EXPLORING VIENNESE TUNING AND ITS BENEFITS FOR THE MODERN DOUBLE BASSIST

The role of the double bass in Vienna during the eighteenth century evolved significantly between 1760 and 1812. During these years, Viennese composers began to view the double bass less as an accompanimental instrument and more as a solo voice. Despite the abundance of music written for the double bass during this time, few of these compositions are regularly performed today. This dissertation serves three purposes. I explore how learning eighteenth-century Viennese compositions in the original tuning can influence modern performances of these works. Secondly, I document the arrangement of a lesser-know work for the modern tuned bass using the manuscript as the source material. Finally, by performing a variety of eighteenth-century bass works, I bring this music to the public's attention. The research for this dissertation has been presented in two forms. The recitals present both solo and chamber works from eighteenth-century Vienna. The repertoire for the three recitals was chosen so that each recital addresses one of the three purposes mentioned above. The research paper presents performance practices of the eighteenth century, challenges the modern double bassist faces when playing this literature, as well as a look into how to arrange one of these works for the modern tuned double bass. The three recitals were performed on the campus of the University of Maryland in the Leah M. Smith Hall, Gildenhorn Recital Hall and the Ulrich Recital Hall, respectively. Recordings of all three recitals can be found in the Digital Repository at the University of Maryland (DRUM).

Estimating the demand curve for sustainable use of pesticides from contingent-valuation data

Stated-preference valuation techniques are often used to assess consumers' willingness-to-pay for food items produced in farming systems that adopt a sustainable use of pesticides (SUP). We propose an innovative valuation methodology in which dichotomous-choice contingent valuation is used to estimate the demand curve (price-quantity relationship) for such food items where price means price premium for the SUP output, quantity is the probability of choosing SUP and the conventional food product is kept available in the market at the current market price. This methodology can be used to evaluate market differentiation as a policy option to promote the SUP. The methodology is tested with data from a sample of urban consumers of fruits and vegetables in Portugal. The estimated demand curve is used to define the price level maximizing the total premium revenue for the SUP sector as a whole. This optimal level of the price premium is €77.55 (or 163% of the value of the monthly basket of fruits and vegetables at current prices). Adopting the optimal price premium will decrease the number of consumers of SUP food by 54%. The reduction is even higher for low income consumers (80%) leaving them more exposed to the risks of pesticide use.

Using a CGE Model to Identify the Policy Trade-Off between Unemployment and Inflation: The Efficient Phillips Curve

This paper provides a new reading of a classical economic relation: the short-run Phillips curve. Our point is that, when dealing with inflation and unemployment, policy-making can be understood as a multicriteria decisionmaking problem. Hence, we use so-called multiobjective programming in connection with a computable general equilibrium (CGE) model to determine the combinations of policy instruments that provide efficient combinations of inflation and unemployment. This approach results in an alternative version of the Phillips curve labelled as efficient Phillips curve. Our aim is to present an application of CGE models to a new area of research that can be especially useful when addressing policy exercises with real data. We apply our methodological proposal within a particular regional economy, Andalusia, in the south of Spain. This tool can give some keys for policy advice and policy implementation in the fight against unemployment and inflation.

Radiogenic isotopes in the Mediterranean Sea: water mass exchange and precessional variability during the Messinian

During the late Miocene, exchange between the Mediterranean Sea and Atlantic Ocean changed dramatically, culminating in the Messinian Salinity Crisis (MSC). Understanding Mediterranean-Atlantic exchange at that time could answer the enigmatic question of how so much salt built up within the Mediterranean, while furthering the development of a framework for future studies attempting to understand how changes may have impacted global thermohaline circulation. Due to their association with specific water masses at different scales, radiogenic Sr, Pb, and Nd isotope records were generated from various archives contained within marine deposits to endeavour to understand better late Miocene Mediterranean-Atlantic exchange. The archives used include foraminiferal calcite (Sr), fish teeth and bone (Nd), dispersed authigenic ferromanganese oxyhydroxides (Nd, Pb), and a ferromanganese crust (Pb). The primary focus is on sediments preserved at one end of the Betic corridor, a gateway that once connected the Mediterranean to the Atlantic through southern Spain, although other locations are investigated. The Betic gateway terminated within several marginal sub-basins before entering the Western Mediterranean; one of these is the Sorbas Basin, a well-studied location whose sediments have been astronomically tuned at high temporal resolution, providing the necessary age control for sub-precessional resolution records. Since the climatic history of the Mediterranean is strongly controlled by precessional changes in regional climate, the aim was to produce records at high (sub-precessional) temporal resolution, to be able to observe clearly any precessional cyclicity driven by regional climate which could be superimposed over longer trends. This goal was achieved for all records except the ferromanganese crust record. The 87Sr/86Sr isotope record (Ch. 3) shows precessional frequency excursions away from the global seawater curve. As precessional frequency oscillations are unexpected for this setting, a numerical box model was used to determine the mechanisms causing the excursions. To enable parameterisation of model variables, regional Sr characteristics, data from general circulation model HadCM3L, and new benthic foraminiferal assemblage data are employed. The model results imply that the Sorbas Basin likely had a positive hydrologic budget in the late Miocene, very different to that of today. Moreover, the model indicates that the mechanism controlling the Sr isotope ratio of Sorbas Basin seawater was not restriction, but a lack of density-driven exchange with the Mediterranean. Beyond improving our understanding of how marginal Mediterranean sub-basins may evolve different isotope signatures, these results have implications for astronomical tuning and stratigraphy in the region, findings which are crucial considering the geological and climatic history of the late Miocene Mediterranean is based entirely on marginal deposits. An improved estimate for the Nd isotope signature of late Miocene Mediterranean Outflow (MO) was determined by comparing Nd isotope signatures preserved in the deeper Alborán Sea at ODP Site 978 with literature data as well as the signature preserved in the Sorbas Basin (Ch. 4; -9.34 to -9.92 ± 0.37 εNd(t)). It was also inferred that it is unlikely that Nd isotopes can be used reliably to track changes in circulation within the shallow settings characteristic of the Mediterranean-Atlantic connections; this is significant in light of a recent publication documenting corridor closure using Nd isotopes. Both conclusions will prove useful for future studies attempting to understand changes in Mediterranean-Atlantic exchange. Excursions to high values, with precessional frequency, are also observed in the radiogenic Pb isotope record for the Sorbas Basin (Ch. 5). Widening the scope to include locations further away from the gateways, records were produced for late Miocene sections on Sicily and Northern Italy, and similar precessional frequency cyclicity was observed in the Pb isotope records for these sites as well. Comparing these records to proxies for Saharan dust and available whole rock data indicates that, while further analysis is necessary to draw strong conclusions, enhanced dust production during insolation minima may be driving the observed signal. These records also have implications for astronomical tuning; peaks in Pb isotope records driven by Saharan dust may be easier to connect directly to the insolation cycle, providing improved astronomical tuning points. Finally, a Pb isotope record derived using in-situ laser ablation performed on ferromanganese crust 3514-6 from the Lion Seamount, located west of Gibraltar within the MO plume, has provided evidence that plume depth shifted during the Pliocene. The record also suggests that Pb isotopes may not be a suitable proxy for changes in late Miocene Mediterranean-Atlantic exchange, since the Pb isotope signatures of regional water masses are too similar. To develop this record, the first published instance of laser ablation derived 230Thexcess measurements are combined with 10Be dating.

Economic development and Environmental quality: The environmental Kuznets curve for water pollution

The main aim of this study was to analyze evidence of an environmental Kuznets curve for water pollution in the developing and developed countries. The study was conducted based on a panel data set of 54 countries – that were categorized into six groups of “developed countries”, “developing countries”, “developed countries with low income”, “developed countries with high income” and “coastal countries”- between the years 1995 to 2006. The results do not confirm the inverted U-shape of EKC curve for the developed countries with low income. Based on the estimated turning points and the average GDP per capita, the study revealed at which point of the EKC the countries are. Furthermore, impacts of capital-and-labor ratio as well as trade openness are drawn by estimating different models for the EKC. The magnitude role of each explanatory variable on BOD was calculated by estimating the associated elasticity.

Materials design for ambipolar devices: tuning orbital energetics in oligothiophene-naphthalimides semiconductors

Ambipolar organic field-effect transistors (OFETs), which can efficiently transport both holes and electrons, using a single type of electrode, are currently of great interest due to their possible applications in complementary metal oxide semiconductor (CMOS)-like circuits, sensors, and in light-emitting transistors. Several theoretical and experimental studies have argued that most organic semiconductors should be able to transport both types of carrier, although typically unipolar behavior is observed. One factor that can compromise ambipolar transport in organic semiconductors is poor solid state overlap between the HOMO (p-type) or LUMO (n-type) orbitals of neighboring molecules in the semiconductor thin film. In the search of low-bandgap ambipolar materials, where the absence of skeletal distortions allows closer intermolecular π-π stacking and enhanced intramolecular π-conjugation, a new family of oligothiophene-naphthalimide assemblies have been synthesized and characterized, in which both donor and acceptor moieties are directly conjugated through rigid linkers. In previous works we found that oligothiophene-napthalimide assemblies connected through amidine linkers (NDI derivates) exhibit skeletal distortions (50-60º) arising from steric hindrance between the carbonyl group of the arylene core and the sulphur atom of the neighbored thiophene ring (see Figure 1). In the present work we report novel oligo- and polythiophene–naphthalimide analogues NAI-3T, NAI-5T and poly-NAI-8C-3T, in which the connections of the amidine linkage have been inverted in order to prevent steric interactions. Thus, the nitrogen atoms are directly connected to the naphthalene moiety in NAI derivatives while they were attached directly to the thiophene moiety in the previously investigated NDI-3T and NDI-5T. In Figure 1 is depicted the calculated molecular structure of NAI-3T together with that of NDI-3T showing how the steric interactions are not present in the novel NAI derivative. The planar skeletons in these new family induce higher degree of crystallinity and the carrier charge transport can be switched from n-type to ambipolar behaviour. The highest FET performance is achieved for vapor-deposited films of NAI-3T with mobilities of 1.95x10-4cm2V-1s-1 and 2.00x10-4cm2V-1s-1 for electrons and holes, respectively. Finally, these planar semiconductors are compared with their NDI derivates analogues, which exhibit only n-type mobility, in order to understand the origin of the ambipolarity in this new series of molecular semiconductors.

Breaking the curve with candels: a Bayesian approach to reveal the non-universality of the dust-attenuation law at high redshift

Dust attenuation affects nearly all observational aspects of galaxy evolution, yet very little is known about the form of the dust-attenuation law in the distant universe. Here, we model the spectral energy distributions of galaxies at z ~ 1.5–3 from CANDELS with rest-frame UV to near-IR imaging under different assumptions about the dust law, and compare the amount of inferred attenuated light with the observed infrared (IR) luminosities. Some individual galaxies show strong Bayesian evidence in preference of one dust law over another, and this preference agrees with their observed location on the plane of infrared excess (IRX, L_TIR/L_UV) and UV slope (β). We generalize the shape of the dust law with an empirical model, A_ λ,σ =E(B-V)k_ λ (λ / λ v)^ σ where k_λ is the dust law of Calzetti et al., and show that there exists a correlation between the color excess E(B-V) and tilt δ with δ =(0.62±0.05)log(E(B-V))+(0.26±0.02). Galaxies with high color excess have a shallower, starburst-like law, and those with low color excess have a steeper, SMC-like law. Surprisingly, the galaxies in our sample show no correlation between the shape of the dust law and stellar mass, star formation rate, or β. The change in the dust law with color excess is consistent with a model where attenuation is caused by scattering, a mixed star–dust geometry, and/or trends with stellar population age, metallicity, and dust grain size. This rest-frame UV-to-near-IR method shows potential to constrain the dust law at even higher redshifts (z>3).

Design of biobased additives for tuning the properties of biopolymers

This work mainly arises from the necessity to support the rapid introduction of different biobased polymers that the industrial sector has been facing lately. Indeed, while considerable efforts are being made to find environmentally and economically sustainable materials, less attention is paid to their need to be properly compounded to fulfil increasingly rigorous technical and quality requirements. Therefore, there is a strong demand for the development of a novel generation of compatible additives able to improve the properties of biobased polymers while respecting sustainability. With this in mind, a new class of biobased plasticizers is herein proposed. Five different ketal-diesters were selectively synthesized starting from levulinic acid, a promising renewable chemical platform. These molecules were added to poly(vinyl chloride) as model polymer to test their plasticizing effectiveness. Complete morphological, thermal and viscoelastic characterizations showed a clear correlation between the structural features of the ketal-esters and the properties of the material. In addition, no significant leaching was found in both hydrophilic and lipophilic environments. Importantly, the proposed ketal-diesters performed comparably and, in some cases, even better than commercial plasticizers. The same molecules were then added to bacterial poly(3-hydroxybutyrate), a semicrystalline polyester characterized by poor thermal and mechanical properties. Morphology assessments showed no phase separation and the plasticizing effectiveness was confirmed by thermal and viscoelastic analyses, while leaching tests showed low extraction values. Readily usable fractions with controlled structure and tailored properties were obtained from highly heterogeneous industrial grade Kraft lignin. These fractions were then added to poly(vinyl alcohol). Promising preliminary results in terms of compatibility were achieved, with thermograms showing only one glass transition temperature. Finally, a fully biobased glycerol-trilevulinate was successfully synthesized by means of a mild and solvent-free route. Its plasticizing effectiveness was evaluated on poly(vinyl chloride), showing a significant decrease of the glass transition temperature of the material.

New functional polythiophene based materials: fine-tuning of photovoltaic or chiroptical properties

There is a remarkable level of interest in the development of π-conjugated polymers (ICPs) which have been employed, thanks to their promising optical and electronic properties, in numerous applications including photovoltaic cells, light emitting diodes and thin-film transistors. Although high power conversion efficiency can be reached using poly(3-alkylthiophenes) (P3ATs) as electron-donating materials in polymeric solar cells of the Bulk-Heterojunction type (BHJ), their relatively large band gap limits the solar spectrum fraction that can be utilized. The research work described in this dissertation thus concerns the synthesis, characterization and study of the optical and photoactivity properties of new organic semiconducting materials based on polythiophenes. In detail, various narrow band gap polymers and copolymers were developed through different approaches and were characterized by several complementary techniques, such as gel permeation chromatography (GPC), NMR spectroscopy, thermal analyses (DSC, TGA), UV-Vis/PL spectroscopy and cyclic voltammetry (CV), in order to investigate their structural and chemical/photophysical properties. Moreover, the polymeric derivatives were tested as active material in air-processed organic solar cells. The activity has also been devoted to investigate the behavior of polythiophenes with chiral side chain, that are fascinating materials capable to assume helix supramolecular structures, exhibiting optical activity in the aggregated state.

Peptidomimetic ligands for tuning integrin-mediated signalling: rational design, synthesis and theranostic applications

Integrins are α/β-heterodimeric transmembrane adhesion receptors that mediate cell-cell and cell-ECM interactions. Integrins are bidirectional signalling receptors that respond to external signals (“outside-in” signalling) and in parallel, transduce internal signals to the matrix (“inside-out” signalling), to regulate vital cellular functions including migration, survival, growth and differentiation. Therefore, dysregulation of these tightly regulated processes often results in uncontrolled integrin activation and abnormal tissue expression that is responsible for many diseases. Because of their important roles in physiological and pathological events, they represent a validated target for therapeutic and diagnostic purposes. The aim of the present Thesis was focused on the development of peptidic ligands for α4β1 and αvβ3 integrin subtypes, involved in inflammatory responses (leukocytes recruitment and extravasation) and cancer progression (angiogenesis, tumor growth, metastasis), respectively. Following the peptidomimetic strategy, we designed and synthesized a small library of linear and cyclic hybrid α/β-peptidomimetics based on the phenylureido-LDV scaffolds for the treatment of chronic inflammatory autoimmune diseases. In order to implement a fast and non-invasive diagnostic method for monitoring the course of the inflammatory processes, a flat glass-surface of dye-loaded Zeolite L-crystal nanoparticles was coated with bioactive α4β1-peptidomimetics to detect specific integrin-expressing cells as biomarkers of inflammatory diseases. Targeted drug delivery has been considered a promising alternative to overcome the pharmacokinetic limitations of conventional anticancer drugs. Thus, a novel Small-Molecule Drug Conjugate was synthesized by connecting the highly cytotoxic Cryptophycin to the tumor-targeting RGDfK-peptide through a protease-cleavable linker. Finally, in view to making the peptide synthesis more sustainable and greener, we developed an alternative method for peptide bonds formation employing solvent-free mechanochemistry and ultra-mild minimal solvent-grinding conditions in common, inexpensive laboratory equipment. To this purpose, standard amino acids, coupling agents and organic-green solvents were used in the presence of nanocrystalline hydroxyapatite as a reusable, bio-compatible inorganic basic catalyst.

Intermediate linguistic task fine-tuning on Multi-lingual models

State-of-the-art NLP systems are generally based on the assumption that the underlying models are provided with vast datasets to train on. However, especially when working in multi-lingual contexts, datasets are often scarce, thus more research should be carried out in this field. This thesis investigates the benefits of introducing an additional training step when fine-tuning NLP models, named Intermediate Training, which could be exploited to augment the data used for the training phase. The Intermediate Training step is applied by training models on NLP tasks that are not strictly related to the target task, aiming to verify if the models are able to leverage the learned knowledge of such tasks. Furthermore, in order to better analyze the synergies between different categories of NLP tasks, experimentations have been extended also to Multi-Task Training, in which the model is trained on multiple tasks at the same time.

Modellazione assistita di curve di probabilità (POD) per il rilevamento di difetti strutturali mediante fibre ottiche

I sensori a fibre ottiche rappresentano una delle tecnologie più promettenti per il monitoraggio di varie strutture ingegneristiche. Tali sensori, dopo che sono stati incollati su differenti tipologie di strutture grazie a un dispositivo optoelettronico, restituiscono il profilo di deformazione del materiale ospite. Tuttavia, risulta piuttosto complicato ottenere queste curve, in quanto sono necessari numerosi provini che richiedono spese onerose e molto tempo per i singoli esperimenti. In più, si deve tenere in considerazione che i provini non sono mai completamente identici e che l’operatore può commettere errori. In questo studio si genera un programma attraverso cui si simulano diversi andamenti di deformazione, cercando di riprodurre al meglio i vari casi sperimentali. Infine, utilizzando un codice già esistente, si ricavano le curve di probabilità di rilevamento del danno in funzione della lunghezza di cricca. Una volta creato il codice, si modificano alcuni parametri, in particolare si alterano lo shear lag e alcune caratteristiche meccaniche della fibra ottica, ovvero il raggio e il modulo di Young, per vedere l’influenza che hanno sulle curve di probabilità. I risultati hanno dimostrato che lo shear lag della fibra ottica deve essere il più possibile alto e di conseguenza il raggio e il modulo di Young della fibra devono essere bassi, in quanto quest’ultimi si trovano a denominatore della formula usata per calcolare lo shear lag.

Analisi di curve di luce del pianeta XO-2b tramite la tecnica della variazione dei tempi di transito.

La ricerca di esopianeti è un ambito astrofisico in continua evoluzione. Nuovi metodi vengono proposti con l’obiettivo di individuare pianeti con una varietà di caratteristiche sempre più ampia, per poter definire al meglio la storia di formazione ed evoluzione dei sistemi planetari. Un metodo recente in grado di caratterizzare pianeti di piccola massa è lo studio della variazione del tempo di transito (TTV), basato sulla modulazione del periodo orbitale di un pianeta noto causata dalla perturbazione di un corpo aggiuntivo. In questo lavoro proponiamo l’analisi delle curve di luce del pianeta XO-2Nb al fine di individuare TTV. Questo sistema è di particolare rilevanza poiché ospitato dalla prima stella binaria wide in cui entrambe le componenti presentano un proprio sistema planetario. Tra le due stelle solo XO-2N presenta un pianeta transitante, requisito per l’applicazione del metodo proposto. L’analisi dei dati è stata svolta utilizzando il metodo della fotometria differenziale di apertura, normalizzando la curva di luce del target ad altre due stelle di riferimento presenti nel campo di vista dello strumento. I risultati ottenuti evidenziano l’assenza di variazioni di periodo orbitale per XO-2Nb e sono consistenti con un’effemeride lineare. La nuova effemeride calcolata risulta tre volte più precisa rispetto al più recente studio in letteratura, e permetterà di predire futuri transiti con una precisione migliore di un minuto fino al 2035. Abbiamo stabilito un limite superiore all’ampiezza del TTV permessa dai nostri dati, ricavando il valore massimo della massa di un eventuale pianeta perturbatore, pari a 0.15 masse terrestri. Abbiamo ricavato in maniera indipendente i parametri fisici ed orbitali di XO-2Nb, confermando e raffinando i valori presenti in letteratura. I risultati ottenuti suggeriscono che, in determinati casi, l’analisi fotometrica eseguita utilizzando telescopi medio-piccoli da terra può essere competitiva con i più avanzati telescopi spaziali.

Mechanisms Predisposing Penile Fracture And Long-term Outcomes On Erectile And Voiding Functions.

Purpose. To determine the mechanisms predisposing penile fracture as well as the rate of long-term penile deformity and erectile and voiding functions. Methods. All fractures were repaired on an emergency basis via subcoronal incision and absorbable suture with simultaneous repair of eventual urethral lesion. Patients' status before fracture and voiding and erectile functions at long term were assessed by periodic follow-up and phone call. Detailed history included cause, symptoms, and single-question self-report of erectile and voiding functions. Results. Among the 44 suspicious cases, 42 (95.4%) were confirmed, mean age was 34.5 years (range: 18-60), mean follow-up 59.3 months (range 9-155). Half presented the classical triad of audible crack, detumescence, and pain. Heterosexual intercourse was the most common cause (28 patients, 66.7%), followed by penile manipulation (6 patients, 14.3%), and homosexual intercourse (4 patients, 9.5%). Woman on top was the most common heterosexual position (n = 14, 50%), followed by doggy style (n = 8, 28.6%). Four patients (9.5%) maintained the cause unclear. Six (14.3%) patients had urethral injury and two (4.8%) had erectile dysfunction, treated by penile prosthesis and PDE-5i. No patient showed urethral fistula, voiding deterioration, penile nodule/curve or pain. Conclusions. Woman on top was the potentially riskiest sexual position (50%). Immediate surgical treatment warrants long-term very low morbidity.