Tuzla City (BiH): an example of geohazard induced by salt extraction

Salt deposits characterize the subsurface of Tuzla (BiH) and made it famous since the ancient times. Archeological discoveries demonstrate the presence of a Neolithic pile-dwelling settlement related to the existence of saltwater springs that contributed to make the most of the area a swampy ground. Since the Roman times, the town is reported as “the City of Salt deposits and Springs”; "tuz" is the Turkish word for salt, as the Ottomans renamed the settlement in the 15th century following their conquest of the medieval Bosnia (Donia and Fine, 1994). Natural brine springs were located everywhere and salt has been evaporated by means of hot charcoals since pre-Roman times. The ancient use of salt was just a small exploitation compared to the massive salt production carried out during the 20th century by means of classical mine methodologies and especially wild brine pumping. In the past salt extraction was practised tapping natural brine springs, while the modern technique consists in about 100 boreholes with pumps tapped to the natural underground brine runs, at an average depth of 400-500 m. The mining operation changed the hydrogeological conditions enabling the downward flow of fresh water causing additional salt dissolution. This process induced severe ground subsidence during the last 60 years reaching up to 10 meters of sinking in the most affected area. Stress and strain of the overlying rocks induced the formation of numerous fractures over a conspicuous area (3 Km2). Consequently serious damages occurred to buildings and infrastructures such as water supply system, sewage networks and power lines. Downtown urban life was compromised by the destruction of more than 2000 buildings that collapsed or needed to be demolished causing the resettlement of about 15000 inhabitants (Tatić, 1979). Recently salt extraction activities have been strongly reduced, but the underground water system is returning to his natural conditions, threatening the flooding of the most collapsed area. During the last 60 years local government developed a monitoring system of the phenomenon, collecting several data about geodetic measurements, amount of brine pumped, piezometry, lithostratigraphy, extension of the salt body and geotechnical parameters. A database was created within a scientific cooperation between the municipality of Tuzla and the city of Rotterdam (D.O.O. Mining Institute Tuzla, 2000). The scientific investigation presented in this dissertation has been financially supported by a cooperation project between the Municipality of Tuzla, The University of Bologna (CIRSA) and the Province of Ravenna. The University of Tuzla (RGGF) gave an important scientific support in particular about the geological and hydrogeological features. Subsidence damage resulting from evaporite dissolution generates substantial losses throughout the world, but the causes are only well understood in a few areas (Gutierrez et al., 2008). The subject of this study is the collapsing phenomenon occurring in Tuzla area with the aim to identify and quantify the several factors involved in the system and their correlations. Tuzla subsidence phenomenon can be defined as geohazard, which represents the consequence of an adverse combination of geological processes and ground conditions precipitated by human activity with the potential to cause harm (Rosenbaum and Culshaw, 2003). Where an hazard induces a risk to a vulnerable element, a risk management process is required. The single factors involved in the subsidence of Tuzla can be considered as hazards. The final objective of this dissertation represents a preliminary risk assessment procedure and guidelines, developed in order to quantify the buildings vulnerability in relation to the overall geohazard that affect the town. The historical available database, never fully processed, have been analyzed by means of geographic information systems and mathematical interpolators (PART I). Modern geomatic applications have been implemented to deeply investigate the most relevant hazards (PART II). In order to monitor and quantify the actual subsidence rates, geodetic GPS technologies have been implemented and 4 survey campaigns have been carried out once a year. Subsidence related fractures system has been identified by means of field surveys and mathematical interpretations of the sinking surface, called curvature analysis. The comparison of mapped and predicted fractures leaded to a better comprehension of the problem. Results confirmed the reliability of fractures identification using curvature analysis applied to sinking data instead of topographic or seismic data. Urban changes evolution has been reconstructed analyzing topographic maps and satellite imageries, identifying the most damaged areas. This part of the investigation was very important for the quantification of buildings vulnerability.

Organocatalytic asymmetric mannich-type reactions: an easy approach to optically active amine derivatives

The topics I came across during the period I spent as a Ph.D. student are mainly two. The first concerns new organocatalytic protocols for Mannich-type reactions mediated by Cinchona alkaloids derivatives (Scheme I, left); the second topic, instead, regards the study of a new approach towards the enantioselective total synthesis of Aspirochlorine, a potent gliotoxin that recent studies indicate as a highly selective and active agent against fungi (Scheme I, right). At the beginning of 2005 I had the chance to join the group of Prof. Alfredo Ricci at the Department of Organic Chemistry of the University of Bologna, starting my PhD studies. During the first period I started to study a new homogeneous organocatalytic aza-Henry reaction by means of Cinchona alkaloid derivatives as chiral base catalysts with good results. Soon after we introduced a new protocol which allowed the in situ synthesis of N-carbamoyl imines, scarcely stable, moisture sensitive compounds. For this purpose we used α-amido sulfones, bench stable white crystalline solids, as imine precursors (Scheme II). In particular we were able to obtain the aza-Henry adducts, by using chiral phase transfer catalysis, with a broad range of substituents as R-group and excellent results, unprecedented for Mannich-type transformations (Scheme II). With the optimised protocol in hand we have extended the methodology to the other Mannich-type reactions. We applied the new method to the Mannich, Strecker and Pudovik (hydrophosphonylation of imines) reactions with very good results in terms of enantioselections and yields, broadening the usefulness of this novel protocol. The Mannich reaction was certainly the most extensively studied work in this thesis (Scheme III). Initially we developed the reaction with α-amido sulfones as imine precursors and non-commercially available malonates with excellent results in terms of yields and enantioselections.3 In this particular case we recorded 1 mol% of catalyst loading, very low for organocatalytic processes. Then we thought to develop a new Mannich reaction by using simpler malonates, such as dimethyl malonate.4 With new optimised condition the reaction provided slightly lower enantioselections than the previous protocol, but the Mannich adducts were very versatile for the obtainment of β3-amino acids. Furthermore we performed the first addition of cyclic β-ketoester to α-amido sulfones obtaining the corresponding products in good yield with high level of diastereomeric and enantiomeric excess (Scheme III). Further studies were done about the Strecker reaction mediated by Cinchona alkaloid phase-transfer quaternary ammonium salt derivatives, using acetone cyanohydrin, a relatively harmless cyanide source (Scheme IV). The reaction proceeded very well providing the corresponding α-amino nitriles in good yields and enantiomeric excesses. Finally, we developed two new complementary methodologies for the hydrophosphonylation of imines (Scheme V). As a result of the low stability of the products derived from aromatic imines, we performed the reactions in mild homogeneous basic condition by using quinine as a chiral base catalyst giving the α-aryl-α-amido phosphonic acid esters as products (Scheme V, top).6 On the other hand, we performed the addition of dialkyl phosphite to aliphatic imines by using chiral Cinchona alkaloid phase transfer quaternary ammonium salt derivatives using our methodology based on α-amido sulfones (Scheme V, bottom). The results were good for both procedures covering a broad range of α-amino phosphonic acid ester. During the second year Ph.D. studies, I spent six months in the group of Prof. Steven V. Ley, at the Department of Chemistry of the University of Cambridge, in United Kingdom. During this fruitful period I have been involved in a project concerning the enantioselective synthesis of Aspirochlorine. We provided a new route for the synthesis of a key intermediate, reducing the number of steps and increasing the overall yield. Then we introduced a new enantioselective spirocyclisation for the synthesis of a chiral building block for the completion of the synthesis (Scheme VI).

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Analysis of ion channel stochastic signals for biosensing

In biological world, life of cells is guaranteed by their ability to sense and to respond to a large variety of internal and external stimuli. In particular, excitable cells, like muscle or nerve cells, produce quick depolarizations in response to electrical, mechanical or chemical stimuli: this means that they can change their internal potential through a quick exchange of ions between cytoplasm and the external environment. This can be done thanks to the presence of ion channels, proteins that span the lipid bilayer and act like switches, allowing ionic current to flow opening and shutting in a stochastic way. For a particular class of ion channels, ligand-gated ion channels, the gating processes is strongly influenced by binding between receptive sites located on the channel surface and specific target molecules. These channels, inserted in biomimetic membranes and in presence of a proper electronic system for acquiring and elaborating the electrical signal, could give us the possibility of detecting and quantifying concentrations of specific molecules in complex mixtures from ionic currents across the membrane; in this thesis work, this possibility is investigated. In particular, it reports a description of experiments focused on the creation and the characterization of artificial lipid membranes, the reconstitution of ion channels and the analysis of their electrical and statistical properties. Moreover, after a chapter about the basis of the modelling of the kinetic behaviour of ligand gated ion channels, a possible approach for the estimation of the target molecule concentration, based on a statistical analysis of the ion channel open probability, is proposed. The fifth chapter contains a description of the kinetic characterisation of a ligand gated ion channel: the homomeric α2 isoform of the glycine receptor. It involved both experimental acquisitions and signal analysis. The last chapter represents the conclusions of this thesis, with some remark on the effective performance that may be achieved using ligand gated ion channels as sensing elements.

Un percorso fra natura e storia. Il museo della citta' di Cesena lungo il fiume Savio

“Il museo sta cambiando. In passato, era un luogo di certezze assolute, fonte di definizioni, di valori e di dottrina in materia d'arte, a tutto campo; era il luogo in cui non ci si ponevano interrogativi ma si davano autorevoli risposte.[...]“ 1 Il collezionismo d'arte comincia con il Rinascimento italiano, che sviluppa un particolare senso della storia, un entusiasmo per i prodotti dell'Antichità classica e per tutti i generi dell'arte contemporanea, pensati per la residenza privata, e in realtà, per esse fabbricati: dipinti di soggetto mitologico, quadri di artisti fiamminghi, piccoli bronzi e, al nord arte grafica. Il collezionismo in senso stretto fu agli inizi del secolo connesso solo con le antichità. Verso la fine del Cinquecento, vanno manifestandosi parecchie innovazioni. Per la prima volta compare la parola museo, che era già stata adottata in Alessandria durante il periodo Ellenistico per designare tutto l'ambito degli edifici per la cultura in cui era compresa la biblioteca. Inizialmente tutte le collezioni erano private, ma potevano essere visitate dalle élite sociali. L‟istituzione del museo che noi oggi conosciamo, nasce dall‟ Europa illuminista del XVIII secolo: infatti in questo periodo fu deliberatamente progettato uno spazio architettonico appropriato che desse forma universalmente riconoscibile all‟idea di museo. Poniamo gli esempi del Museo di Villa Albani nel 1746 e il Museo Pio Clementino in Vaticano nel 1775, che per primi si pongono il problema della progettazione architettonica, dell‟allestimento e ordinamento adeguati a un museo aperto al pubblico. Mentre per Villa Albani si trattava pur sempre di una raccolta privata visitabile, il museo voluto dai papi Clemente XIV e Pio VI per le collezioni archeologiche era già pensato come un‟istituzione di interesse pubblico. Gli ultimi tre secoli del secondo millennio hanno visto la crescita dell‟istituzione del museo, diventata esponenziale negli ultimi decenni del XX secolo. I tempi hanno coinciso con la nascita, l‟affermazione rivoluzionaria, il trionfo e il consolidamento della cultura nell‟età della borghesia. 2 “Mentre prima il museo non era che un luogo pieno di oggetti, oggi è diventato un luogo pieno di idee, che vengono suggerite dalle indicazioni e dalle descrizioni accompagnanti gli oggetti esposti, dato che il museo è come un libro aperto che si offre allo studioso e a chi desidera formarsi una coltura.[...]3 1 Karsten Schubert, Museo. Storia di un'idea - dalla Rivoluzione francese ad oggi, il Saggiatore, Milano 2004, p.17. 2 Alessandra Mottola Molfino, Il libro dei musei, Umberto Alemandi & C., Torino 1991, pp. 11-22 3 Daniele Donghi, Manuale dell'architetto Volume II, Unione Tipografico Editrice Torinese, Torino 1935, p. 11. 8 Un museo non è definito solo in base all'importanza e alla qualità delle sue raccolte, ma soprattutto da come vengono recepite da chi le esamina, sia per motivi di studio che per interesse personale. Per questo motivo si deve mettere in grado le diverse categorie di fruitori, di accedere al museo con il minor spreco di tempo possibile e con il maggior profitto. L'effetto che si vuole ottenere deriva sia dal metodo di esposizione degli oggetti, sia da una buona soluzione tecnica relativa alle dimensioni, alla forma, alla distribuzione, riscaldamento e ventilazione dei locali, all'illuminazione degli oggetti e ai mezzi di loro conservazione e sicurezza. Il museo moderno dovrà coniugare al suo interno museografia e museologia. Dove“[...]per museografia si intende l'insieme delle azioni progettuali, scientifiche e tecniche, tendenti alla sistemazione organizzativa del museo (distributiva, impiantistica, tecnica, architettonica, allestitiva, informatica); appartiene in genere all'opera dell'architetto, con la collaborazione di strutturisti, impiantisti e informatici. Al contrario per museologia si intende l'insieme delle azioni di ricerca storica, filologica, di comparazione critica che presiede all'ordinamento dell'esposizione delle opere; generalmente appartiene allo storico dell'arte, allo storico della scienza, all'archeologo, all'antropologo [...].”4 Confrontando progetti museografici e museali dei primi musei con esempi moderni e contemporanei, si intendono ricavare i caratteri fondamentali che permettano di presentare un progetto per museo coerente all'area di studio, e che riesca a rivelare la vera natura degli oggetti che andrà a ospitare attraverso uno studio specifico dei percorsi e degli allestimenti.

Progetto di un museo marittimo sul canale Candiano a Ravenna

L’intenzione di questo progetto, all’interno di un’area complessa come la Darsena di città, è quella di comporre un nuovo museo per la città, un museo del mare. Perchè il museo del mare? A Ravenna esistono tanti musei che riguardano la cultura, l’arte, la scienza, l’archeologia ecc., ma tra tutti questi musei di funzione varia non c’è nessun’altro legato a quell’elemento fonte su cui si è basata tutta la storia e essenza di Ravenna – l’acqua. Per questo motivo, il nuovo progetto sulla Darsena e prima di tutto sul Canale Candiano vuole costruire un nuovo complesso per la città che comprende tutto quello che insieme all’acqua è diventato un patrimonio da conservare e mostrare.