Stereochemical Aspects of Sulfoxides and Metal Sulfoxide Complexes

Structural parameters of free and metal coordinated sulfoxides are reviewed and updated average values are derived. For uncoordinated sulfoxides, the average S−O bond distance is 1.4918(9) Å. This value is lengthened to 1.528(1) Å upon O-coordination to metal ions, while it is reduced to 1.4731(6) Å upon S-coordination. The sulfoxide bonding and bridging modes are discussed together with some stereochemical features

Analysis of J/Psi production with the CMS detector at the Large Hadron Collider

The J/psi particle is a vector meson with a mass of 3096.916±0.011 MeV. It has been observed in 1974 by two experiments at Stanford and Brookhaven, and is the first bound state of a charm quark and an anticharm quark ever discovered in the history of particle physics. Differently from lighter quarks, the charm quark is characterized by a rest mass significantly greater than the typical energy scale of Quantum Chromo Dynamics processes, which take place during the binding of the meson. This greater mass results in its constituent quarks being relatively "slow" inside it, justifying a non-relativistic description of its production process. The J/psi, along with other charm-anticharm bound states, represents an important laboratory where the theoretical models of the strong interaction are verified. Heavy mesons are produced in copious amounts in high energy proton-proton collisions, and the recent beginning of experiments at the CERN Large Hadron Collider has given an opportunity to study the behavior of J/psi production at a center-of-mass energy of 7 TeV with the CMS detector. This detector has been designed as a general-purpose one and is capable of good performance in this kinds of studies, especially in the J/psi to mu+ mu- decay channel. Indeed, the past 20 years have seen a revival of interest in the study of the production process of the J/psi. A measurement performed by the CDF experiment in 1992-1993 at the Tevatron p-pbar collider found the production cross-section to be larger than the theoretical prediction by a factor of 50. Consequently, the model in use at the time - the Color Singlet Model - had to be abandoned in favor of a Non-Relativistic QCD description called the Color Octet Model. Recently, also this model has been put into discussion, as the predictions it makes on the polarization of the J/psi seem not to match experimental data by the E866, HERA-B and CDF II experiments, and even more puzzling is the fact that the E866 and HERA-B measurement are inconsistent. A possible explanation of these inconsistencies may be hidden in the different experimental conditions under which these experiments took place (mainly, the detector acceptances), and the fact that the measurements were performed in different frames of reference. Once identified the importance of the cross-section and polarization measurements, I present the cross-section measurement performed on data taken in 2010 with the CMS detector and present the ongoing effort in measuring the J/psi polarization by the CMS collaboration - in which I have worked as a student for the purpose of this thesis. In my thesis I introduce a frame-invariant approach which should overcome these elements and provide a clear picture of the behavior of the polarization (longitudinal, transverse or a combination of these states) as a function of transverse momentum. The measurement requires a series of introductory steps aimed at understanding all aspects of detector response to muons, among them is the calculation of the detector acceptance for the muon pairs with Monte Carlo simulations, the study based on real data of the tracking efficiency, that of muon identification efficiency and that of trigger efficiency, the latter being one of my responsibilities during my work. The efficiency study has been performed by the use of the "Tag and Probe" method for resonances decaying to dimuons, where a muon of the pair is required to pass a series of very tight cuts. The pairs surviving this extreme skimming have the other muon analyzed, in order to perform a statistical measurement on the relevant variable

Finite orbits of the action of the pure braid group on the character variety of the Riemann sphere with five boundary components

In this thesis, we classify finite orbits of the action of the pure braid group over a certain large open subset of the SL(2,C) character variety of the Riemann sphere with five boundary components, i.e. Σ5. This problem arises in the context of classifying algebraic solutions of the Garnier system G2, that is the two variable analogue of the famous sixth Painleve equation PVI. The structure of the analytic continuation of these solutions is described in terms of the action of the pure braid group on the fundamental group of Σ5. To deal with this problem, we introduce a system of co-adjoint coordinates on a big open subset of the SL(2,C) character variety of Σ5. Our classifica- tion method is based on the definition of four restrictions of the action of the pure braid group such that they act on some of the co-adjoint coordi- nates of Σ5 as the pure braid group acts on the co-adjoint coordinates of the character variety of the Riemann sphere with four boundary components, i.e. Σ4, for which the classification of all finite orbits is known. In order to avoid redundant elements in our final list, a group of symmetries G of the large open subset is introduced and the final classification is achieved modulo the action of G. We present a final list of 54 finite orbits

Comparación preliminar entre el sondeo de Pocala y una cueva innominada en Borgo Grotta Gigante, Karst de Trieste

[Abstract] In 2000 five boring were performed in a unroofle cave at Borgo Grotta gigante, the third in particular is correlable with the boring outside Pocala Cave. The first result has been obtained by observing the absence of collapsed rocks, in particular in the unroofle cave of Borgo Grotta Gigante. Clearly limestones have dissolve

Potential Applications of High Pressure Homogenization in Winemaking: A Review

High pressure homogenization (HPH) is an emerging technology with several possible applications in food sector, such as nanoemulsion preparation, microbial and enzymatic inactivation, cell disruption for the extraction of intracellular components, as well as modification of food biopolymer structure to steer their functionalities. All these effects are attributable to the intense mechanical stresses, such as cavitation and shear forces, suffered by the product during the passage through the homogenization valve. The exploitation of the disruptive forces delivered during HPH was recently proposed also for winemaking applications. In this review, after a general description of HPH and its main applications in food processing, the survey will be extended to the use of this technology for the production of wine and fermented beverages, particularly focusing on the effects of HPH on the inactivation of wine microorganisms and the induction of yeast autolysis. Further enological applications of HPH technology, such as its use for the production of inactive dry yeast preparations, will be also discusse

Debris Flow Phenomena: A Short Overview?

Summary: On the day of 29 August 2003 in the extreme northern part of Italy, the Friuli-Venezia Giulia region was invested by a violent and intense rainfall that caused several instability phenomena. Along the sides of the Val Canale valley were mobilized over a thousand of landslides, most of whom were of first generation. The rainfall started at midnight, firstly affecting the areas belonging to the upper sector of the mountains around Cucco, Malborghetto and Ugovizza, then it gradually moved downwards with increasing intensity (Calligaris et al., 2010). A total value of 293 mm rainfall was recorded by the Pontebba rain gauge from 02h00 to 18h00. Around 18h30, some impressive waves plunged with unexpected violence, power and noise, an avalanche of water, big rocks and trunks crashed against courtyards, houses and went inside windows (Russo, 2003). This event caused the death of two people, 300 lost their homes, 260 buildings were damaged and substantial damages occurred to infrastructures that remained out of action for several days. The event was so extreme and particular that the return time has a considerable variation in its value depending on the period: between 1 and 24 h, the time of delivery is between 50 and 100 years; for 12 h it is between 200 and 500 years, while, for a period from 3 to 6 h, return period varies between 500 and 1000 years (Borga et al., 2007; Calligaris et al., 2010). This area has been chosen as test site due to the important amount of data availability. Many studies have been realized to characterize the debris flow occurred. The Geological Survey of FVG Region had the necessity to better understand the occurred phenomena in order to prevent future disasters and to proceed to a better and more coscientious territorial planning. In this context, many approaches were used. Back analysis simulation thought commercial and innovative software permitted to delimit the flooded areas. The debris flow is often considered to be a mixture of viscous slurry, consisting of finer grain sizes and water, and coarse particles (Scotto di Santolo, 2008). The volume and the composition of the mixture are the main factors that contribute to determine the hazards associated with such phenomena, since they govern the mobility and impact energy of the debris (Iverson, 1997; Jakob, 2005). During the last years, several simulation models and approaches have been implemented (Cesco Bolla, 2008; Pirulli, 2005; Rickenmann, 1999) and created to reconstruct a debris-flow phenomena, but a believable scenario can be obtained only by resorting to real parameters that are suitable to characterise the involved material (Sosio et al., 2006). Thus, it is necessary to calibrate those computational codes through back-analysis simulations and laboratory analysis (Tecca et al., 2006). The input variable needed by the codes are so aleatory that is a strongly felt need to isolate each one of them and to go deep inside their meaning. Rheological parameters of viscous debris flows are one of these variables; they are influenced by a great amount of factors and are therefore extremely difficult to estimate. Viscosity and yield stress are the one that define the debris flow behaviour. For these reasons laboratory rheometer analysis have been realized in order to better characterize them, to apply the obtained results at the available codes and to proceed to new outlines of the invested areas

Oil Structuring for Improving Healthy and Sustainable Diets: The Case Study of Extra Virgin Olive Oil Oleogelation

The aim of this PhD research project is to develop novel and sustainable strategies to structure liquid oils into pseudoplastic materials, called oleogels, to be used as saturated fat substitutes or as functional components able to modulate lipolysis during human digestion as well as deliver bioactive lipophilic molecules. In this context, the use of extra virgin olive oil (EVOO) as a target oil to be gelled would be particularly interesting due to its well- recognized health-promoting capacity. In this case study, EVOO-based oleogels were developed by using different gelation strategies. The oleogels, after structural characterization, were in vitro digested to study the impact of oil structure on the free fatty acids (FFA) release and polyphenols’ bioaccessibility. 1. Introduction In accordance with the PhD thesis project previously described (Ciuffarin, 2021), this poster reports the main results of the following activities: (A1) Study of strategies for oil structuring (e.g., methods and selection of gelators). (A3) Evaluation of the effect of oleogelation on the gastrointestinal behavior of oleogels by determining the bioaccessibility of selected bioactive molecules (e.g., polyphenols) as well as the lipolysis degree by using in vitro digestion methodologies. 2. Materials and Methods Oleogels were obtained by adding 10 % (w/w) of saturated monoglycerides (MG), rice bran waxes (RW), sunflower waxes (SW), and β-sitosterol/γ-oryzanol mixture (PS) in EVOO heated at temperatures higher than the melting temperatures of the different gelators. Additionally, a whey protein-based oleogel (WP) was prepared by mixing EVOO with a WP aerogel prepared following the methodology of Plazzotta et al. (2020). The final oil content in WP-based oleogels was 80% (w/w). Oleogels were characterized for their structure using a texture analyzer (35 mm-diameter cylindrical probe for 5 mm of distance at a crosshead speed of 1.5 mm/s, TA. XT Plus, Stable Micro Systems Ltd, Godalming, UK) and an accelerated release test by centrifuging samples (10000g for 15 min, Mikro 120, Hettich Zentrifugen, Andreas Hettich GmbH and Co, Tuttlingen, Germany). Unstructured EVOO and oleogels were then subjected to in vitro digestion according to the protocol proposed by Brodkorb et al. (2019). The FFAs released during digestion were assessed by titration (pH-stat). The bioaccessibility of tyrosol (T) and hydroxytyrosol (HT) was evaluated as the percentage ratio between the concentration of these components included in the micellar phase after intestinal in vitro digestion and their concentration in the undigested sample. The polyphenols were determined by HPLC. 3. Results and Discussion 3.1 Oleogel physical properties Table 1 shows the oil retention capacity and firmness of the considered oleogels. All the samples presented a very high oil retention capacity upon centrifugation (<99%) despite the different firmness. The MG-based oleogel was the weakest gel, followed by WP, RW, SW, and PS. These mechanical properties can be associated with the different natures of the networks structuring EVOO. In agreement with the literature, MG, RW, and SW formed a crystalline network (da Pieve et al., 2010; Doan et al., 2015), PS generated a fibrillar structure (Scharfe et al., 2019) and protein aerogels absorbed oil in the protein porous structure (Plazzotta et al., 2021). 3.2 In-vitro digestion: FFA release and bioaccessibility Figure 1 shows the FFA release as a function of the digestion time of structured into oleogels and unstructured EVOO. The typical curve of lipid hydrolysis was obtained. The unstructured oil presented FFA release % of about 68%, followed by PS, SW, RW, and MG with 59.1, 50.8, 50.7, and 42.8% respectively. A different behavior was acquired for WP- based oleogels showing the complete digestion of the oil. These results clearly show that the extent of lipid lipolysis was significantly affected by oil structure. In the case of liposoluble gelators (i.e., MG, RW, SW, PS), it can be inferred that the lipase activity was hindered by the presence of a structuring network behaving like a physical barrier to the access of the enzyme to the substrate sites. On the contrary, WP probably completely dissolved in the gastrointestinal environment thus favouring the emulsification of the oil and thus the lipase activity. In summary, the results demonstrated that the digestibility of the oil can be steered by selecting the proper oleogelator. In the next part of the study, the bioaccessibility of the major EVOO polyphenols (i.e., tyrosol and hydroxytyrosol) was assessed. Despite the higher content of hydroxytyrosol (HT) in EVOO than tyrosol (T) (HT: 248 mg/kg, T: 96 mg/kg), the bioaccessibility of T was significantly higher than that of HT. This result can be explained by considering the different susceptibility to oxidation of the two molecules during digestion (Alberdi-Cedeño et al., 2020). Moreover, differences were recorded among oleogels. Unstructured oil and WP presented the higher T bioaccessibility values, followed by SW, MG and RW, and PS. Since it is impossible to observe a direct effect of gel strength on polyphenol bioaccessibility, it can be speculated a possible interaction between the polyphenols and oleogel network structures. In fact, as well-known, polyphenols are surface-active molecules with the potentiality to interact with other food components. In conclusion, the results reported in the present study confirm that oleogelation could be a profitable strategy to modulate lipid digestion while delivering bioactive molecules. 4. References Alberdi-Cedeño, J., Ibargoitia, M. L., & Guillén, M. D. (2020). Study of the in vitro digestion of olive oil enriched or not with antioxidant phenolic compounds. Relationships between bioaccessibility of main components of different oils and their composition. Antioxidants, 9(6). Brodkorb, A., Egger, L., Alminger, M., Alvito, P., Assunção, R., Ballance, S., Bohn, T., Bourlieu-Lacanal, C., Boutrou, R., Carrière, F., Clemente, A., Corredig, M., Dupont, D., Dufour, C., Edwards, C., Golding, M., Karakaya, S., Kirkhus, B., le Feunteun, S., ... Recio, I. (2019). INFOGEST static in vitro simulation of gastrointestinal food digestion. Nat. Protoc., 14(4), 991–1014. da Pieve, S., Calligaris, S., Co, E., Nicoli, M. C., & Marangoni, A. G. (2010). Shear Nanostructuring of monoglyceride organogels. Food Biophys., 5(3), 211–217. Doan, C. D., van de Walle, D., Dewettinck, K., & Patel, A. R. (2015). Evaluating the oil-gelling properties of natural waxes in rice bran oil: Rheological, thermal, and microstructural study. JAOCS,92(6). Plazzotta, S., Calligaris, S., & Manzocco, L. (2020). Structural characterization of oleogels from whey protein aerogel particles. Int. Food Res. J., 132, 109099. Plazzotta, S., Jung, I., Schroeter, B., Subrahmanyam, R. P., Smirnova, I., Calligaris, S., Gurikov, P., & Manzocco, L. (2021). Conversion of whey protein aerogel particles into oleogels: Effect of oil type on structural features. Polym. J., 13(23). Scharfe, M., Ahmane, Y., Seilert, J., Keim, J., & Flöter, E. (2019). On the Effect of Minor Oil Components on β- Sitosterol/γ-oryzanol Oleogels. Eur. J. Lipid Sci. Technol., 121(8)

Le acque del Carso classico : Progetto Hydrokarst

Dopo quasi 200 anni dalle prime ricerche sul Timavo, prende il via il Progetto HYDROKARST nato dalle idee di ricercatori italiani e sloveni che da anni studiano insieme l\u2019idrogeologia carsica (www.hydrokarstproject.eu). Il progetto ha come obiettivo la gestione coordinata e la tutela dell\u2019acquifero transfrontaliero del Reka-Timavo attraverso l\u2019istituzionalizzazione di una rete di monitoraggio quantitativo e qualitativo delle acque ipogee e del territorio del Carso Classico. Il progetto si propone di garantire, attraverso delle partnership stabili, una gestione sostenibile della risorsa acqua rafforzando quella coesione territoriale transfrontaliera che deve portare alla redazione di protocolli congiunti per permettere di uniformare le metodologie di raccolta dati e la loro rappresentazione e codifica, primo passo per la definizione delle aree di salvaguardia delle sorgenti e dei pozzi captati a scopo idropotabile. Va ricordato che ad oggi, le acque del Reka-Timavo non sono legalmente tutelate, cosa che invece accade per quelle del fiume Isonzo-So\u10da. Il progetto \ue8 suddiviso in sette diversi Workpakages (WP). WP1: Progettazione e costruzione del quadro logico per la gestione del progetto. Monitoraggio coordinamento e rendicontazioni. WP2: Ideazione, preparazione e definizione dell\u2019idea progettuale. WP3: Raccolta ed elaborazione dei dati idrodinamici, idrochimici e biologici dell\u2019acquifero del Reka-Timavo. WP4: Vulnerabilit\ue0 degli acquiferi carsici e protocolli di individuazione delle aree di salvaguardia. Uso del suolo. Analisi della stabilit\ue0 della rete di distribuzione e delle necessit\ue0 di approvvigionamento idrico. WP5: Elaborazione della cartografia unificata del Carso Classico. WP6: Elaborazione di protocolli per la gestione condivisa delle risorse e delle riserve acquifere del Carso Classico. WP7: Piano di comunicazione. La fase di condivisione dati ha portato alla realizzazione di una base cartografica unificata e di una banca dati georeferenziata (GIS) di tutto il bacino del Carso Classico. Attraverso la raccolta dati prima, e l\u2019elaborazione poi, si \ue8 giunti alla definizione di un modello concettuale dell\u2019intero acquifero del Reka-Timavo. Buona parte di questi dati hanno successivamente permesso l\u2019elaborazione delle carte di vulnerabilit\ue0, a loro volta determinanti per la delimitazione delle aree di salvaguardia. Il monitoraggio della rete acquedottistica di distribuzione e la realizzazione di interventi per il risparmio idrico hanno permesso di promuovere progetti di minimizzazione delle perdite, ottimizzando tratti poco efficienti delle reti. Scopo ultimo del progetto era pertanto l\u2019elaborazione: \u2013 di accordi di cooperazione e di azioni per la promozione ed attuazione di sistemi per la riduzione delle emissioni inquinanti con particolare riferimento all\u2019acqua potabile; \u2013 di sistemi di intervento congiunti nelle situazioni di emergenza; \u2013 di strategie congiunte per prevenire e ridurre i rischi; \u2013 di interventi per il risparmio idrico, l\u2019efficienza nella gestione della rete idrica ed il miglioramento della qualit\ue0 dell\u2019acqua potabile. Skoraj dvesto let po prvih raziskavah reke Timave so italijanski in slovenski raziskovalci, ki \u17ee ve\u10d let skupaj preu\u10dujejo kra\u161ko hidrogeologijo, oblikovali Projekt HYDROKARST (www.hydrokarst-project.eu). Cilj projekta je koordinirano upravljanje in za\u161\u10dita \u10dezmejnega vodonosnika Reka-Timava z institucionalizacijo omre\u17eja za koli\u10dinsko in kakovostno spremljanje podzemnih voda na obmo\u10dju klasi\u10dnega Krasa. Namen projekta je, da se z vzpostavitvijo stalnega partnerstva zagotovi trajnostno upravljanje vodnega vira, \u10dezmejna teritorialna kohezija in priprava skupnih strokovnih podlag, ki bodo omogo\u10dale poenotenje metodologij zbiranja, prikazovanja in kodifikacije podatkov, kar je prvi korak v smeri definicije za\u161\u10ditenih obmo\u10dij izvirov in zajemali\u161\u10d pitne vode. Naj spomnimo, da vse do dana\u161njih dni vodonosnik Reka-Timava ni bil dele\u17een nikakr\u161ne pravne za\u161\u10dite \u2013 v nasprotju na primer s So\u10do (Isonzo). Projekt sestavlja sedem razli\u10dnih delovnih sklopov (WP): WP1: Oblikovanje \u201cstoritvenega sistema\u201d in priprava logi\u10dnega okvira za upravljanje projekta. Spremljanje projekta, koordiniranje in finan\u10dno poro\u10danje. WP2: Oblikovanje, priprava in dolo\u10ditev projektne ideje. WP3: Meritve in obdelava hidrodinami\u10dnih podatkov vodonosnika Reka-Timava. WP4: Ranljivost kra\u161kih vodonosnikov in protokoli za dolo\u10ditev vodovarstvenih obmo\u10dij. Raba tal. Analiza stabilnosti distribucijskegaomre\u17eja in potreb po vodni preskrbi. WP5: Priprava skupnih kartografskih prikazov mati\u10dnega Krasa. WP6: Priprava protokolov za skupno upravljanje virov in zalog mati\u10dnega Krasa. WP7: Komunikacijska kampanja o razvoju projekta in dose\u17eenih ciljih. Faza izmenjave podatkov je omogo\u10dila vzpostavitev enotnih kartografskih podlag in enotne georeferencirane podatkovne baze (GIS) za celotno obmo\u10dje mati\u10dnega Krasa. Z zbiranjem in obdelavo podatkov smo izdelali konceptualni model celotnega vodonosnika Reka-Timava. Ti podatki so nadalje omogo\u10dili izdelavo kart ranljivosti, ki so bistvenega pomena za dolo\u10ditev vodovarstvenih obmo\u10dij. Spremljanje distribucijskega vodovodnega omre\u17eja in izvajanje ukrepov za var\u10devanje z vodo je omogo\u10dilo implementacijo projektov za zmanj\u161anje izgub z izbolj\u161avami na neu\u10dinkovitih delih omre\u17eja. Kon\u10dni cilj projekta je torej: \u2013 sklenitev protokolov o sodelovanju in dolo\u10ditev ukrepov promocije in uresni\u10denja sistemov za zmanj\u161anje onesna\u17eevalnih emisij, predvsem tistih, ki se nana\u161ajo na pitno vodo; \u2013 razvoj sistemov skupnega poseganja v nujnih primerih; \u2013 oblikovanje skupnih strategij za prepre\u10devanje in zmanj\u161evanje tveganj; \u2013 promocija posegov za var\u10devanje z vodo, u\u10dinkovito upravljanje vodovodnega omre\u17eja in izbolj\u161anje kakovosti pitne vode