AMS Tesi di Dottorato

    Investigation of heterogeneous catalysts for the synthesis of fine chemicals

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    In order to match the more stringent environmental regulations, heterogenization of traditional homogeneous processes is one of the main challenges of the modern chemical industry. Great results have been achieved in the fields of petrochemicals and base chemicals, whereas in fine chemical industry most of the synthetic procedures are based on multistep processes catalyzed by homogeneous catalysts mainly used in stoichiometric amounts. In the fine chemicals manufacture not so much efforts have been devoted to the investigation of suitable solid catalysts for the development of greener processes, then this sector represent a very attractive field of research. In this context, the present work deals with the extensive investigation of the possibility to heterogenize existing processes, in particular two different classes of reactions have been studied: alkylation of aromatic and heteroaromatic compounds and selective oxidation of aromatic alcohols. Traditional solid acid catalysts, such as zeolites, clays and alumina have been tested in the gas phase alkylation of 1,2-methylendioxybenzene, core building block of many drugs, pesticides and fragrances. The observed reactivity were clarified through a deep FTIR investigation complemented by ab initio calculation. The same catalysts were tested in the gas phase isopropylation of thiophene with the aim of clearly attribute the role of the reaction parameters in the reaction proceeding and verify the possibility to enhance the selectivity of one of the two possible isomers. Finally various Au/CeO2 catalysts were tested in the synthesis of benzaldehyde and piperonal, two aldehydes largely employed in the manufacture of fine chemical products, through liquid phase oxidation of the corresponding alcohols in very mild conditions

    Non-thermal emission in the lobes of radio galaxies.

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    Radio and gamma-ray measurements of radiogalaxy lobes are useful to determine whether emission in these widely separated spectral regions is mainly by non-thermal (NT) electrons. This is of interest as there is yet no proof for a significant emission component from pion decay following NT proton interactions in the ambient lobe gas. An assessment of the hadronic yield needs full accounting of the local (FGL) and background (EBL, CMB) radiation fields in the lobes. Assuming a truncated single-PL electron energy distribution, exact calculation of the emission by NT electrons in the magnetized plasma in the Fornax A lobes leads to the conclusion that its Fermi-LAT emission is mostly IC/GFL: this result weakens earlier conclusions on the hadronic origin of the LAT emission. Similar analyses of the lobe emissions of Cen A, Cen B, and NGC 6251 suggest their measured LAT emissions, too, to be of IC/(EBL, CFGL, CMB) nature. Measured emissions of distant radio-galaxy lobes (3C98, Pictor A, DA240, Cygnus A, 3C326, and 3C236) are currently limited to the radio and X-ray bands: they can give no information on the presence of NT protons, but do trace the properties of NT electrons, and allow calculations of the related IC gamma-ray emission to be performed. The e/B energy density ratios, U_e/U_B, turn out to be in the range ~1-100. The NT proton energy density, U_p, is spectrally constrained to be less than a few tens of eV/cm3. Despite this limit, arguably U_p >> U_e -- as suggested by arguments of lobe internal vs external pressure. Thus the lobes' NT energy budget is likely dominated by particles. Given the low thermal energy densities measured in lobes, NT energy dominance is probably a general feature of lobe energetics

    Non invasive assessment of right ventricle in patients with operated tetralogy of Fallot

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    The objective of this study was to evaluate right ventricular function in patients with right ventricular volume overload in patients with (tetralogy of Fallot, and pulmonary atresia + VSD ) underwent corrective surgery; with echocardiography measure that can be easily applied; and to study the relationship between ProBNP and the contractile function of the right ventricle, dilated right atrium, and the consequences of pulmonary insufficiency . Methods: The study included 50 patients (50% males, mean age 30.64 ± 13.30 years) with prior cardiac surgical intervention of TDF (90%) or pulmonary atresia + VSD (10%). (49 pz) have performed a cardiac MRI and clinical evaluation, (47 pz) echocardiogram, (48 pz) ECG, (34 pz) a cardiopulmonary exercise testing, (29 pz) a dosage of ProBNP. Results: The S-wave velocity (p 35. ProBNP correlated positively and significantly with the area of the right atrium (p = 0.0001), and negative and significant with VO2 max (p = 0.04). Those who have increased pulmonary insufficiency (PVR fraction> 30%) have a significantly increased RVED volume (p = 0.01), reduced VO2 max (p = 0.04), and lower ejection fraction of LV (p = 0.02) than the group of patients with PVR ≤ 30. Conclusion: The TAPSE and S-wave velocity are fundamental and may become the technique of choice for routine assessment of RV systolic function in adult patients with TOF. The monitoring of the Pro BNP is probably a choice, given the simplicity and their information that correlate with the test cardiopulmonary. In view of the ventricular-ventricular interaction, so measures to maintain or restore the functioning of the pulmonary valve could preserve biventricular function

    Quantifying and modeling ecosystem services provided by urban greening in cities of the Southern Alps, N Italy

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    Population growth in urban areas is a world-wide phenomenon. According to a recent United Nations report, over half of the world now lives in cities. Numerous health and environmental issues arise from this unprecedented urbanization. Recent studies have demonstrated the effectiveness of urban green spaces and the role they play in improving both the aesthetics and the quality of life of its residents. In particular, urban green spaces provide ecosystem services such as: urban air quality improvement by removing pollutants that can cause serious health problems, carbon storage, carbon sequestration and climate regulation through shading and evapotranspiration. Furthermore, epidemiological studies with controlled age, sex, marital and socio-economic status, have provided evidence of a positive relationship between green space and the life expectancy of senior citizens. However, there is little information on the role of public green spaces in mid-sized cities in northern Italy. To address this need, a study was conducted to assess the ecosystem services of urban green spaces in the city of Bolzano, South Tyrol, Italy. In particular, we quantified the cooling effect of urban trees and the hourly amount of pollution removed by the urban forest. The information was gathered using field data collected through local hourly air pollution readings, tree inventory and simulation models. During the study we quantified pollution removal for ozone, nitrogen dioxide, carbon monoxide and particulate matter (<10 microns). We estimated the above ground carbon stored and annually sequestered by the urban forest. Results have been compared to transportation CO2 emissions to determine the CO2 offset potential of urban streetscapes. Furthermore, we assessed commonly used methods for estimating carbon stored and sequestered by urban trees in the city of Bolzano. We also quantified ecosystem disservices such as hourly urban forest volatile organic compound emissions

    Designing Electricity Auctions in the Presence of Transmission Constraints

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    This paper analyzes the effect that different designs in the access to fnancial transmission rights has on spot electricity auctions. In particular, I characterize the equilibrium in the spot electricity market when financial transmission rights are assigned to the grid operator and when financial transmission rights are assigned to the firm that submits the lowest bid in the spot electricity auction. When financial transmission rights are assigned to the grid operator, my model, in contrast with the models available in the literature, works out the equilibrium for any transmission capacity. Moreover, I have found that an increase in transmission capacity not only increases competition between markets but also within a single market. When financial transmission rights are assigned to the firm that submits the lowest bid in the spot electricity auction, firms compete not only for electricity demand, but also for transmission rights and the arbitrage profits derived from its hold. I have found that introduce competition for transmission rights reduces competition in spot electricity auctions

    Fine Mapping of qroot-yield-1.06, a QTL for Root, Plant Vigor and Yield in Maize

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    Root-yield-1.06 is a major QTL affecting root system architecture (RSA) and other agronomic traits in maize. The effect of this QTL has been evaluated with the development of near isogenic lines (NILs) differing at the QTL position. The objective of this study was to fine map qroot-yield-1.06 by marker-assisted searching for chromosome recombinants in the QTL interval and concurrent root phenotyping in both controlled and field conditions, through successive generations. Complementary approaches such as QTL meta-analysis and RNA-seq were deployed in order to help prioritizing candidate genes within the QTL target region. Using a selected group of genotypes, field based root analysis by ‘shovelomics’ enabled to accurately collect RSA information of adult maize plants. Shovelomics combined with software-assisted root imaging analysis proved to be an informative and relatively highly automated phenotyping protocol. A QTL interval mapping was conducted using a segregating population at the seedling stage grown in controlled environment. Results enabled to narrow down the QTL interval and to identify new polymorphic markers for MAS in field experiments. A collection of homozygous recombinant NILs was developed by screening segregating populations with markers flanking qroot-yield-1.06. A first set of lines from this collection was phenotyped based on the adapted shovelomics protocol. QTL analysis based on these data highlighted an interval of 1.3 Mb as completely linked with the target QTL but, a larger safer interval of 4.1 Mb was selected for further investigations. QTL meta-analysis allows to synthetize information on root QTLs and two mQTLs were identified in the qroot-yield-1.06 interval. Trascriptomics analysis based on RNA-seq data of the two contrasting QTL-NILs, confirmed alternative haplotypes at chromosome bin 1.06. qroot-yield-1.06 has now been delimited to a 4.1-Mb interval, and thanks to the availability of additional untested homozygous recombinant NILs, the potentially achievable mapping resolution at qroot-yield-1.06 is c. 50 kb

    Threshold Limit Value for biomechanical risk factors (ACGIH-TLV®): a cohort study on carpal tunnel syndrome in manual workers

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    OBIETTIVI: Per esplorare il contributo dei fattori di rischio biomeccanico, ripetitività (hand activity level – HAL) e forza manuale (peak force - PF), nell’insorgenza della sindrome del tunnel carpale (STC), abbiamo studiato un’ampia coorte di lavoratori dell’industria, utilizzando come riferimento il valore limite di soglia (TLV©) dell’American Conference of Governmental Industrial Hygienists (ACGIH). METODI: La coorte è stata osservata dal 2000 al 2011. Abbiamo classificato l’esposizione professionale rispetto al limite di azione (AL) e al TLV dell’ACGIH in: “accettabile” (sotto AL), “intermedia” (tra AL e TLV) e “inaccettabile” (sopra TLV). Abbiamo considerato due definizioni di caso: 1) sintomi di STC; 2) sintomi e positività allo studio di conduzione nervosa (SCN). Abbiamo applicato modelli di regressione di Poisson aggiustati per sesso, età, indice di massa corporea e presenza di patologie predisponenti la malattia. RISULTATI: Nell’intera coorte (1710 lavoratori) abbiamo trovato un tasso di incidenza (IR) di sintomi di STC di 4.1 per 100 anni-persona; un IR di STC confermata dallo SCN di 1.3 per 100 anni-persona. Gli esposti “sopra TLV” presentano un rischio di sviluppare sintomi di STC di 1.76 rispetto agli esposti “sotto AL”. Un andamento simile è emerso per la seconda definizione di caso [incidence rate ratios (IRR) “sopra TLV”, 1.37 (intervallo di confidenza al 95% (IC95%) 0.84–2.23)]. Gli esposti a “carico intermedio” risultano a maggior rischio per la STC [IRR per i sintomi, 3.31 (IC95% 2.39–4.59); IRR per sintomi e SCN positivo, 2.56 (IC95% 1.47–4.43)]. Abbiamo osservato una maggior forza di associazione tra HAL e la STC. CONCLUSIONI: Abbiamo trovato un aumento di rischio di sviluppare la STC all’aumentare del carico biomeccanico: l’aumento di rischio osservato già per gli esposti a “carico intermedio” suggerisce che gli attuali valori limite potrebbero non essere sufficientemente protettivi per alcuni lavoratori. Interventi di prevenzione vanno orientati verso attività manuali ripetitive.OBJECTIVES: To explore the role of workplace physical factors, particularly repetition (hand activity level – HAL) and manual force (normalized peak force – PF), in the development of carpal tunnel syndrome (CTS), we studied a large cohort of industrial workers with reference to a threshold limit value (TLV©) proposed by the American Conference of Governmental Industrial Hygienists (ACGIH). METHODS: Industrial workers were followed from 2000-2011. We classified subjects with respect to action limit (AL) and TLV. Case definitions were: (i) self-reported symptoms; and (ii) a combination of symptoms and positive nerve conduction studies (NCS). Poisson regression models including age, gender, body mass index, and presence of predisposing pathologies were conducted to estimate incidence rate ratios (IRR) of CTS. RESULTS: There were 1710 subjects with complete information at baseline and with at least one follow-up. We found an incidence rate (IR) of 4.1 per 100 person-years for CTS symptoms, and an IR of 1.3 per 100 person-years for CTS confirmed by NCS. “Unacceptable overload” (above TLV) was associated with a 1.76-fold risk of CTS symptoms, as compared with “acceptable load” (below the AL). A similar trend also emerged for CTS confirmed by NCS, but was not significant [IRR above TLV, 1.37 (95% confidence interval ( 95% CI) 0.84–2.23)]. Workers exposed between AL and TLV appeared at higher risk for CTS [IRR for symptoms, 3.31 (95% CI 2.39–4.59); IRR for symptoms and positive NCS, 2.56 (95% CI 1.47–4.43)]. HAL was a strong predictor of the outcome variables. CONCLUSIONS: Workplace risk factors contribute to the risk for CTS. Our study shows an increased risk for workers exposed between AL and TLV, suggesting that the current limits might not be sufficiently protective for some workers. Preventive efforts should target repetitive movements
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