Preliminary structure-activity relationship studies on some novel s-substituted aliphatic analogues of 5-{1-[(4- chlorophenyl) sulfonyl]-3-piperidinyl}-1, 3, 4-oxadiazol-2-yl sulfide

Purpose: To study the structure-activity relationships of synthetic multifunctional sulfides through evaluation of lipoxygenase and anti-bacterial activities. Methods: S-substituted derivatives of the parent compound 5-(1-(4-chlorophenylsulfonyl) piperidin-3- yl)-1, 3, 4-oxadiazole-2-thiol were synthesized through reaction with different saturated and unsaturated alkyl halides in DMF medium, with NaH catalyst. Spectral characterization of each derivative was carried out with respect to IR, 1H - NMR, 13C - NMR and EI - MS. The lipoxygenase inhibitory and antibacterial activities of the derivatives were determined using standard procedures. Results: Compound 5e exhibited higher lipoxygenase inhibitory potential than the standard (Baicalein®), with % inhibition of 94.71 ± 0.45 and IC50 of 20.72 ± 0.34 μmoles/L. Compound 5b showed significant antibacterial potential against all the bacterial strains with % inhibition ranging from 62.04 ± 2.78, 69.49 ± 0.41, 63.38 ± 1.97 and 59.70 ± 3.70 to 78.32 ± 0.41, while MIC ranged from 8.18 ± 2.00, 10.60 ± 1.83, 10.84 ± 3.00, 9.81 ± 1.86 and 11.73 ± 5.00 μmoles/L for S. typhi, E. coli, P. aeruginosa, B. subtilis and S. aureus, respectively. Compounds 5d, 5e and 5g showed good antibacterial activity against S. typhi and B. subtilis bacterial strains. Conclusion: The results suggest that compound 5e bearing n-pentyl group is a potent lipoxygenase inhibitor, while compound 5b with n-propyl substitution is a strong antibacterial agent. In addition, compounds 5d, 5e and 5g bearing n-butyl, n-pentyl and n-octyl groups, respectively, are good antibacterial agents against S. typhi and B. subtilis.

Packaging and Deployment of Large Planar Spacecraft Structures

This thesis presents a set of novel methods to biaxially package planar structures by folding and wrapping. The structure is divided into strips connected by folds that can slip during wrapping to accommodate material thickness. These packaging schemes are highly efficient, with theoretical packaging efficiencies approaching 100%. Packaging tests on meter-scale physical models have demonstrated packaging efficiencies of up to 83%. These methods avoid permanent deformation of the structure, allowing an initially flat structure to be deployed to a flat state.

Also presented are structural architectures and deployment schemes that are compatible with these packaging methods. These structural architectures use either in-plane pretension -- suitable for membrane structures -- or out-of-plane bending stiffness to resist loading. Physical models are constructed to realize these structural architectures. The deployment of these types of structures is shown to be controllable and repeatable by conducting experiments on lab-scale models.

These packaging methods, structural architectures, and deployment schemes are applicable to a variety of spacecraft structures such as solar power arrays, solar sails, antenna arrays, and drag sails; they have the potential to enable larger variants of these structures while reducing the packaging volume required. In this thesis, these methods are applied to the preliminary structural design of a space solar power satellite. This deployable spacecraft, measuring 60 m x 60 m, can be packaged into a cylinder measuring 1.5 m in height and 1 m in diameter. It can be deployed to a flat configuration, where it acts as a stiff lightweight support framework for multifunctional tiles that collect sunlight, generate electric power, and transmit it to a ground station on Earth.

Ammonia effects on proton conductivity properties of coordination polymers

Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed.

Urban Agriculture Oriented towards Self-Supply, Social and Commercial Purpose: A Typology

Urban agriculture, a dynamic multifunctional phenomenon, affects the spatial diversification of urban land use, its valorization and its governance. Literature acknowledges its contribution to the development of sustainable cities. The dimension and extent of this contribution depends significantly on the particular form and function of urban agriculture. However, the complexity of interests and dimensions is insufficiently covered by theory. This paper proposes a typology for urban agriculture, supporting both theory building and practical decision processes. We reviewed and mapped the diversity of the types of agriculture found along three beneficial dimensions (self-supply, socio-cultural, commercial) for product distribution scale and actors. We distinguish between ideal types, subtypes and mixed types. Our intention is to include a dynamic perspective in the typology of urban agricultural land use because transition processes between types are observable due to the existence of complex motivations and influences. In a pilot study of 52 urban agriculture initiatives in Germany, we tested the validity of the typology and discussed it with stakeholders, proving novelty and relevance for profiling discussions.

Emergy analysis of a silvo-pastoral system, a case study in southern Portugal

The Mediterranean silvo-pastoral system known as Montado, in Portugal, is a complex land use system composed of an open tree stratum in various densities and an herbaceous layer, used for livestock grazing. Livestock also profit from the acorns, and the grazing contributes to avoid shrub encroachment. In the last 20 years, subsidies from the European Union have greatly promoted cattle rearing in this system and the introduction of heavy breeds, at the expense of sheep, goats or the native cattle breeds. The balance of the traditional system is thus threatened, and a precise assessment of the balance between the different components of the system, therefore is highly needed. The goal of this study was to gain a better under- standing of a Montado farm system with cattle rearing as the major economic activity by applying the emergy evaluation method to calculate indices of yield, investment, environmental loading and sustainability. By integrating different ecosystem components, the emergy evaluation method allows a comprehensive evaluation of this complex and multifunctional system at the scale of an individual farm. This method provides a set of indices that can help us understand the system and design management strategies that maximize emergy flow in the farm. In this paper, we apply the emergy evaluation method to a Montado farm with cattle rearing, as a way to gain a better understanding of this system at the farm scale. The value for the transformity of veal (2.66E?06 sej J-1) is slightly higher, when compared to other systems producing protein. That means that the investment of nature and man in this product was higher and it requires a premium price on the market. The renewa- bility for Holm Oaks Farm (49 %), lower than for other similar systems, supports the assumption that this is a farm in which, comparing with others, the number of purchased inputs in relation to renewable inputs provided by nature, is higher. The Emergy Investment Ratio is 0.91 for cattle rearing compared to a value of 0.49 for cork and 0.43 for firewood harvesting, making it clear that cattle rearing is a more labor demanding activity comparing with extractive activities as cork and firewood harvesting.

I danni punitivi nel sistema della responsabilità civile

Il concetto di danno punitivo evoca una peculiare forma di risarcimento del danno la cui funzione, lungi dal risolversi in una prospettiva meramente compensativa del soggetto danneggiato, si carica di una valenza punitiva e deterrente. L’obiettivo del presente lavoro è quello di indagare l’ammissibilità e la compatibilità dell’istituto con la sistematica della responsabilità da illecito aquiliano. Un piano di indagine sollecitato dal recente fervore pretorio sul tema, soprattutto in relazione alla verifica dialettica della compatibilità dell’istituto in parola con il concetto di ordine pubblico interno e internazionale: l’attuale impianto normativo dell’illecito aquiliano può legittimamente ambire ad una vocazione polifunzionale e dinamica in una più ampia prospettiva di effettività e completezza della tutela non solo interprivata ma anche superindividuale, nella consapevolezza, che “una responsabilità civile che non accarezzi la deterrenza non è una vera responsabilità civile”.

Valorization of by-products from olive oil industry and their utilization for innovative food formulation

The purpose of this thesis work was the valorization of the main by-products obtained from olive oil production chain (wastewater and pomace) and their utilization in innovative food formulation. In the first part of the thesis, an olive mill wastewater extract rich in phenols were used in the formulation of 3 innovative meat products: beef hamburgers, cooked ham and würstels. These studies confirms that olive mill wastewaters extract rich in phenols could be an alternative for the reduction/total replacement of additives (i.e., nitrites) in ground and cooked meat preparations, which would promote the formulation of healthier clean label products and improve the sustainability of the olive oil industry with a circular economy approach, by further valorizing this olive by-product. In the second part of the thesis, the lipid composition and oxidative stability of a spreadable product obtained from a fermented and biologically de-bittered olive pomace, was assessed during a shelf-life study. This study confirmed that olive pomace represents an excellent ingredient for the formulation of functional foods In the third and last part of the thesis, carried out at the Universidad de Navarra (Pamplona, Spain), during a period abroad (3 months), three extracts obtained from purification of olive mill wastewaters, were subjected to in-vitro digestion and characterized. From the analysis of the three phenolic extracts, it emerged that the most promising extract to be used in the food field is the spry-dried one. Thanks to its formulation containing maltodextrins it manages to maintain its antioxidant capacity even after being underwent to in-vitro digestion. This thesis work is a part of the PRIN 2015 project (PROT: 20152LFKAT) "Olive phenols as multifunctional bioactives for healthier food: evaluation of simplified formulation to obtain safe meat products and new foods with higher functionality", coordinated by University of Perugia.

Development and characterization of innovative graphene-based composites

Over the last decade, graphene and related materials (GRM) have drawn significant interest and resources for their development into the next generation of composite materials. This is because these nanoparticles have the ability to operate as reinforcing additives capable of imparting considerable mechanical property increases while also embedding multi-functional advantages on the host matrix. Because graphene and 2D materials are still in their early stages, the relative maturity of different types of composite systems varies. As a result, certain nanocomposite systems are currently commercially accessible, while others are not yet sufficiently developed to enter the market. A substantial emphasis has been placed on developing thermoplastic and thermosetting materials that combine a variety of mechanical and functional qualities. These include higher strength and stiffness, increased thermal and electrical conductivity, improved barrier properties, fire retardancy, and others, with the ultimate goal of providing multifunctionality to already employed composites. The work presented in this thesis investigates the use and benefits that GRM could bring to composites for a variety of applications, with the goal of realizing multifunctional components with improved properties that leads to lightweight and, as a result, energy and cost savings and pollution reduction in the environment. In particular, we worked on the following topics: • Benchmarking of commercial GRM-based master batches; • GRM-coatings for water uptake reduction; • GRM as thermo-electrical anti-icing /de-icing system; • GRM for Out of Oven curing of composites.

Functional engineering of hybrid heterostructures for application in electronic, optical and optoelectronic nanostructured devices

Interfacing materials with different intrinsic chemical-physical characteristics allows for the generation of a new system with multifunctional features. Here, this original concept is implemented for tailoring the functional properties of bi-dimensional black phosphorus (2D bP or phosphorene) and organic light-emitting transistors (OLETs). Phosphorene is highly reactive under atmospheric conditions and its small-area/lab-scale deposition techniques have hampered the introduction of this material in real-world applications so far. The protection of 2D bP against the oxygen by means of functionalization with alkane molecules and pyrene derivatives, showed long-term stability with respect to the bare 2D bP by avoiding remarkable oxidation up to 6 months, paving the way towards ultra-sensitive oxygen chemo-sensors. A new approach of deposition-precipitation heterogeneous reaction was developed to decorate 2D bP with Au nanoparticles (NP)s, obtaining a “stabilizer-free” that may broaden the possible applications of the 2D bP/Au NPs interface in catalysis and biodiagnostics. Finally, 2D bP was deposited by electrospray technique, obtaining oxidized-phosphorous flakes as wide as hundreds of µm2 and providing for the first time a phosphorous-based bidimensional system responsive to electromechanical stimuli. The second part of the thesis focuses on the study of organic heterostructures in ambipolar OLET devices, intriguing optoelectronic devices that couple the micro-scaled light-emission with electrical switching. Initially, an ambipolar single-layer OLET based on a multifunctional organic semiconductor, is presented. The bias-depending light-emission shifted within the transistor channel, as expected in well-balanced ambipolar OLETs. However, the emitted optical power of the single layer-based device was unsatisfactory. To improve optoelectronic performance of the device, a multilayer organic architecture based on hole-transporting semiconductor, emissive donor-acceptor blend and electron-transporting semiconductor was optimized. We showed that the introduction of a suitable electron-injecting layer at the interface between the electron-transporting and light-emission layers may enable a ≈ 2× improvement of efficiency at reduced applied bias.

A corpus-assisted approach to apology-like expressions in Japanese computer-mediated discourse

This thesis provides a corpus-assisted pragmatic investigation of three Japanese expressions commonly signalled as apologetic, namely gomen, su(m)imasen and mōshiwake arimasen, which can be roughly translated in English with ‘(I’m) sorry’. The analysis is based on a web corpus of 306,670 tokens collected from the Q&A website Yahoo! Chiebukuro, which is examined combining quantitative (statistical) and qualitative (traditional close reading) methods. By adopting a form-to-function approach, the aim of the study is to shed light on three main topics of interest: the pragmatic functions of apology-like expressions, the discursive strategies they co-occur with, and the behaviours that warrant them. The overall findings reveal that apology-like expressions are multifunctional devices whose meanings extend well beyond ‘apology’ alone. These meanings are affected by a number of discursive strategies that can either increase or decrease the perceived (im)politeness level of the speech act to serve interactants’ face needs and communicative goals. The study also identifies a variety of behaviours that people frame as violations, not necessarily because they are actually face-threatening to the receiver, but because doing so is functional to the projection of the apologiser as a moral persona. An additional finding that emerged from the analysis is the pervasiveness of reflexive usages of apology-like expressions, which are often employed metadiscursively to convey, negotiate and challenge opinions on how language should be used. To conclude, the study provides a unique insight into the use of three expressions whose pragmatic meanings are more varied than anticipated. The findings reflect the use of (im)politeness in an online and non-Western context and, hopefully, represent a step towards a more inclusive notion of ‘apologies’ and related speech acts.

“Study of Electro-thermal Effects on PLA Materials Fed with AC Currents”

Given the rise in the emergence of new composite materials, their multifunctional properties, and possible applications in simple and complex structural components, there has been a need to unravel the characterization of these materials. The possibility of printing these conductive composite materials has opened a new area in the design of structural components which can conduct, transmit, and modulate electric signals with no limitation from complex geometry. Although several works have researched the behaviour of polymeric composites due to the immediate growth, however, the electrothermal behaviour of the material when subjected to varying AC applied voltage (Joule’s effect) has not been thoroughly researched. This study presents the characterization of the electrothermal behaviour of conductive composites of a polylactic acid matrix reinforced with conductive carbon black particles (CB-PLA). An understanding of this behaviour would contribute to the improved work in additive manufacturing of functional electro-mechanical conductive materials with potential application in energy systems, bioelectronics, etc. In this study, the electrothermal interplay is monitored under applied AC voltage, varying lengths, and filament printing orientations (longitudinal, oblique, and transverse). Each sample was printed using the fused deposition modeling technique such that each specimen has three different lengths (1L, 2L, 2.75L). To this end, deductions were made on properties that affect composite’s efficiency and life expectancy. The result of this study shows a great influence of printing orientation on material properties of 3D printed conductive composites of CB-PLA. The result also identifies the contribution of AC applied voltage to composites' stabilization time. This knowledge is important to provide experimental background for components' electrothermal interplay, estimate possible degradation and operating limits of composite structures when used in applications.