Synthesis in millireactor system and stability of intermediates for the functionalization of imidazole

This Master thesis presents the results obtained in the curricular traineeship, carried out within the laboratories of the Department of Chemistry of the University of Bergen, during the Erasmus period, and within the Department of Industrial Chemistry of the University of Bologna. The project followed in Bergen concerned the synthesis of key intermediates used for the functionalization of the backbone of imidazole, using N,N'- diiodo-5,5-dimethylhydantoin (“DIH”) as an iodinating agent, and employing an innovative kind of chemical reactor: the “Multijet Oscillating Disc Millireactor” (MJOD Reactor). Afterwards, the work performed in Bologna consisted in verifying the stability in solution of the above mentioned N,N'-diiodo-5,5-dimethylhydantoin utilising spectrophotometric techniques and High Performance Liquid Chromatography analyses (HPLC).

Stability of the tunnel face reinforced by bolts under seepage flow conditions

Il presente lavoro tratta la stabilità del fronte di scavo, rinforzato con barre di consolidamento ed interessato da drenaggi in avanzamento, di gallerie sotto falda in rocce tenere o terreni. Tale studio è stato sviluppato dal progetto di Tesi attraverso l’analisi all’equilibrio limite che approssima il fronte di scavo con un rettangolo e considera un meccanismo di rottura composto da un cuneo, a tergo del fronte, caricato da un prisma. Il metodo descritto consente di tenere conto dell’effetto stabilizzante delle barre, mediante una distribuzione della pressione di supporto non uniforme. Nel caso di gallerie sotto falda, lo stesso metodo permette inoltre di considerare l’effetto destabilizzante dei gradienti idraulici. Sono state ricavate soluzioni analitiche per la valutazione della stabilità, ed implementate successivamente nel software di analisi numerica MATLAB. Dalle analisi condotte è emerso che il numero minimo di barre per garantire la stabilità del fronte di scavo è in molti casi elevato e risulta impossibile da porre in opera in terreni scarsamente coesivi o in gallerie sotto elevati battenti d’acqua. Per risolvere questa situazione si può prevedere l’inserimento di drenaggi in avanzamento, con lo scopo di diminuire i gradienti idraulici nei pressi del fronte della galleria. Il modello che descrive il nuovo andamento dei carichi idraulici, considerando la presenza di dreni, è stato realizzato con il software commerciale agli elementi finiti COMSOL. Una volta determinati gli andamenti dei carichi idraulici, sono stati condotti studi parametrici sull’effetto dei dreni combinato con gli elementi di rinforzo. Dopo tali analisi sono stati ricavati nomogrammi adimensionali che tengano conto della presenza contemporanea delle barre e dei dreni. Tali diagrammi costituiscono uno strumento utile e valido per la progettazione del rinforzo del fronte di scavo. Infine sono stati realizzati confronti fra casi di studio reali e risultati ottenuti dal modello.

Investigation of spectral stability of X-ray tubes by simulations and experimental spectrum measurements

L'obiettivo di questo lavoro è quello di analizzare la stabilità di uno spettro raggi X emesso da un tubo usurato per analisi cardiovascolari, in modo da verificare il suo comportamento. Successivamente questo tipo di analisi sarà effettuata su tubi CT. Per raggiungere questo scopo è stato assemblato un particolare set-up con un rivelatore al germanio criogenico in modo da avere la miglior risoluzione energetica possibile ed alcuni particolari collimatori così da ridurre il flusso fotonico per evitare effetti di pile-up. Il set-up è stato costruito in modo da avere il miglior allineamento possibile nel modo più veloce possibile, e con l'obiettivo di rendere l'intero sistema portabile. Il tubo usato è un SRM Philips tube per analisi cardiovascolari; questa scelta è stata fatta in modo da ridurre al minimo i fattori esterni (ottica elettromagnetica, emettitori) e concentrare l'attenzione solo sugli effetti, causati dalle varie esposizioni, sull'anodo (roughness e bending) e sul comportamento di essi durante il surriscaldamento e successivo raffreddamento del tubo. I risultati mostrano come durante un'esposizione alcuni fattori di usura del tubo possono influire in maniera sostanziale sullo spettro ottenuto e quindi alterare il risultato. Successivamente, nell'elaborato, mediante il software Philips di ricostruzione e simulazione dello spettro si è cercato di riprodurre, variando alcuni parametri, la differenza riscontrata sperimentalmente in modo da poter simulare l'instabilità e correggere i fattori che la causano. I risultati sono interessanti non solo per questo esperimento ma anche in ottica futura, per lo sviluppo di applicazioni come la spectral CT. Il passo successivo sarà quello di spostare l'attenzione su un CT tube e verificare se l'instabilità riscontrata in questo lavoro è persiste anche in una analisi più complessa come quella CT.

Stability of Contour Augmentation and Esthetic Outcomes of Implant Supported Single Crowns in the Esthetic Zone. 3-Year Results of a Prospective Study With Early Implant Placement Post Extraction

Early implant placement is one of the treatment options after tooth extraction. Implant surgery is performed after a healing period of 4 to 8 weeks and combined with a simultaneous contour augmentation using the guided bone regeneration technique to rebuild stable esthetic facial hard- and soft-tissue contours.

The use of weightbearing radiographs to assess the stability of supination-external rotation fractures of the ankle

Isolated lateral malleolar fractures usually result from a supination-external rotation (SER) injury and may include a deltoid ligament rupture. The necessity of operative treatment is based on the recognition of a relevant medial soft-tissue disruption. Currently used tests to assess ankle stability include manual stress radiographs and gravity stress radiographs, but seem to overestimate the need for fracture fixation.

Long-term stability of surgical bone regenerative procedures of peri-implantitis lesions in a prospective case-control study over 3 years

Objectives: To evaluate the extent of bone fill over 3 years following the surgical treatment of peri-implantitis with bone grafting with or without a membrane. Material and Methods: In a non-submerged wound-healing mode, 15 subjects with 27 implants were treated with a bone substitute (Algipore®) alone and 17 subjects with 29 implants were treated with the bone substitute and a resorbable membrane (Osseoquest®). Implants with radiographic bone loss ≥1.8 mm following the first year in function and with bleeding and/or pus on probing were included. Following surgery, subjects were given systemic antibiotics (10 days) and rinsed with chlorhexidine. After initial healing, the subjects were enrolled in a strict maintenance programme. Results: Statistical analysis failed to demonstrate changes in bone fill between 1 and 3 years both between and within procedure groups. The mean defect fill at 3 years was 1.3 ± (SD) 1.3 mm if treated with the bone substitute alone and 1.6 ± (SD) 1.2 mm if treated with an adjunct resorbable membrane, (p=0.40). The plaque index decreased from approximately 40–10%, remaining stable during the following 2 years. Conclusion: Defect fill using a bone substitute with or without a membrane technique in the treatment of peri-implantitis can be maintained over 3 years.

I know what I like: Stability of aesthetic preference in Alzheimer's disease

Two studies explored the stability of art preference in patients with Alzheimer’s disease and age-matched control participants. Preferences for three different styles of paintings, displayed on art postcards, were examined over two sessions. Preference for specific paintings differed among individuals but AD and non-AD groups maintained about the same stability in terms of preference judgments across two weeks, even though the AD patients did not have explicit memory for the paintings. We conclude that aesthetic responses can be preserved in the face of cognitive decline. This should encourage caregivers and family to engage in arts appreciation activities with patients, and reinforces the validity of a preference response as a dependent measure in testing paradigms.

Stability of Art Preference in Frontotemporal Dementia

We examined aesthetic preference for reproductions of paintings among frontotemporal dementia (FTD) patients, in two sessions separated by 2 weeks. The artworks were in three different styles: representational, quasirepresentational, and abstract. Stability of preference for the paintings was equivalent to that shown by a matched group of Alzheimer's disease patients and a group of healthy controls drawn from an earlier study. We expected that preference for representational art would be affected by disruptions in language processes in the FTD group. However, this was not the case and the FTD patients, despite severe language processing deficits, performed similarly across all three art styles. These data show that FTD patients maintain a sense of aesthetic appraisal despite cognitive impairment and should be amenable to therapies and enrichment activities involving art.

Clinical stability of slipped capital femoral epiphysis does not correlate with intraoperative stability

The most important objective of clinical classifications of slipped capital femoral epiphysis (SCFE) is to identify hips associated with a high risk of avascular necrosis (AVN)--so-called unstable or acute slips; however, closed surgery makes confirmation of physeal stability difficult. Performing the capital realignment procedure in SCFE treatment we observed that clinical estimation of physeal stability did not always correlate with intraoperative findings at open surgery. This motivated us to perform a systematic comparison of the clinical classification systems with the intraoperative observations.

Characterization of Molecular Determinants of the Conformational Stability of Macrophage Migration Inhibitory Factor: Leucine 46 Hydrophobic Pocket

Macrophage Migration Inhibitory Factor (MIF) is a key mediator of inflammatory responses and innate immunity and has been implicated in the pathogenesis of several inflammatory and autoimmune diseases. The oligomerization of MIF, more specifically trimer formation, is essential for its keto-enol tautomerase activity and probably mediates several of its interactions and biological activities, including its binding to its receptor CD74 and activation of certain signaling pathways. Therefore, understanding the molecular factors governing the oligomerization of MIF and the role of quaternary structure in modulating its structural stability and multifunctional properties is crucial for understanding the function of MIF in health and disease. Herein, we describe highly conserved intersubunit interactions involving the hydrophobic packing of the side chain of Leu46 onto the β-strand β3 of one monomer within a hydrophobic pocket from the adjacent monomer constituted by residues Arg11, Val14, Phe18, Leu19, Val39, His40, Val41, Val42, and Pro43. To elucidate the structural significance of these intersubunit interactions and their relative contribution to MIF’s trimerization, structural stability and catalytic activity, we generated three point mutations where Leu46 was replaced by glycine (L46G), alanine (L46A) and phenylalanine (L46F), and their structural properties, stability, oligomerization state, and catalytic activity were characterized using a battery of biophysical methods and X-ray crystallography. Our findings provide new insights into the role of the Leu46 hydrophobic pocket in stabilizing the conformational state of MIF in solution. Disrupting the Leu46 hydrophobic interaction perturbs the secondary and tertiary structure of the protein but has no effect on its oligomerization state.