairing (HIP), which allows solubilising enzymes in apolar solvents by an ion pairing between the protein and a surfactant, has been investigated as effective enzymatic derivatisation technique to improve the catalytic activity under homogeneous conditions in non conventional media. The results showed that the complex enzyme-surfactant was much more active both in fluorous solvents and in supercritical carbon dioxide than the native form of the enzyme. Ionic liquids, especially imidazolium salts, have been proposed some years ago as fully green alternative solvents; however this epithet does not take into account several brown aspects such as their synthesis from petro-chemical starting materials, their considerable eco-toxicity, toxicity and resistance to biodegradation, and the difficulty of clearly outline applications in which ionic liquids are really more advantageous than traditional solvents. For all of these reasons in this Thesis a critical analysis of ionic liquids has been focused on three main topics: i) alternative synthesis by introducing structural moieties which could reduce the toxicity of the most known liquid salts, and by using starting materials from renewable resources; ii) on the evaluation of their environmental impact through eco-toxicological tests (Daphnia magna and Vibrio fischeri acute toxicity tests, and algal growth inhibition), toxicity tests (MTT test, AChE inhibition and LDH release tests) and fate and rate of aerobic biodegradation in soil and water; iii) and on the demonstration of their effectiveness as reaction media in organo-catalysis and as extractive solvents in the recovery of vegetable oil from terrestrial and aquatic biomass. The results about eco-toxicity tests with Daphnia magna, Vibrio fischeri and algae, and toxicity assay using cultured cell lines, clearly indicate that the difference in toxicity between alkyl and oxygenated cations relies in differences of polarity, according to the general trend of decreasing toxicity by decreasing the lipophilicity. Independently by the biological approach in fact, all the results are in agreement, showing a lower toxicity for compounds with oxygenated lateral chains than for those having purely alkyl lateral chains. These findings indicate that an appropriate choice of cation and anion structures is important not only to design the IL with improved and suitable chemico-physical properties but also to obtain safer and eco-friendly ILs. Moreover there is a clear indication that the composition of the abiotic environment has to be taken into account when the toxicity of ILs in various biological test systems is analysed, because, for example, the data reported in the Thesis indicate a significant influence of salinity variations on algal toxicity. Aerobic biodegradation of four imidazolium ionic liquids, two alkylated and two oxygenated, in soil was evaluated for the first time. Alkyl ionic liquids were shown to be biodegradable over the 6 months test period, and in contrast no significant mineralisation was observed with oxygenated derivatives. A different result was observed in the aerobic biodegradation of alkylated and oxygenated pyridinium ionic liquids in water because all the ionic liquids were almost completely degraded after 10 days, independently by the number of oxygen in the lateral chain of the cation. The synthesis of new ionic liquids by using renewable feedstock as starting materials, has been developed through the synthesis of furan-based ion pairs from furfural. The new ammonium salts were synthesised in very good yields, good purity of the products and wide versatility, combining low melting points with high decomposition temperatures and reduced viscosities. Regarding the possible applications as surfactants and biocides, furan-based salts could be a valuable alternative to benzyltributylammonium salts and benzalkonium chloride that are produced from non-renewable resources. A new procedure for the allylation of ketones and aldehydes with tetraallyltin in ionic liquids was developed. The reaction afforded high yields both in sulfonate-containing ILs and in ILs without sulfonate upon addition of a small amount of sulfonic acid. The checked reaction resulted in peculiar chemoselectivity favouring aliphatic substrates towards aromatic ketones and good stereoselectivity in the allylation of levoglucosenone. Finally ILs-based systems could be easily and successfully recycled, making the described procedure environmentally benign. The potential role of switchable polarity solvents as a green technology for the extraction of vegetable oil from terrestrial and aquatic biomass has been investigated. The extraction efficiency of terrestrial biomass rich in triacylglycerols, as soy bean flakes and sunflower seeds, was comparable to those of traditional organic solvents, being the yield of vegetable oils recovery very similar. Switchable polarity solvents as been also exploited for the first time in the extraction of hydrocarbons from the microalga Botryococcus braunii, demonstrating the efficiency of the process for the extraction of both dried microalgal biomass and directly of the aqueous growth medium. The switchable polarity solvents exhibited better extraction efficiency than conventional solvents, both with dried and liquid samples. This is an important issue considering that the harvest and the dewatering of algal biomass have a large impact on overall costs and energy balance.
Resumo:
Throughout the world, pressures on water resources are increasing, mainly as a result of human activity. Because of their accessibility, groundwater and surface water are the most used reservoirs. The evaluation of the water quality requires the identification of the interconnections among the water reservoirs, natural landscape features, human activities and aquatic health. This study focuses on the estimation of the water pollution linked to two different environmental issues: salt water intrusion and acid mine drainage related to the exploitation of natural resources. Effects of salt water intrusion occurring in the shallow aquifer north of Ravenna (Italy) was analysed through the study of ion- exchange occurring in the area and its variance throughout the year, applying a depth-specific sampling method. In the study area were identified ion exchange, calcite and dolomite precipitation, and gypsum dissolution and sulphate reduction as the main processes controlling the groundwater composition. High concentrations of arsenic detected only at specific depth indicate its connexion with the organic matter. Acid mine drainage effects related to the tin extraction in the Bolivian Altiplano was studied, on water and sediment matrix. Water contamination results strictly dependent on the seasonal variation, on pH and redox conditions. During the dry season the strong evaporation and scarce water flow lead to low pH values, high concentrations of heavy metals in surface waters and precipitation of secondary minerals along the river, which could be released in oxidizing conditions as demonstrated through the sequential extraction analysis. The increase of the water flow during the wet season lead to an increase of pH values and a decrease in heavy metal concentrations, due to dilution effect and, as e.g. for the iron, to precipitation.
Resumo:
The dissertation is structured in three parts. The first part compares US and EU agricultural policies since the end of WWII. There is not enough evidence for claiming that agricultural support has a negative impact on obesity trends. I discuss the possibility of an exchange in best practices to fight obesity. There are relevant economic, societal and legal differences between the US and the EU. However, partnerships against obesity are welcomed. The second part presents a socio-ecological model of the determinants of obesity. I employ an interdisciplinary model because it captures the simultaneous influence of several variables. Obesity is an interaction of pre-birth, primary and secondary socialization factors. To test the significance of each factor, I use data from the National Longitudinal Survey of Adolescent Health. I compare the average body mass index across different populations. Differences in means are statistically significant. In the last part I use the National Survey of Children Health. I analyze the effect that family characteristics, built environment, cultural norms and individual factors have on the body mass index (BMI). I use Ordered Probit models and I calculate the marginal effects. I use State and ethnicity fixed effects to control for unobserved heterogeneity. I find that southern US States tend have on average a higher probability of being obese. On the ethnicity side, White Americans have a lower BMI respect to Black Americans, Hispanics and American Indians Native Islanders; being Asian is associated with a lower probability of being obese. In neighborhoods where trust level and safety perception are higher, children are less overweight and obese. Similar results are shown for higher level of parental income and education. Breastfeeding has a negative impact. Higher values of measures of behavioral disorders have a positive and significant impact on obesity, as predicted by the theory.
Resumo:
Nellambito del progetto multidisciplinare Coastal Salt Water Intrusion, che si propone di indagare lIntrusione salina nella costa ravennate con i conseguenti impatti territoriali-ambientali, connessi al previsto innalzamento del livello marino per cause climatiche e di subsidenza, si inserisce il presente studio con lobiettivo di fornire una caratterizzazione idrogeochimica delle acque di falda e superficiali e un modello geochimico generale sui processi di salinizzazione o desalinizzazione in atto nella falda freatica costiera della costa ravennate. E stato fatto un confronto fra tre metodiche di estrazione del complesso di scambio della matrice solida dellacquifero che utilizzano rispettivamente acetato di ammonio, cloruro di bario e argento-tiourea. Sono stati posizionati 5 transetti perpendicolari alla linea di costa per un totale di 44 punti di campionamento con due campagne di prelievi, al termine della primavera e al termine dellestate. La caratterizzazione dei processi di mixing e scambio ionico con la matrice solida dellacquifero avvenuta mediante analisi dei cationi ed anioni fondamentali, determinazione della CEC sulla matrice solida dellacquifero, modellizzazione mixing/scambio ionico, modellizzazione della composizione teorica della frazione scambiabile in funzione della composizione acqua allequilibrio e interpolazione geostatistica dei dati raccolti e costruzione di mappe geochimiche (curve di iso-concentrazione). La metodologia di estrazione che utilizza il bario-cloruro risultata la pi affidabile. Le acque prelevate dalla falda superficiale evidenziano miscelazione in varie proporzioni acqua marina/acqua dolce, scambi ionici per interazione acqua/sedimento, dissoluzione di CaSO4.2H2O. I processi di salinizzazione e/o addolcimento mostrano una significativa variabilit nello spazio (variabilit legata alla distanza dalla costa, al profilo topografico e alla distribuzione dei corpi sabbiosi litoranei) e nel tempo (variabilit legata alla piovosit e alla gestione delle acque superficiali e del sottosuolo). La complessa variabilit spazio-temporale dei processi in atto nella falda superficiale non consente di evidenziare una complessiva prevalenza di fenomeni di salinizzazione rispetto a quelli di addolcimento.
Resumo:
This doctorate was funded by the Regione Emilia Romagna, within a Spinner PhD project coordinated by the University of Parma, and involving the universities of Bologna, Ferrara and Modena. The aim of the project was: - Production of polymorphs, solvates, hydrates and co-crystals of active pharmaceutical ingredients (APIs) and agrochemicals with green chemistry methods; - Optimization of molecular and crystalline forms of APIs and pesticides in relation to activity, bioavailability and patentability. In the last decades, a growing interest in the solid-state properties of drugs in addition to their solution chemistry has blossomed. The achievement of the desired and/or the more stable polymorph during the production process can be a challenge for the industry. The study of crystalline forms could be a valuable step to produce new polymorphs and/or co-crystals with better physical-chemical properties such as solubility, permeability, thermal stability, habit, bulk density, compressibility, friability, hygroscopicity and dissolution rate in order to have potential industrial applications. Selected APIs (active pharmaceutical ingredients) were studied and their relationship between crystal structure and properties investigated, both in the solid state and in solution. Polymorph screening and synthesis of solvates and molecular/ionic co-crystals were performed according to green chemistry principles. Part of this project was developed in collaboration with chemical/pharmaceutical companies such as BASF (Germany) and UCB (Belgium). We focused on on the optimization of conditions and parameters of crystallization processes (additives, concentration, temperature), and on the synthesis and characterization of ionic co-crystals. Moreover, during a four-months research period in the laboratories of Professor Nair Rodriguez-Hormedo (University of Michigan), the stability in aqueous solution at the equilibrium of ionic co-crystals (ICCs) of the API piracetam was investigated, to understand the relationship between their solid-state and solution properties, in view of future design of new crystalline drugs with predefined solid and solution properties.
Resumo:
During the PhD program in chemistry at the University of Bologna, the environmental sustainability of some industrial processes was studied through the application of the LCA methodology. The efforts were focused on the study of processes under development, in order to assess their environmental impacts to guide their transfer on an industrial scale. Processes that could meet the principles of Green Chemistry have been selected and their environmental benefits have been evaluated through a holistic approach. The use of renewable sources was assessed through the study of terephthalic acid production from biomass (which showed that only the use of waste can provide an environmental benefit) and a new process for biogas upgrading (whose potential is to act as a carbon capture technology). Furthermore, the basis for the development of a new methodology for the prediction of the environmental impact of ionic liquids has been laid. It has already shown good qualities in identifying impact trends, but further research on it is needed to obtain a more reliable and usable model. In the context of sustainable development that will not only be sector-specific, the environmental performance of some processes linked to the primary production sector has also been evaluated. The impacts of some organic farming practices in the wine production were analysed, the use of the Cereal Unit parameter was proposed as a functional unit for the comparison of different crop rotations, and the carbon footprint of school canteen meals was calculated. The results of the analyses confirm that sustainability in the industrial production sector should be assessed from a life cycle perspective, in order to consider all the flows involved during the different phases. In particular, it is necessary that environmental assessments adopt a cradle-to-gate approach, to avoid shifting the environmental burden from one phase to another.
Resumo:
The city of tomorrow is a major integrating stake, which crosses a set of major broad spectrum domains. One of these areas is the instrumentation of this city and the ubiquity of the exchange of data, which will give the pulse of this city (sensors) and its breathing in a hyper-connected world within indoor and outdoor dense areas (data exchange, 5G and 6G). Within this context, the proposed doctorate project has the objective to realize cost- and energy- effective, short-range communication systems for the capillary wireless coverage of in-door environments with low electromagnetic impact and for highly dense outdoor networks. The result will be reached through the combined use of: 1) Radio over Fiber (RoF) Technology, to bring the Radio Frequency (RF) signal to the different areas to be covered. 2) Beamforming antennas to send in real time the RF power just in the direction(s) where it is really necessary.