MEDIUM-CHAIN-LENGTH POLY(3-HYDROXYALKANOATE) NANOPARTICLE SUSPENSIONS

The main goal of this thesis was to prepare medium-chain-length poly-3-hydroxyalkanoate (mcl-PHA) nanoparticle suspensions at high solids content (≥ 10 % w/v). A two-stage emulsification-solvent evaporation process was employed to produce poly-3-hydroxydecanoate (PHD) suspensions. The formulation and processing conditions including ultrasonication time and amplitude, selection of solvent, and selection of surfactants and their concentrations were investigated to make concentrated suspensions (10 and 30 % (w/v)) of PHD with particles less than 300 nm. Among the ionic surfactants tested to stabilize the suspension, the anionic, sodium dodecyl sulphate (SDS), and the cationic, dodecyltrimethylammonium bromide (DTAB) surfactants produced the smallest particle sizes (~100 nm). However, more stabilized nanoparticles were obtained when the ionic surfactant, SDS, was combined with any of the non-ionic surfactants tested, with polyoxyethylene octyl phenyl ether (Triton X-100) or polyoxyethylene (20) sorbitan monooleate (Tween 80) resulting in a slight increase in zeta potential over 30 days while the zeta potential with other non-ionic surfactants decreased. Mcl-PHA containing 11 and 18 % of carboxyl groups was synthesized via free radical addition reaction of 11-mercaptoundecanoic acid to the pendant double bonds of unsaturated poly-3-hydroxynonanoate (PHNU). Colloidal suspensions prepared by ultrasonication needed a surfactant to maintain stability, even at 0.4 % solids of mcl-PHA containing 11 % carboxylation (PHNC-1) unlike the stable suspensions prepared without surfactants by the titration method. Similar particle sizes (155.6 ± 8.4 to 163.4 ± 11.3 nm) and polydispersity indices (0.42 ± 0.03 to 0.49 ± 0.04) were obtained when several non-ionic surfactants were tested to minimize particle agglomeration, with the smallest particles obtained with Triton X-100. When Triton X-100 was combined with a variety of ionic surfactants, smaller nanoparticles (97.1 ± 1.1 to 121.7 ± 5.7 nm) with a narrower particle size distribution (0.21 ± 0.001 to 0.25 ± 0.003) were produced. The SDS and Triton X-100 combination was chosen to evaluate other mcl-PHAs at 10 % (w/v) solids content. Slightly smaller nanoparticles were formed with carboxylated mcl-PHAs compared to mcl-PHAs having aliphatic pendant side chains. Mcl-PHA consisting of 18 % carboxylation (PHNC-2) formed a much smaller nanoparticles and higher zeta potential.

Biochemical and epidemiological investigations of non-steroidal anti-inflammatory drug usage and related side effects in equids

Non-steroidal anti-inflammatory drugs (NSAIDs) are widely used in equine veterinary practice. These drugs exert their effect by inhibiting cyclooxygenase (COX) enzymes, which control prostaglandin production, a major regulator of tissue perfusion. Two isoforms of COX enzymes exist: COX-1 is physiologically present in tissues, while COX-2 is up-regulated during inflammation and has been indicated as responsible for the negative effects of an inflammatory response. Evidence suggests that NSAIDs that inhibit only COX-2, preserving the physiological function of COX-1 might have a safer profile. Studies that evaluate the effect of NSAIDs on COX enzymes are all performed under experimental conditions and none uses actual clinical patients. The biochemical investigations in this work focus on describing the effect on COX enzymes activity of flunixin meglumine and phenylbutazone, two non-selective COX inhibitors and firocoxib, a COX-2 selective inhibitor, in clinical patients undergoing elective surgery. A separate epidemiological investigation was aimed at describing the impact that the findings of biochemical data have on a large population of equids. Electronic medical records (EMRs) from 454,153 equids were obtained from practices in the United Kingdom, United States of America and Canada. Information on prevalence and indications for NSAIDs use was extracted from the EMRs via a text mining technique, improved from the literature and described and validated within this Thesis. Further the prevalence of a clinical sign compatible with NSAID toxicity, such as diarrhoea, is reported along with analysis evaluating NSAID administration in light of concurrent administration of other drugs and comorbidities. This work confirms findings from experimental settings that NSAIDs firocoxib is COX-2 selective and that flunixin meglumine and phenylbutazone are non-selective COX inhibitors and therefore their administration carries a greater risk of toxicity. However the impact of this finding needs to be interpreted with caution as epidemiological data suggest that the prevalence of toxicity is in fact small and the use of these drugs at the labelled dose is quite safe.

Maintenance or loss of dialect Andalusian features: Internal and external factors

In the last sixty years a steadily maintained process of convergence towards the Castilian national standard has been occurring in Southern Spain affecting urban middle-class speakers’ varieties, particularly phonology and lexis. As a consequence, unmarked features characterising innovative southern pronunciation have become less frequent and, at the same time, certain standard marked features have been adapted to the southern phonemic inventory. Then, urban middle-class varieties have progressively been stretching out the distance separating them from working-class and rural varieties, and bringing them closer to central Castilian varieties. Intermediate, yet incipient koineised varieties have been described including also transitional Murcia and Extremadura dialects (Hernández & Villena 2009, Villena, Vida & von Essen 2015). (1) Some of the standard phonologically marked features have spread out among southern speakers exclusively based on their mainstream social prestige and producing not only changes in obstruent phoneme inventory –i.e. acquisition of /s/ vs. /θ/ contrast, but also standstill and even reversion of old consonant push- or pull-chain shifts –e.g. /h/ or /d/ fortition, affricate /ʧ/, etc. as well as traditional lexis shift (Villena et al. 2016). Internal (grammar and word frequency) and external (stratification, network and style) factors constraining those features follow similar patterns in the Andalusian speech communities analysed so far (Granada, Malaga) but when we zoom in on central varieties, which are closer to the national standard and then more conservative, differences in frequency increase and conflict sites emerge. (2) Unmarked ‘natural’ phonological features characterising southern dialects, particularly deletion of syllable-final consonant, do not keep pace with this trend of convergence towards the standard. Thus a combination of southern innovative syllable-final and standard conservative onset-consonant features coexist. (3). The main idea is that this intermediate variety is formed through changes suggesting that Andalusian speakers look for the best way of accepting marked prestige features without altering coherence within their inventory. Either reorganisation of the innovative phonemic system in such a way that it may include Castilian and standard /s/ vs. /θ/ contrast or re-syllabification of aspirated /s/ before dental stop are excellent examples of how and why linguistic features are able to integrate intermediate varieties between the dialect-standard continuum.

Europeanization beyond the EU: The case of Georgia.

320 p.

L’analyse biomécanique du sprint sur ergomètre non-motorisé : interaction entre les asymétries cinétiques et cinématiques lors d’un sprint de 40 verges

Au sprint 100 mètres et dans de nombreux sport de puissance, la phase d’accélération est un déterminant majeure de la performance. Toutefois, les asymétries cinétiques et cinématiques peuvent avoir une incidence sur la performance. L’objectif de cette étude était d’identifier la présence d’interaction entre différentes variables cinétiques et cinématiques angulaires aux membres inférieures (MI) d’un sprint de haute intensité sur un ergomètre non-motorisé avec résistance (NMR). Suite à une rencontre de familiarisation, 11 sujets ont exécuté des sprints de 40 verges. Les données cinétiques ont été obtenues par l’entremise de plateformes de force intégrées aux appuis de l’ergomètre NMR à 10 Hz et les données cinématiques ont été amassées à l’aide du système Optitrack et du logiciel Motive Tracker à 120Hz. Nous avons effectué un test de corrélation linéaire (Corrélation linéaire de Pearson) pour déterminer la relation entre les données cinétiques et cinématiques (p < 0,05). L’analyse des données a révélée (1) une corrélation positive entre la moyenne d’amplitude articulaire à la cheville et la moyenne des pics de puissance développés (W/kg) lors de la phase de maintien (r = 0,62), (2) une corrélation négative entre l’extension maximale moyenne (calculé à partir de l’angle de flexion le plus petit) à la hanche et la moyenne de pics de puissance développées en fin de poussée lors de la totalité et de la phase de maintien (r = -0,63 et r = -0,69 respectivement), et finalement (3) une corrélation négative entre la différence de dorsiflexion maximale à la cheville et la différence des pics de puissance développés aux MI lors du contact du pied au sol en phase de maintien ( r = -0,62). Les résultats obtenus dans cette étude permettront d’améliorer l’intervention des préparateurs physiques et la pratique des athlètes de sport de puissance en plus d’aider au développant de nouvelles technologies et outils d’entrainement complémentaire au sprint et particulièrement à la phase d’accélération.

Medium-Chain-Length Poly (3-Hydroxyalkanoate) Nanoparticle Suspensions

Thesis (Master, Chemical Engineering) -- Queen's University, 2016-08-16 04:58:55.749

L’analyse biomécanique du sprint sur ergomètre non-motorisé : interaction entre les asymétries cinétiques et cinématiques lors d’un sprint de 40 verges

Au sprint 100 mètres et dans de nombreux sport de puissance, la phase d’accélération est un déterminant majeure de la performance. Toutefois, les asymétries cinétiques et cinématiques peuvent avoir une incidence sur la performance. L’objectif de cette étude était d’identifier la présence d’interaction entre différentes variables cinétiques et cinématiques angulaires aux membres inférieures (MI) d’un sprint de haute intensité sur un ergomètre non-motorisé avec résistance (NMR). Suite à une rencontre de familiarisation, 11 sujets ont exécuté des sprints de 40 verges. Les données cinétiques ont été obtenues par l’entremise de plateformes de force intégrées aux appuis de l’ergomètre NMR à 10 Hz et les données cinématiques ont été amassées à l’aide du système Optitrack et du logiciel Motive Tracker à 120Hz. Nous avons effectué un test de corrélation linéaire (Corrélation linéaire de Pearson) pour déterminer la relation entre les données cinétiques et cinématiques (p < 0,05). L’analyse des données a révélée (1) une corrélation positive entre la moyenne d’amplitude articulaire à la cheville et la moyenne des pics de puissance développés (W/kg) lors de la phase de maintien (r = 0,62), (2) une corrélation négative entre l’extension maximale moyenne (calculé à partir de l’angle de flexion le plus petit) à la hanche et la moyenne de pics de puissance développées en fin de poussée lors de la totalité et de la phase de maintien (r = -0,63 et r = -0,69 respectivement), et finalement (3) une corrélation négative entre la différence de dorsiflexion maximale à la cheville et la différence des pics de puissance développés aux MI lors du contact du pied au sol en phase de maintien ( r = -0,62). Les résultats obtenus dans cette étude permettront d’améliorer l’intervention des préparateurs physiques et la pratique des athlètes de sport de puissance en plus d’aider au développant de nouvelles technologies et outils d’entrainement complémentaire au sprint et particulièrement à la phase d’accélération.

Analisi multi-obiettivo in ottica lean-green della reverse logistics dei veicoli a fine vita (ELV)

La gestione del fine vita dei prodotti è un argomento di interesse attuale per le aziende; sempre più spesso l’imprese non possono più esimersi dall’implementare un efficiente sistema di Reverse Logistics. Per rispondere efficacemente a queste nuove esigenze diventa fondamentale ampliare i tradizionali sistemi logistici verso tutte quelle attività svolte all’interno della Reverse Logitics. Una gestione efficace ed efficiente dell’intera supply chain è un aspetto di primaria importanza per un’azienda ed incide notevolmente sulla sua competitività; proprio per perseguire questo obiettivo, sempre più aziende promuovono politiche di gestione delle supply chain sia Lean che Green. L’obiettivo di questo lavoro, nato dalle esigenze descritte sopra, è quello di applicare un modello innovativo che consideri sia politiche di gestione Lean, che dualmente politiche Green, alla gestione di una supply chain del settore automotive, comprendente anche le attività di gestione dei veicoli fuori uso (ELV). Si è analizzato per prima cosa i principi base e gli strumenti utilizzati per l’applicazione della Lean Production e del Green supply chain management e in seguito si è analizzato le caratteristiche distintive della Reverse Logistics e in particolare delle reti che trattano i veicoli a fine vita. L’obiettivo finale dello studio è quello di elaborare e implementare, tramite l’utilizzo del software AMPL, un modello di ottimizzazione multi-obiettivo (MOP- Multi Objective Optimization) Lean e Green a una Reverse Supply Chain dei veicoli a fine vita. I risultati ottenuti evidenziano che è possibile raggiungere un ottimo compromesso tra le due logiche. E' stata effettuata anche una valutazione economica dei risultati ottenuti, che ha evidenziato come il trade-off scelto rappresenti anche uno degli scenari con minor costi.

Fuori dai binari. Tradurre le identita non binarie nel romanzo Young Adult I Wish You All the Best di Mason Deaver

The goal of this final dissertation is to propose a partial translation of the Young Adult novel I Wish You All the Best by nonbinary author Mason Deaver, which was published in the United States by PUSH in 2019 and is currently still unpublished in Italy. The book follows the story of eighteen-year-old Ben De Backer. After coming out as nonbinary to their parents, they are kicked out of their home; thanks to the help of their older sister, they will manage to get back on their feet and start a new life, although their trauma will continue to pose a great obstacle to their growth and happiness. I Wish You All the Best is one of the first novels with a nonbinary protagonist in the Young Adult category and is particularly interesting from a linguistic standpoint. The first chapter serves as introduction to the author, Mason Deaver, their life and their relationship with gender identity and writing; and also as an introduction to the book itself and how its main characters and themes are developed in relation to the plot. The second chapter looks at the Young Adult genre as a whole; it explores its origins and development through the years and seeks to find a definition for this type of literature which has often been misrepresented both in the eyes of literary critics and the general public. Additionally, the chapter will describe some of the main characteristics of YA literature and analyze them in relation to I Wish You All the Best. The third chapter aims to examine the role of language, and how it can be inclusive to people outside of the gender binary. It will also touch upon the sociocultural contexts in which the speakers of different languages operate. The fourth and final chapter will present the translation of several passages taken from the novel I Wish You All the Best and offer an analysis of the most interesting and difficult aspects of this translation process.

Applicazione ed implicazioni della Corporate Sustainability Due Diligence nella Supply Chain: caso studio Fincantieri S.p.A.

La richiesta dei consumatori di prodotti sostenibili, le lotte per il cambiamento climatico e l'importanza che viene data alla sostenibilità dal mondo finanziario hanno fatto sì che la politica intraprendesse iniziative sulle tematiche sostenibili e di conseguenza le imprese hanno adottato azioni in linea con i criteri ESG. Anche se per le aziende intraprendere un percorso sostenibile non sia economicamente conveniente e per raggiungere determinati obiettivi servono sforzi e tempi lunghi, sono consapevoli dei benefici nel medio-lungo termine a livello economico, di reputazione e vantaggio competitivo. Queste iniziative però si concentrano prevalentemente sul primo anello della supply chain e le società che operano in un mercato globale fanno difficoltà a rispettare le differenti norme giuridiche non compatibili negli Stati in cui è presente la propria value chain. Per risolvere questi problemi la della Commissione Europea il 23/02/2022 ha proposto la direttiva sulla Corporate Sustainability Due Diligence, che impone l’obbligo per le imprese di implementare un processo di due diligence in tutta la value chain per prevenire effetti negativi e potenziali sui diritti umani e sull’ambiente. L’obiettivo dell'elaborato è di analizzare la direttiva di due diligence per comprendere quanto le aziende di oggi siano pronte al monitoraggio di un’intera catena del valore. Il caso studio scelto per lo scopo è quello dell’azienda Fincantieri S.p.A. la quale ha intrapreso da qualche anno un percorso di sostenibilità. Attraverso il confronto fra le azioni in atto dell'azienda e la direttiva, dalla trattazione emerge che la sfida più grande che Fincantieri dovrà affrontare sarà la condivisione delle pratiche già in atto nei livelli più profondi della supply chain. L’approvazione della direttiva, incentivando anche indirettamente le aziende ad operare in ottica di sostenibilità, aiuterà a perseguire l'obiettivo di due diligence in un percorso di crescita e miglioramento con i fornitori

Stato dell'arte delle tecniche lean per la gestione della supply chain

L’idea di focalizzare la tesi sulla supply chain ed in particolare sulle tecniche lean per la sua ottimizzazione deriva dal fatto che si tratta di un nuovo modo di ragionare, di un approccio moderno perfettamente adattabile al contesto socio-economico attuale, teso ad accrescere la flessibilità e l’efficienza dell’impresa attraverso un ripensamento dell’intero flusso di creazione del valore. Verranno analizzate le caratteristiche generali di questo modello organizzativo, per poi addentrarsi nella sua applicazione ed infine i vantaggi e gli eventuali svantaggi che le organizzazioni devono affrontare per implementare operativamente le tecniche lean. L’analisi effettuata nella tesi è strutturata come segue: La parte iniziale del primo capitolo definisce il concetto generale di supply chain sottolineando il contesto di riferimento in cui oggi operano le attività produttive. Vengono poi riportati l’accezione e il valore della supply chain management e le sue problematiche annesse di gestione e controllo. Nella seconda parte del capitolo vengono analizzati e descritti i modelli letterari esistenti utili per descrivere, impostare e classificare una supply chain. Il secondo capitolo, dopo una breve esposizione storica che descrive le origini della metodologia lean production, è orientato alla raccolta delle definizioni e alle loro differenti visioni tratte dal mondo della letteratura. Segue una parte più analitica, dove vengono analizzati in maniera dettagliata gli obiettivi, gli strumenti ed i principi che la filosofia lean prevede. Nel terzo capitolo viene approfondita la VSM, uno degli strumenti di principale importanza secondo le logiche della lean manufacturing. Vengono analizzati gli step necessari per una corretta implementazione, illustrando prima la simbologia internazionale necessaria per una sua comprensione e realizzazione e poi definiti gli step da applicare non solo per una semplice realizzazione, ma per l’ottenimento di una value stream map in ottica lean.

Development of a novel heat treatment for high performances L-PBF Ti6Al4V alloy: microstructural and mechanical characterization

This work presents the experimental development of a novel heat treatment for a high performance Laser Powder Bed Fusion Ti6Al4V alloy. Additive manufacturing production processes for titanium alloys are particularly of interest in cutting-edge engineering fields, however, high frequency laser induced thermal cycles generate a brittle as built microstructure. For this reason, heat treatments compliant with near net shape components are needed before their homologation and usage. The experimental campaign focused on the development of a multi-step heat treatment leading to a bilamellar microstructure. In fact, according to literature, such a microstructure should be promising in terms of mechanical properties both under static and cyclic loads. The heat treatment development has asked for the preliminary analyses of samples annealed and aged in laboratory, implementing several cycles, differing for what concerns temperatures, times and cooling rates. Such a characterization has been carried out through optical and electron microscopy analyses, image analyses, hardness and tensile tests. As a result, the most suitable thermal cycle has been selected and performed using industrial equipment on mini bending fatigue samples with different surface conditions. The same tests have been performed on a batch of traditionally treated samples, to provide with a comparison. This master thesis activity has finally led to the definition of a heat treatment resulting into a bilamellar microstructure, promising in terms of fatigue performances with respect to the traditionally treated alloy ones. The industrial implementation of such a heat treatment will require further improvements, particularly for what concerns the post annealing water quench, in order to prevent any surface alteration potentially responsible for the fatigue performances drop. Further development of the research may also include push-pull fatigue tests, crack grow propagation and residual stresses analyses.

Design and management of a supply chain: a joint location-inventory problem under uncertainty (Part A)

In this paper, a joint location-inventory model is proposed that simultaneously optimises strategic supply chain design decisions such as facility location and customer allocation to facilities, and tactical-operational inventory management and production scheduling decisions. All this is analysed in a context of demand uncertainty and supply uncertainty. While demand uncertainty stems from potential fluctuations in customer demands over time, supply-side uncertainty is associated with the risk of “disruption” to which facilities may be subject. The latter is caused by external factors such as natural disasters, strikes, changes of ownership and information technology security incidents. The proposed model is formulated as a non-linear mixed integer programming problem to minimise the expected total cost, which includes four basic cost items: the fixed cost of locating facilities at candidate sites, the cost of transport from facilities to customers, the cost of working inventory, and the cost of safety stock. Next, since the optimisation problem is very complex and the number of evaluable instances is very low, a "matheuristic" solution is presented. This approach has a twofold objective: on the one hand, it considers a larger number of facilities and customers within the network in order to reproduce a supply chain configuration that more closely reflects a real-world context; on the other hand, it serves to generate a starting solution and perform a series of iterations to try to improve it. Thanks to this algorithm, it was possible to obtain a solution characterised by a lower total system cost than that observed for the initial solution. The study concludes with some reflections and the description of possible future insights.