Coffee and Caffeine Protect against Liver Injury Induced by Thioacetamide in Male Wistar Rats

Coffee intake has been inversely related to the incidence of liver diseases, although there are controversies on whether these beneficial effects on human health are because of caffeine or other specific components in this popular beverage. Thus, this study evaluated the protective effects of coffee or caffeine intake on liver injury induced by repeated thioacetamide (TAA) administration in male Wistar rats. Rats were randomized into five groups: one untreated group (G1) and four groups (G2G5) treated with the hepatotoxicant TAA (200 similar to mg/kg b.w., i.p.) twice a week for 8 similar to weeks. Concomitantly, rats received tap water (G1 and G2), conventional coffee (G3), decaffeinated coffee (G4) or 0.1% caffeine (G5). After 8 similar to weeks of treatment, rats were killed and blood and liver samples were collected. Conventional and decaffeinated coffee and caffeine intake significantly reduced serum levels of alanine aminotransferase (ALT) (p similar to<similar to 0.001) and oxidized glutathione (p similar to<similar to 0.05), fibrosis/inflammation scores (p similar to<similar to 0.001), collagen volume fraction (p similar to<similar to 0.01) and transforming growth factor beta-1 (TGF-beta 1) protein expression (p similar to=similar to 0.001) in the liver from TAA-treated groups. In addition, conventional coffee and caffeine intake significantly reduced proliferating cellular nuclear antigen (PCNA) S-phase indexes (p similar to<similar to 0.001), but only conventional coffee reduced cleaved caspase-3 indexes (p similar to<similar to 0.001), active metalloproteinase 2 (p similar to=similar to 0.004) and the number of glutathione S-transferase placental form (GST-P)-positive preneoplastic lesions (p similar to<similar to 0.05) in the liver from TAA-treated groups. In conclusion, conventional coffee and 0.1% caffeine intake presented better beneficial effects than decaffeinated coffee against liver injury induced by TAA in male Wistar rats.

Evaluation of the efficiencies of helical anchor plates in sand by centrifuge model tests

The uplift capacity of helical anchors normally increases with the number of helical plates. The rate of capacity gain is variable, considering that the disturbance caused by the anchor installation is generally more pronounced in the soil mass above the upper plates than above the lower plates, because the upper soil layers are penetrated more times. The present investigation examines the effect of the number of helices on the performance of helical anchors in sand, based on the results of centrifuge model tests. Uplift loading tests were performed on 12 different types of piles installed in two containers of dry sand prepared with different densities. The measured fractions of the uplift capacity related to each individual helical plate of multi-helix anchors were compared with the fractions predicted by the individual bearing method. The results of this investigation indicate that in double- and triple-helix anchors, the contributions of the second and third plate to the total anchor uplift capacity decreased with the increase of sand relative density and plate diameter. In addition, these experiments demonstrated that the variation of the anchor load-displacement behavior with the number of helices also depends on these parameters.

Efeito de diferentes gomas de mascar sobre o pH salivar de crianças

Objective: To evaluate the effect of different chewing gum brands on the salivary pH of children with primary dentition. Method: Forty children were selected and assigned to four groups: control (no chewing gum); sugarless chewing gum; chewing gum with casein phosphopeptide-amorphous calcium phosphate; and chewing gum with xylitol. The first saliva collection was made after supervised tooth brushing for stabilization of the oral pH. Next, all children were instructed to drink slowly 100 mL of a cola-based soft drink (Coca-Cola®) and a new saliva collection was made 10 min later. Then, each group chewed on the chewing gum for 5 min and discarded it after this time. Saliva was collected again at 5, 10 and 15 min intervals after start using the chewing gum. Measurement of salivary pH was made with colorimetric test papers and a digital pH-meter. Data were analyzed statistically by analysis of variance and Tukey’s test at a 5% significance level. Results: The use of chewing gums accelerated the increase of salivary pH to considerably alkaline levels after consumption of an acidic beverage, especially within the first minutes. The highest levels were obtained in the groups of children that used chewing gums containing xylitol and casein phosphopeptide-amorphous calcium phosphate. Conclusion: Children that used the chewing gums after ingestion of an acidic soft drink presented an increase in salivary pH, with the best results in the groups that used chewing gums containing casein phosphopeptide-amorphous calcium phosphate and xylitol.

Automated system of seedling image analysis (SVIS) and electrical conductivity to assess sun hemp seed vigor

The development of new procedures for quickly obtaining accurate information on the physiological potential of seed lots is essential for developing quality control programs for the seed industry. In this study, the effectiveness of an automated system of seedling image analysis (Seed Vigor Imaging System - SVIS) in determining the physiological potential of sun hemp seeds and its relationship with electrical conductivity tests, were evaluated. SVIS evaluations were performed three and four days after sowing and data on the vigor index and the length and uniformity of seedling growth were collected. The electrical conductivity test was made on 50 seed replicates placed in containers with 75 mL of deionised water at 25 ºC and readings were taken after 1, 2, 4, 8 and 16 hours of imbibition. Electrical conductivity measurements at 4 or 8 hours and the use of the SVIS on 3-day old seedlings can effectively detect differences in vigor between different sun hemp seed lots.

Effect of beverages on bovine dental enamel subjected to erosive challenge with hydrochloric acid

This study evaluated by an in vitro model the effect of beverages on dental enamel previously subjected to erosive challenge with hydrochloric acid. The factor under study was the type of beverage, in five levels: Sprite® Zero Low-calorie Soda Lime (positive control), Parmalat® ultra high temperature (UHT) milk, Ades® Original soymilk, Leão® Ice Tea Zero ready-to-drink low-calorie peach-flavored black teaand Prata® natural mineral water (negative control). Seventy-five bovine enamel specimens were distributed among the five types of beverages (n=15), according to a randomized complete block design. For the formation of erosive wear lesions, the specimens were immersed in 10 mL aqueous solution of hydrochloric acid 0.01 M for 2 min. Subsequently, the specimens were immersed in 20 mL of the beverages for 1 min, twice daily for 2 days at room temperature. In between, the specimens were kept in 20 mL of artificial saliva at 37ºC. The response variable was the quantitative enamel microhardness. ANOVA and Tukey's test showed highly significant differences (p<0.00001) in the enamel exposed to hydrochloric acid and beverages. The soft drink caused a significantly higher decrease in microhardness compared with the other beverages. The black tea caused a significantly higher reduction in microhardness than the mineral water, UHT milk and soymilk, but lower than the soft drink. Among the analyzed beverages, the soft drink and the black tea caused the most deleterious effects on dental enamel microhardness.

Nota científica: teste de aceitação de bebida mista de soja e amora

O objetivo deste trabalho consistiu em elaborar e avaliar a aceitação de bebida mista de extrato hidrossolúvel de soja (EHS) e suco de amora (SA). As bebidas, produzidas com diferentes proporções de EHS e SA (1:1; 1:1,5; 1:2 m/m), e diferentes concentrações de sólidos solúveis (10, 12 e 14 °Brix), foram analisadas sensorialmente e seus resultados foram submetidos à análise de variância e regressão. As diferentes proporções de EHS e SA nas bebidas produzidas interferiram no aroma e na aparência das bebidas; porém, não existiu uma relação direta entre essas proporções e a aceitabilidade desses atributos. O teor de sólidos solúveis, entretanto, influenciou o sabor e a impressão global. A preferência dos provadores, tanto no sabor como na impressão global, recaiu nas bebidas mais doces, havendo uma relação direta entre o teor de açúcar e a aceitação. Todas as bebidas formuladas foram aprovadas pela equipe de provadores.

137Cs Inventory in sedimentary columns from continental shelf of São Paulo State

137Cs is an artificial radioactive isotope produced by 235U fission. This radionuclide has a high fission yield and a half-life of 30 years. It has been detected in the environment since 1945 and its principal contamination source has been nuclear tests in the atmosphere. There are other sources of 137Cs contamination in the environment, such as: release from nuclear and reprocessing plants, radioactive dumping and nuclear accidents (Chernobyl, for example). This paper presents an inventory of 137Cs on the Continental Shelf of São Paulo State, a region located between Cabo de Santa Marta Grande (Santa Catarina state) and Cabo Frio (Rio de Janeiro state). In this area, 9 cores were collected by the Instituto Oceanográfico da Universidade de São Paulo (São Paulo University Institute of Oceanography). The cores were sliced at every 2 cm; sub-samples were lyophilized, grinded and stored in plastic containers. 137Cs was determined by 661 keV photopeak using a gamma spectrometry detector (Ge hyperpure). The analysis was performed by efficiency and background in different counting times. 137Cs concentration activities varied from 0.3 to 3.6 Bq kg-1 with a mean value of 1.2±0.6 Bq kg-1. The inventory of 137Cs in this area was 13±7 Bq m-2. Values obtained are in agreement with the Southern Hemisphere, a region contaminated by atmospheric fallout due to past nuclear explosions.

Dalla città alla casa, dalla casa alla città: la mutevole ricerca di un Piano per il ben-essere urbano

La ricerca si propone di definire le linee guida per la stesura di un Piano che si occupi di qualità della vita e di benessere. Il richiamo alla qualità e al benessere è positivamente innovativo, in quanto impone agli organi decisionali di sintonizzarsi con la soggettività attiva dei cittadini e, contemporaneamente, rende evidente la necessità di un approccio più ampio e trasversale al tema della città e di una più stretta relazione dei tecnici/esperti con i responsabili degli organismi politicoamministrativi. La ricerca vuole indagare i limiti dell’urbanistica moderna di fronte alla complessità di bisogni e di nuove necessità espresse dalle popolazioni urbane contemporanee. La domanda dei servizi è notevolmente cambiata rispetto a quella degli anni Sessanta, oltre che sul piano quantitativo anche e soprattutto sul piano qualitativo, a causa degli intervenuti cambiamenti sociali che hanno trasformato la città moderna non solo dal punto di vista strutturale ma anche dal punto di vista culturale: l’intermittenza della cittadinanza, per cui le città sono sempre più vissute e godute da cittadini del mondo (turisti e/o visitatori, temporaneamente presenti) e da cittadini diffusi (suburbani, provinciali, metropolitani); la radicale trasformazione della struttura familiare, per cui la famiglia-tipo costituita da una coppia con figli, solido riferimento per l’economia e la politica, è oggi minoritaria; l’irregolarità e flessibilità dei calendari, delle agende e dei ritmi di vita della popolazione attiva; la mobilità sociale, per cui gli individui hanno traiettorie di vita e pratiche quotidiane meno determinate dalle loro origini sociali di quanto avveniva nel passato; l’elevazione del livello di istruzione e quindi l’incremento della domanda di cultura; la crescita della popolazione anziana e la forte individualizzazione sociale hanno generato una domanda di città espressa dalla gente estremamente variegata ed eterogenea, frammentata e volatile, e per alcuni aspetti assolutamente nuova. Accanto a vecchie e consolidate richieste – la città efficiente, funzionale, produttiva, accessibile a tutti – sorgono nuove domande, ideali e bisogni che hanno come oggetto la bellezza, la varietà, la fruibilità, la sicurezza, la capacità di stupire e divertire, la sostenibilità, la ricerca di nuove identità, domande che esprimono il desiderio di vivere e di godere la città, di stare bene in città, domande che non possono essere più soddisfatte attraverso un’idea di welfare semplicemente basata sull’istruzione, la sanità, il sistema pensionistico e l’assistenza sociale. La città moderna ovvero l’idea moderna della città, organizzata solo sui concetti di ordine, regolarità, pulizia, uguaglianza e buon governo, è stata consegnata alla storia passata trasformandosi ora in qualcosa di assai diverso che facciamo fatica a rappresentare, a descrivere, a raccontare. La città contemporanea può essere rappresentata in molteplici modi, sia dal punto di vista urbanistico che dal punto di vista sociale: nella letteratura recente è evidente la difficoltà di definire e di racchiudere entro limiti certi l’oggetto “città” e la mancanza di un convincimento forte nell’interpretazione delle trasformazioni politiche, economiche e sociali che hanno investito la società e il mondo nel secolo scorso. La città contemporanea, al di là degli ambiti amministrativi, delle espansioni territoriali e degli assetti urbanistici, delle infrastrutture, della tecnologia, del funzionalismo e dei mercati globali, è anche luogo delle relazioni umane, rappresentazione dei rapporti tra gli individui e dello spazio urbano in cui queste relazioni si muovono. La città è sia concentrazione fisica di persone e di edifici, ma anche varietà di usi e di gruppi, densità di rapporti sociali; è il luogo in cui avvengono i processi di coesione o di esclusione sociale, luogo delle norme culturali che regolano i comportamenti, dell’identità che si esprime materialmente e simbolicamente nello spazio pubblico della vita cittadina. Per studiare la città contemporanea è necessario utilizzare un approccio nuovo, fatto di contaminazioni e saperi trasversali forniti da altre discipline, come la sociologia e le scienze umane, che pure contribuiscono a costruire l’immagine comunemente percepita della città e del territorio, del paesaggio e dell’ambiente. La rappresentazione del sociale urbano varia in base all’idea di cosa è, in un dato momento storico e in un dato contesto, una situazione di benessere delle persone. L’urbanistica moderna mirava al massimo benessere del singolo e della collettività e a modellarsi sulle “effettive necessità delle persone”: nei vecchi manuali di urbanistica compare come appendice al piano regolatore il “Piano dei servizi”, che comprende i servizi distribuiti sul territorio circostante, una sorta di “piano regolatore sociale”, per evitare quartieri separati per fasce di popolazione o per classi. Nella città contemporanea la globalizzazione, le nuove forme di marginalizzazione e di esclusione, l’avvento della cosiddetta “new economy”, la ridefinizione della base produttiva e del mercato del lavoro urbani sono espressione di una complessità sociale che può essere definita sulla base delle transazioni e gli scambi simbolici piuttosto che sui processi di industrializzazione e di modernizzazione verso cui era orientata la città storica, definita moderna. Tutto ciò costituisce quel complesso di questioni che attualmente viene definito “nuovo welfare”, in contrapposizione a quello essenzialmente basato sull’istruzione, sulla sanità, sul sistema pensionistico e sull’assistenza sociale. La ricerca ha quindi analizzato gli strumenti tradizionali della pianificazione e programmazione territoriale, nella loro dimensione operativa e istituzionale: la destinazione principale di tali strumenti consiste nella classificazione e nella sistemazione dei servizi e dei contenitori urbanistici. E’ chiaro, tuttavia, che per poter rispondere alla molteplice complessità di domande, bisogni e desideri espressi dalla società contemporanea le dotazioni effettive per “fare città” devono necessariamente superare i concetti di “standard” e di “zonizzazione”, che risultano essere troppo rigidi e quindi incapaci di adattarsi all’evoluzione di una domanda crescente di qualità e di servizi e allo stesso tempo inadeguati nella gestione del rapporto tra lo spazio domestico e lo spazio collettivo. In questo senso è rilevante il rapporto tra le tipologie abitative e la morfologia urbana e quindi anche l’ambiente intorno alla casa, che stabilisce il rapporto “dalla casa alla città”, perché è in questa dualità che si definisce il rapporto tra spazi privati e spazi pubblici e si contestualizzano i temi della strada, dei negozi, dei luoghi di incontro, degli accessi. Dopo la convergenza dalla scala urbana alla scala edilizia si passa quindi dalla scala edilizia a quella urbana, dal momento che il criterio del benessere attraversa le diverse scale dello spazio abitabile. Non solo, nei sistemi territoriali in cui si è raggiunto un benessere diffuso ed un alto livello di sviluppo economico è emersa la consapevolezza che il concetto stesso di benessere sia non più legato esclusivamente alla capacità di reddito collettiva e/o individuale: oggi la qualità della vita si misura in termini di qualità ambientale e sociale. Ecco dunque la necessità di uno strumento di conoscenza della città contemporanea, da allegare al Piano, in cui vengano definiti i criteri da osservare nella progettazione dello spazio urbano al fine di determinare la qualità e il benessere dell’ambiente costruito, inteso come benessere generalizzato, nel suo significato di “qualità dello star bene”. E’ evidente che per raggiungere tale livello di qualità e benessere è necessario provvedere al soddisfacimento da una parte degli aspetti macroscopici del funzionamento sociale e del tenore di vita attraverso gli indicatori di reddito, occupazione, povertà, criminalità, abitazione, istruzione, etc.; dall’altra dei bisogni primari, elementari e di base, e di quelli secondari, culturali e quindi mutevoli, trapassando dal welfare state allo star bene o well being personale, alla wellness in senso olistico, tutte espressioni di un desiderio di bellezza mentale e fisica e di un nuovo rapporto del corpo con l’ambiente, quindi manifestazione concreta di un’esigenza di ben-essere individuale e collettivo. Ed è questa esigenza, nuova e difficile, che crea la diffusa sensazione dell’inizio di una nuova stagione urbana, molto più di quanto facciano pensare le stesse modifiche fisiche della città.

Gli assetti proprietari e di controllo nell'agroalimentare italiano

The recent default of important Italian agri-business companies provides a challenging issue to be investigated through an appropriate scientific approach. The events involving CIRIO, FERRUZZI or PARMALAT rise an important research question: what are the determinants of performance for Italian companies in the Italian agri – food sector? My aim is not to investigate all the factors that are relevant in explaining performance. Performance depends on a wide set of political, social, economic variables that are strongly interconnected and that are often very difficult to express by formal or mathematical tools. Rather, in my thesis I mainly focus on those aspects that are strictly related to the governance and ownership structure of agri – food companies representing a strand of research that has been quite neglected by previous scholars. The conceptual framework from which I move to justify the existence of a relationship between the ownership structure of a company, governance and performance is the model set up by Airoldi and Zattoni (2005). In particular the authors investigate the existence of complex relationships arising within the company and between the company and the environment that can bring different strategies and performances. They do not try to find the “best” ownership structure, rather they outline what variables are connected and how they could vary endogenously within the whole economic system. In spite of the fact that the Airoldi and Zattoni’s model highlights the existence of a relationship between ownership and structure that is crucial for the set up of the thesis the authors fail to apply quantitative analyses in order to verify the magnitude, sign and the causal direction of the impact. In order to fill this gap we start from the literature trying to investigate the determinants of performance. Even in this strand of research studies analysing the relationship between different forms of ownership and performance are still lacking. In this thesis, after a brief description of the Italian agri – food sector and after an introduction including a short explanation of the definitions of performance and ownership structure, I implement a model in which the performance level (interpreted here as Return on Investments and Return on Sales) is related to variables that have been previously identified by the literature as important such as the financial variables (cash and leverage indices), the firm location (North Italy, Centre Italy, South Italy), the power concentration (lower than 25%, between 25% and 50% and between 50% and 100% of ownership control) and the specific agri – food sector (agriculture, food and beverage). Moreover we add a categorical variable representing different forms of ownership structure (public limited company, limited liability company, cooperative) that is the core of our study. All those variables are fully analysed by a preliminary descriptive analysis. As in many previous contributions we apply a panel least squares analysis for 199 Italian firms in the period 1998 – 2007 with data taken from the Bureau Van Dijck Dataset. We apply two different models in which the dependant variables are respectively the Return on Investments (ROI) and the Return on Sales (ROS) indicators. Not surprisingly we find that companies located in the North Italy representing the richest area in Italy perform better than the ones located in the Centre and South of Italy. In contrast with the Modigliani - Miller theorem financial variables could be significant and the specific sector within the agri – food market could play a relevant role. As the power concentration, we find that a strong property control (higher than 50%) or a fragmented concentration (lower than 25%) perform better. This result apparently could suggest that “hybrid” forms of concentrations could create bad functioning in the decision process. As our key variables representing the ownership structure we find that public limited companies and limited liability companies perform better than cooperatives. This is easily explainable by the fact that law establishes that cooperatives are less profit – oriented. Beyond cooperatives public limited companies perform better than limited liability companies and show a more stable path over time. Results are quite consistent when we consider both ROI and ROS as dependant variables. These results should not lead us to claim that public limited company is the “best” among all possible governance structures. First, every governance solution should be considered according to specific situations. Second more robustness analyses are needed to confirm our results. At this stage we deem these findings, the model set up and our approach represent original contributions that could stimulate fruitful future studies aimed at investigating the intriguing issue concerning the effect of ownership structure on the performance levels.

Studio della gestione integrata dei rifiuti urbani nell'ambito della provincia di Bologna

This work is an analysis of integrated urban waste management in the province of Bologna. It consists of five chapters and one enclosure. Primarily, it focuses on the legislative framework at european, national and local level. Then the study analyses the situation of urban waste system adopted in the reference territory from 2003 to 2007 to show its evolution process. Chapter 3 is based on considerations about the percentage of effective recover of materials derived from separate collection that has been reached in the province of Bologna in 2006. The following chapter describes the urban waste management at national level using dates of 2005 and 2006 by APAT (National Agency for environmental protection). Then, it has been made a comparison with Emilia-Romagna and district of Bologna. Chapter 5 focuses on the description of innovative strategies introduced in the district of Bologna to increase separate collection level and optimize waste management. In particular, it analyses two sperimental projects: one based on door to door collection and the other founded on an integrated collection system which provides the application of two collection models (door to door collection in industrial areas and collection by containers in urban ones). Finally, in the enclosure, it is also descrided best practices of waste management sector about collection models, treatment plants and innovative strategies available at that moment in Europe.

Messung des Landé-gJ-Faktors im Grundzustand von Ca + und Untersuchung des Speicherverhaltens von Elektronen in einem Penningkäfig

Ionenkäfige und speziell Penningfallen stellen sich in der Atomphysik als außergewöhnliche Werkzeuge heraus. Zum einen bieten diese 'Teilchencontainer' die Möglichkeit atomphysikalische Präzisionsmessungen durchzuführen und zum anderen stellen Penningfallen schwingungsfähige Systeme dar, in welchen nichtlineare dynamische Prozesse an gespeicherten Teilchen untersucht werden können. In einem ersten Teil der Arbeit wurde mit der in der Atomphysik bekannten Methode der optischen Mikrowellen-Doppelresonanz Spektroskopie der elektronische g-Faktor von Ca+ mit einer Genauigkeit von 4*10^{-8} zu gJ=2,00225664(9) bestimmt. g-Faktoren von Elektronen in gebundenen ionischen Systemen sind fundamentale Größen der Atomphysik, die Informationen über die atomare Wellenfunktion des zu untersuchenden Zustandes liefern. In einem zweiten Teil der Arbeit wurde hinsichtlich der Untersuchungen zur nichtlinearen Dynamik von parametrisch angeregten gespeicherten Elektronen beobachtet, dass ab bestimmten kritischen Teilchendichten in der Penningfalle die gespeicherten Elektronen kollektive Eigenschaften manifestieren. Weiterhin wurde bei der Anregung der axialen Eigenbewegung ein Schwellenverhalten der gemessenen Subharmonischen zur 2*omega_z-Resonanz beobachtet. Dieser Schwelleneffekt lässt sich mit der Existenz eines Dämpfungsmechanismus erklären, der auf die Elektronenwolke einwirkt, so dass eine Mindestamplitude der Anregung erforderlich ist, um diese Dämpfung zu überwinden. Durch Bestimmung der charakteristischen Kurven der gedämpften Mathieuschen Differentialgleichung konnte das beobachtete Phänomen theoretisch verstanden werden.

Weiterentwicklung einer Produktionsanlage und der Speicherungs- bzw. Transportkonzepte für hochpolarisiertes 3He

Der Bedarf an hyperpolarisiertem 3He in Medizin und physikalischer Grundlagenforschung ist in den letzten ca. 10-15 Jahren sowohl in Bezug auf die zu Verfügung stehende Menge, als auch auf den benötigten Grad der Kernspinpolarisation stetig gestiegen. Gleichzeitig mußten Lösungen für die polarisationserhaltende Speicherung und den Transport gefunden werden, die je nach Anwendung anzupassen waren. Als Ergebnis kann mit dieser Arbeit ein in sich geschlossenes Gesamtkonzept vorgestellt werden, daß sowohl die entsprechenden Mengen für klinische Anwendungen, als auch höchste Polarisation für physikalische Grundlagenfor-schung zur Verfügung stellen kann. Verschiedene unabhängige Polarimetriemethoden zeigten in sich konsistente Ergebnisse und konnten, neben ihrer eigenen Weiterentwicklung, zu einer verläßlichen Charakterisierung des neuen Systems und auch der Transportzellen und –boxen eingesetzt werden. Die Polarisation wird mittels „Metastabilem Optischen Pumpen“ bei einem Druck von 1 mbar erzeugt. Dabei werden ohne Gasfluß Werte von P = 84% erreicht. Im Flußbetrieb sinkt die erreichbare Polarisation auf P ≈ 77%. Das 3He kann dann weitgehend ohne Polarisationsver-luste auf mehrere bar komprimiert und zu den jeweiligen Experimenten transportiert werden. Durch konsequente Weiterentwicklung der vorgestellten Polarisationseinheit an fast allen Komponenten kann somit jetzt bei einem Fluß von 0,8 barl/h eine Polarisation von Pmax = 77% am Auslaß der Apparatur erreicht werden. Diese skaliert linear mit dem Fluß, sodaß bei 3 barl/h die Polarisation immer noch bei ca. 60% liegt. Dabei waren die im Rahmen dieser Arbeit durchgeführten Verbesserungen an den Lasern, der Optik, der Kompressionseinheit, dem Zwischenspeicher und der Gasreinigung wesentlich für das Erreichen dieser Polarisatio-nen. Neben dem Einsatz eines neuen Faserlasersystems ist die hohe Gasreinheit und die lang-lebige Kompressionseinheit ein Schlüssel für diese Leistungsfähigkeit. Seit Herbst 2001 er-zeugte das System bereits über 2000 barl hochpolarisiertes 3He und ermöglichte damit zahl-reiche interdisziplinäre Experimente und Untersuchungen. Durch Verbesserungen an als Prototypen bereits vorhandenen Transportboxen und durch weitgehende Unterdrückung der Wandrelaxation in den Transportgefäßen aufgrund neuer Erkenntnisse über deren Ursachen stellen auch polarisationserhaltende Transporte über große Strecken kein Problem mehr dar. In unbeschichteten 1 Liter Kolben aus Aluminosilikatglä-sern werden nun problemlos Speicherzeiten von T1 > 200h erreicht. Im Rahmen des europäi-schen Forschungsprojektes „Polarized Helium to Image the Lung“ wurden während 19 Liefe-rungen 70barl 3He nach Sheffield (UK) und bei 13 Transporten 100 barl nach Kopenhagen (DK) per Flugzeug transportiert. Zusammenfassend konnte gezeigt werden, daß die Problematik der Kernspinpolarisationser-zeugung von 3He, die Speicherung, der Transport und die Verwendung des polarisierten Ga-ses in klinischer Diagnostik und physikalischen Grundlagenexperimenten weitgehend gelöst ist und das Gesamtkonzept die Voraussetzungen für allgemeine Anwendungen auf diesen Gebieten geschaffen hat.

Photoreactive polyorganosiloxane nanoparticles and the fabrication of photocleavable microcapsules

In this thesis, we have presented the preparation of highly crosslinked spherical photoreactive colloidal particles of radius about 10 nm based on the monomer trimethoxysilane. These particles are labeled chemically with two different dye systems (coumarin, cinnamate) which are known to show reversible photodimerization. By analyzing the change in particle size upon UV irradiation with dynamic light scattering, we could demonstrate that the partially reversible photoreaction in principle can be utilized to control increase and decrease of colloidal clusters. Here, selection of the appropriate wavelengths during the irradiation employing suitable optical filters proved to be very important. Next, we showed how photocrosslinking of our nanoparticles within the micrometer-sized thin oil shell of water-oil-water emulsion droplets leads to a new species of optically addressable microcontainers. The inner water droplet of these emulsions may contain drugs, dyes or other water-soluble components, leading to filled containers. Thickness, mechanical stability and light resistance of the container walls can be controlled in a simple way by the amount and adjustable photoreactivity (= No. of labels/particle) of the nanoparticles. Importantly, the chemical bonds between the nanoparticles constituting the microcapsule shell can be cleaved photochemically by irradiation with uv light. An additional major advantage is that filling our microcapsules with water-soluble substrate molecules is extremely simple using a solution of the guest molecules as inner water phase of the W/O/W-emulsion. This optically controlled destruction of our microcontainers thus opens up a pathway to controlled release of the enclosed components as illustrated by the example of enclosed cyclodextrin molecules.

Core-shell macromolecules with dendritic polyphenylene core and polymer shells

Core-shell macromolecules with dendritic polyphenylene core and polymer shell Zusammenfassung / Abstract Core-shell macromolecular structures have become of great interest in materials science because they gave an opportunity to combine a large variety of chemical and physical properties in the single molecule, by combination of different (in terms of chemistry and physics) cores and shells. The interest in such complex structures was provoked by their potential applications in the coating and painting industry (latexes), as supports for catalysts in polymer industry, or as nano-containers and transporters for genes or drug delivery. The aim of this study was the synthesis, characterization and further application of core-shell macromolecules possessing a hydrophobic stiff core (polyphenylene dendrimers) surrounded with a hydrophilic, soft, covalently bonded polymer shell (poly(ethylene oxide) and its copolymers). The requirements for such complex substances were that they should be well-defined in terms of molecular weight (narrow molecular weight distribution) and in molecular structure. The preparation of core-shell molecules containing dendrimer as a core was possible via two synthetic routs: “grafting-onto” and “grafting-from”. The resulting core-shell macromolecules possessed narrow polydispersity as guaranteed by the excellent structural and functional definition of the dendrimer and the narrow polydispersity of the PEO, PS-b-PEO and PI-b-PEO attached to the dendrimer surface. Additional investigation of the size of the particles indicated a relation between both the length and the number of the polymer chains and the hydrodynamic radius determined by Dynamic Light Scattering and Fluorescent Correlation Spectroscopy. Core-shell nano-particles were applied as metallocene supports in heterogeneous olefin polymerizations. Our results indicate that such catalyst systems, that have a size of at least one order of magnitude smaller than the used by now organic supports, could be very useful as model compounds for investigations on catalyst fragmentation and its influence on the product parameters.

Analisi congiunta di parametri chimici e sensoriali per la valutazione della qualità di oli extravergini di oliva monovarietali

Il termine extravergine, per un olio di alta qualità, rappresenta solo un pre-requisito: la categoria merceologica, intesa come conformità ad una serie di analisi chimico-sensoriali previste dalla normativa Europea, non è sufficiente ad esaltare il valore aggiunto che un olio può avere in termini di attributi di qualità sensoriale e salutistica. Questi ultimi sono fortemente influenzati dalla presenza di alcuni composti minori, come le molecole volatili e quelle a struttura fenolica (biofenoli). I composti volatili sono i principali responsabili dell'aroma di un olio extravergine d’oliva, mentre i biofenoli lo sono per gli attributi positivi, di amaro e piccante, già normati dal legislatore. Lo studio ha riguardato le relazioni esistenti tra le sostanze volatili e biofenoliche e le percezioni sensoriali ad esse associate. Tra gli oli extravergini di oliva partecipanti all’International Olive Oil Award di Zurigo 2012, sono stati selezionati 28 campioni monovarietali di diversa provenienza geografica (principalmente Italia, Spagna e Grecia). La valutazione sensoriale è stata eseguita dal panel dell’Institute of Food and Beverage Innovation di Zurigo con l’impiego di una scheda di profilo più descrittiva di quella ufficiale (Reg. CE 640/2008), contenente numerosi attributi positivi secondari valutati su scala discreta a 4 punti, oltre ad armonia e persistenza, su scala continua di 10 cm. I campioni sono stati sottoposti alla caratterizzazione della frazione biofenolica (indice di amaro, contenuto in fenoli totali ed analisi delle principali molecole fenoliche mediante HPLC-DAD/MSD) e dei composti volatili (SPME/GC-MSD). I dati ottenuti sono stati elaborati con l’ausilio di tecniche di analisi multivariata nel tentativo di valutare le correlazioni esistenti tra le variabili e di individuare gruppi omogenei di oli. La finalità di questo lavoro è stata quella di suggerire attributi discriminanti la qualità sensoriale di oli di pregio, che possano essere impiegati come leve di promozione dei prodotti, così come indicatori addizionali di autenticità.