Diminished Mycophenolic Acid Exposure Caused by Omeprazole May Be Clinically Relevant in the First Week Posttransplantation

Background: Some studies have reported a decreased absorption of mycophenolic acid (MPA) from mycophenolate mofetil (MMF) in renal transplanted (RTx) patients under proton-pump inhibitors (PPIs). There is still a lack of information regarding (1) whether this effect occurs when MMF is administered with either tacrolimus or cyclosporine A [calcineurin inhibitors (CNIs)], (2) whether the effect has the same amplitude during the first year after RTx, and finally (3) whether this decrease in exposure is clinically relevant. Methods: We retrospectively analyzed the omeprazole effect in 348 12-hour pharmacokinetic samplings [area under the curve (AUC) 0-12h] performed on days 7, 14, 30, 60, 180, and 360 after RTx in 77 patients who participated in previous trials. Results: For all periods, the groups with and without PPI did not differ in all variables. By mixed-model analysis of variance, PPI reduced the MPA AUC(0-12h) (P < 0.0008) in the patients under both CNIs mainly due to decreased absorption (P = 0.049). In the tacrolimus group, a lower exposure seemed also due to a decreased MPA reabsorption at 10-12 hours. The PPI effect remains throughout the first year but was clinically more important on day 7. By Cox analysis, the use of PPI was associated with a 25% less chance of being adequately exposed to MPA (95% confidence interval 0.58-0.99, P = 0.04). Similarly, the number of patients underexposed to MPA (AUC < 30 ng.h/mL) was higher at most periods in the PPI group but again not statistically significant. Conclusions: These data indicate that PPI decreases the MPA exposure when associated with both CNIs but particularly in the first week after RTx. In this period, the MMF dose should be increased. This effect lasts throughout the first year but does not seem to be clinically relevant after the first week.

THE FIRST DETERMINATION OF THE VISCOSITY PARAMETER IN THE CIRCUMSTELLAR DISK OF A Be STAR

Be stars possess gaseous circumstellar decretion disks, which are well described using standard alpha-disk theory. The Be star 28 CMa recently underwent a long outburst followed by a long period of quiescence, during which the disk dissipated. Here we present the first time-dependent models of the dissipation of a viscous decretion disk. By modeling the rate of decline of the V-band excess, we determine that the viscosity parameter alpha = 1.0 +/- 0.2, corresponding to a mass injection rate (M) over dot = (3.5 +/- 1.3) x 10(-8) M-circle dot yr(-1). Such a large value of a suggests that the origin of the turbulent viscosity is an instability in the disk whose growth is limited by shock dissipation. The mass injection rate is more than an order of magnitude larger than the wind mass-loss rate inferred from UV observations, implying that the mass injection mechanism most likely is not the stellar wind, but some other mechanism.

First report of Trypanosoma vivax outbreak in dairy cattle in Sao Paulo state, Brazil

This is the first description of a trypanosoma vivax outbreak in the state of Sao Paulo (municipality of Lins). Fever, jaundice, decreased milk production, weight loss, profuse diarrhea, abortion, anemia, leukocytosis and hyperfibrinogenemia were observed in the affected animals. Thirty-one cows and calves died out of a total of 1080 in the herd. Three cows showed neurological symptoms like dysmetria, ataxia, muscle weakness, ptyalism, lymph node enlargement and submandibular edema. Flagellated hemoparasites were observed in blood smears. The species was diagnosed as T vivax by means of PCR. This T vivax strain showed resistance to diaminazene aceturate and the infection spread quickly at the herd. From the ELISA test, 599 serum samples (98.36%) were positive for anti-T. vivax IgG antibodies. This outbreak occurred during a very dry period, which indicates that other factors were involved in the outbreak, such as absence of tabanids and large populations of Haematobia irritans and Stomoxys calcitrans. The increases in these populations may have been due to the use of biosolid waste from sugar and ethanol plants in the sugarcane plantations surrounding the dairy farm.

Use of a Single L1 GPS Receiver for Monitoring Structures: First Results of the Detection of Millimetric Dynamic Oscillations

This paper presents preliminary results to determine small displacements of a global positioning system (GPS) antenna fastened to a structure using only one L1 GPS receiver. Vibrations, periodic or not, are common in large structures, such as bridges, footbridges, tall buildings, and towers under dynamic loads. The behavior in time and frequency leads to structural analysis studies. The hypothesis of this article is that any large structure that presents vibrations in the centimeter-to-millimeter range can be monitored by phase measurements of a single L1 receiver with a high data rate, as long as the direction of the displacement is pointing to a particular satellite. Within this scenario, the carrier phase will be modulated by antenna displacement. During a period of a few dozen seconds, the relative displacement to the satellite, the satellite clock, and the atmospheric phase delays can be assumed as a polynomial time function. The residuals from a polynomial adjustment contain the phase modulation owing to small displacements, random noise, receiver clock short time instabilities, and multipath. The results showed that it is possible to detect displacements of centimeters in the phase data of a single satellite and millimeters in the difference between the phases of two satellites. After applying a periodic nonsinusoidal displacement of 10 m to the antenna, it is clearly recovered in the difference of the residuals. The time domain spectrum obtained by the fast Fourier transform (FFT) exhibited a defined peak of the third harmonic much more than the random noise using the proposed third-degree polynomial model. DOI: 10.1061/(ASCE)SU.1943-5428.0000070. (C) 2012 American Society of Civil Engineers.

First report of Trypanosoma vivax outbreak in dairy cattle in São Paulo state, Brazil

This is the first description of a Trypanosoma vivax outbreak in the state of São Paulo (municipality of Lins). Fever, jaundice, decreased milk production, weight loss, profuse diarrhea, abortion, anemia, leukocytosis and hyperfibrinogenemia were observed in the affected animals. Thirty-one cows and calves died out of a total of 1080 in the herd. Three cows showed neurological symptoms like dysmetria, ataxia, muscle weakness, ptyalism, lymph node enlargement and submandibular edema. Flagellated hemoparasites were observed in blood smears. The species was diagnosed as T. vivax by means of PCR. This T.vivax strain showed resistance to diaminazene aceturate and the infection spread quickly at the herd. From the ELISA test, 599 serum samples (98.36%) were positive for anti-T.vivax IgG antibodies. This outbreak occurred during a very dry period, which indicates that other factors were involved in the outbreak, such as absence of tabanids and large populations of Haematobia irritans and Stomoxys calcitrans. The increases in these populations may have been due to the use of biosolid waste from sugar and ethanol plants in the sugarcane plantations surrounding the dairy farm.

Mountain centered icefields in northern Scandinavia

Mountain centered glaciers have played a major role throughout the last three million years in the Scandinavian mountains. The climatic extremes, like the present warm interglacial or cold glacial maxima, are very short-lived compared to the periods of intermediate climate conditions, characterized by the persistence of mountain based glaciers and ice fields of regional size. These have persisted in the Scandinavian mountains for about 65% of the Quaternary. Mountain based glaciers thus had a profound impact on large-scale geomorphology, which is manifested in large-scale glacial landforms such as fjords, glacial lakes and U-shaped valleys in and close to the mountain range. Through a mapping of glacial landforms in the northern Scandinavian mountain range, in particular a striking set of lateral moraines, this thesis offers new insights into Weichselian stages predating the last glacial maximum. The aerial photograph mapping and field evidence yield evidence that these lateral moraines were overridden by glacier ice subsequent to their formation. The lateral moraines were dated using terrestrial cosmogenic nuclide techniques. Although the terrestrial cosmogenic nuclide signature of the moraines is inconclusive, an early Weichselian age is tentatively suggested through correlations with other landforms and stratigraphical archives in the region. The abundance and coherent spatial pattern of the lateral moraines also allow a spatial reconstruction of this ice field. The ice field was controlled by topography and had nunataks protruding also where it was thickest close to the elevation axis of the Scandinavian mountain range. Outlet glaciers discharged into the Norwegian fjords and major valleys in Sweden. The process by which mountain based glaciers grow into an ice sheet is a matter of debate. In this thesis, a feedback mechanism between debris on the ice surface and ice sheet growth is presented. In essence, the growth of glaciers and ice sheets may be accelerated by an abundance of debris in their ablation areas. This may occur when the debris cover on the glacier surface inhibits ablation, effectively increasing the glaciers mass balance. It is thus possible that a dirty ablation area may cause the glacier to advance further than a clean glacier under similar conditions. An ice free period of significant length allows soil production through weathering, frost shattering, and slope processes. As glaciers advance through this assemblage of sediments, significant amounts of debris end up on the surface due to both mass wastage and subglacial entrainment. Evidence that this chain of events may occur, is given by large expanses of hummocky moraine (local name Veiki moraine) in the northern Swedish lowlands. Because the Veiki moraine has been correlated with the first Weichselian advance following the Eemian, it implies a heavily debris charged ice sheet emanating from the mountain range and terminating in a stagnant fashion in the lowlands.

High-resolution stratigraphy of Central and Southern Adriatic Quaternary deposits of sub-Milankovian climate change on Mediterranean circulation

This volume is a collection of the work done in a three years-lasting PhD, focused in the analysis of Central and Southern Adriatic marine sediments, deriving from the collection of a borehole and many cores, achieved thanks to the good seismic-stratigraphic knowledge of the study area. The work was made out within European projects EC-EURODELTA (coordinated by Fabio Trincardi, ISMAR-CNR), EC-EUROSTRATAFORM (coordinated by Phil P. E. Weaver, NOC, UK), and PROMESS1 (coordinated by Serge Bernè, IFREMER, France). The analysed sedimentary successions presented highly expanded stratigraphic intervals, particularly for the last 400 kyr, 60 kyr and 6 kyr BP. These three different time-intervals resulted in a tri-partition of the PhD thesis. The study consisted of the analysis of planktic and benthic foraminifers’ assemblages (more than 560 samples analysed), as well as in preparing the material for oxygen and carbon stable isotope analyses, and interpreting and discussing the obtained dataset. The chronologic framework of the last 400 kyr was achieved for borehole PRAD1-2 (within the work-package WP6 of PROMESS1 project), collected in 186.5 m water depth. The proposed chronology derives from a multi-disciplinary approach, consisting of the integration of numerous and independent proxies, some of which analysed by other specialists within the project. The final framework based on: micropaleontology (calcareous nannofossils and foraminifers’ bioevents), climatic cyclicity (foraminifers’ assemblages), geochemistry (oxygen stable isotope, made out on planktic and benthic records), paleomagnetism, radiometric ages (14C AMS), teprhochronology, identification of sapropel-equivalent levels (Se). It’s worth to note the good consistency between the oxygen stable isotope curve obtained for borehole PRAD1-2 and other deeper Mediterranean records. The studied proxies allowed the recognition of all the isotopic intervals from MIS10 to MIS1 in PRAD1-2 record, and the base of the borehole has been ascribed to the early MIS11. Glacial and interglacial intervals identified in the Central Adriatic record have been analysed in detail for the paleo-environmental reconstruction, as well. For instance, glacial stages MIS6, MIS8 and MIS10 present peculiar foraminifers’ assemblages, composed by benthic species typical of polar regions and no longer living in the Central Adriatic nowadays. Moreover, a deepening trend in the paleo-bathymetry during glacial intervals was observed, from MIS10 (inner-shelf environment) to MIS4 (mid-shelf environment).Ten sapropel-equivalent levels have been recognised in PRAD1-2 Central Adriatic record. They showed different planktic foraminifers’ assemblages, which allowed the first distinction of events occurred during warm-climate (Se5, Se7), cold-climate (Se4, Se6 and Se8) and temperate-intermediate-climate (Se1, Se3, Se9, Se’, Se10) conditions, consistently with literature. Cold-climate sapropel equivalents are characterised by the absence of an oligotrophic phase, whereas warm-temeprate-climate sapropel equivalents present both the oligotrophic and the eutrophic phases (except for Se1). Sea floor conditions vary, according to benthic foraminifers’ assemblages, from relatively well oxygenated (Se1, Se3), to dysoxic (Se9, Se’, Se10), to highly dysoxic (Se4, Se6, Se8) to events during which benthic foraminifers are absent (Se5, Se7). These two latter levels are also characterised by the lamination of the sediment, feature never observed in literature in such shallow records. The enhanced stratification of the water column during the events Se8, Se7, Se6, Se5, Se4, and the concurring strong dilution of shallow water, pointed out by the isotope record, lead to the hypothesis of a period of intense precipitation in the Central Adriatic region, possibly due to a northward shift of the African Monsoon. Finally, the expression of Central Adriatic PRAD1-2 Se5 equivalent was compared with the same event, as registered in other Eastern Mediterranean areas. The sequence of substantially the same planktic foraminifers’ bioevents has been consistently recognised, indicating a similar evolution of the water column all over the Eastern Mediterranean; yet, the synchronism of these events cannot be demonstrated. A high resolution analysis of late Holocene (last 6000 years BP) climate change was carried out for the Adriatic area, through the recognition of planktic and benthic foraminifers’ bioevents. In particular, peaks of planktic Globigerinoides sacculifer (four during the last 5500 years BP in the most expanded core) have been interpreted, based on the ecological requirements of this species, as warm-climate, arid intervals, correspondent to periods of relative climatic optimum, such as, for instance, the Medieval Warm Period, the Roman Age, the Late Bronze Age and the Copper Age. Consequently, the minima in the abundance of this biomarker could correspond to relatively cooler and more rainy periods. These conclusions are in good agreement with the isotopic and the pollen data. The Last Occurrence (LO) of G. sacculifer has been dated in this work at an average age of 550 years BP, and it is the best bioevent approximating the base of the Little Ice Age in the Adriatic. Recent literature reports the same bioevent in the Levantine Basin, showing a rather consistent age. Therefore, the LO of G. sacculifer has the potential to be extended to all the Eastern Mediterranean. Within the Little Ice Age, benthic foraminifer V. complanata shows two distinct peaks in the shallower Adriatic cores analysed, collected hundred kilometres apart, inside the mud belt environment. Based on the ecological requirements of this species, these two peaks have been interpreted as the more intense (cold and rainy) oscillations inside the LIA. The chronologic framework of the analysed cores is robust, being based on several range-finding 14C AMS ages, on estimates of the secular variation of the magnetic field, on geochemical estimates of the activity depth of 210Pb short-lived radionuclide (for the core-top ages), and is in good agreement with tephrochronologic, pollen and foraminiferal data. The intra-holocenic climate oscillations find out in the Adriatic have been compared with those pointed out in literature from other records of the Northern Hemisphere, and the chronologic constraint seems quite good. Finally, the sedimentary successions analysed allowed the review and the update of the foraminifers’ ecobiostratigraphy available from literature for the Adriatic region, thanks to the achievement of 16 ecobiozones for the last 60 kyr BP. Some bioevents are restricted to the Central Adriatic (for instance the LO of benthic Hyalinea balthica , approximating the MIS3/MIS2 boundary), others occur all over the Adriatic basin (for instance the LO of planktic Globorotalia inflata during MIS3, individuating Dansgaard-Oeschger cycle 8 (Denekamp)).

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).

Metamorfismo ercinico di bassa-pressione: evoluzione tettonico-metamorfica del complesso di mandatoriccio (massiccio della Sila - Calabria)

Low-pressure/high-temperature (LP/HT) metamorphic belts are characterised by rocks that experienced abnormal heat flow in shallow crustal levels (T > 600 °C; P < 4 kbar) resulting in anomalous geothermal gradients (60-150 °C/km). The abnormal amount of heat has been related to crustal underplating of mantle-derived basic magmas or to thermal perturbation linked to intrusion of large volumes of granitoids in the intermediate crust. In particular, in this latter context, magmatic or aqueous fluids are able to transport relevant amounts of heat by advection, thus favouring regional LP/HT metamorphism. However, the thermal perturbation consequent to heat released by cooling magmas is responsible also for contact metamorphic effects. A first problem is that time and space relationships between regional LP/HT metamorphism and contact metamorphism are usually unclear. A second problem is related to the high temperature conditions reached at different crustal levels. These, in some cases, can completely erase the previous metamorphic history. Notwithstanding this problem is very marked in lower crustal levels, petrologic and geochronologic studies usually concentrate in these attractive portions of the crust. However, only in the intermediate/upper-crustal levels of a LP/HT metamorphic belt the tectono-metamorphic events preceding the temperature peak, usually not preserved in the lower crustal portions, can be readily unravelled. The Hercynian Orogen of Western Europe is a well-documented example of a continental collision zone with widespread LP/HT metamorphism, intense crustal anatexis and granite magmatism. Owing to the exposure of a nearly continuous cross-section of the Hercynian continental crust, the Sila massif (northern Calabria) represents a favourable area to understand large-scale relationships between granitoids and LP/HT metamorphic rocks, and to discriminate regional LP/HT metamorphic events from contact metamorphic effects. Granulite-facies rocks of the lower crust and greenschist- to amphibolite-facies rocks of the intermediate-upper crust are separated by granitoids emplaced into the intermediate level during the late stages of the Hercynian orogeny. Up to now, advanced petrologic studies have been focused mostly in understanding P-T evolution of deeper crustal levels and magmatic bodies, whereas the metamorphic history of the shallower crustal levels is poorly constrained. The Hercynian upper crust exposed in Sila has been subdivided in two different metamorphic complexes by previous authors: the low- to very low-grade Bocchigliero complex and the greenschist- to amphibolite-facies Mandatoriccio complex. The latter contains favourable mineral assemblages in order to unravel the tectono-metamorphic evolution of the Hercynian upper crust. The Mandatoriccio complex consists mainly of metapelites, meta-arenites, acid metavolcanites and metabasites with rare intercalations of marbles and orthogneisses. Siliciclastic metasediments show a static porphyroblastic growth mainly of biotite, garnet, andalusite, staurolite and muscovite, whereas cordierite and fibrolite are less common. U-Pb ages and internal features of zircons suggest that the protoliths of the Mandatoriccio complex formed in a sedimentary basin filled by Cambrian to Silurian magmatic products as well as by siliciclastic sediments derived from older igneous and metamorphic rocks. In some localities, metamorphic rocks are injected by numerous aplite/pegmatite veins. Small granite bodies are also present and are always associated to spotted schists with large porphyroblasts. They occur along a NW-SE trending transcurrent cataclastic fault zone, which represents the tectonic contact between the Bocchigliero and the Mandatoriccio complexes. This cataclastic fault zone shows evidence of activity at least from middle-Miocene to Recent, indicating that brittle deformation post-dated the Hercynian orogeny. P-T pseudosections show that micaschists and paragneisses of the Mandatoriccio complex followed a clockwise P-T path characterised by four main prograde phases: thickening, peak-pressure condition, decompression and peak-temperature condition. During the thickening phase, garnet blastesis started up with spessartine-rich syntectonic core developed within micaschists and paragneisses. Coevally (340 ± 9.6 Ma), mafic sills and dykes injected the upper crustal volcaniclastic sedimentary sequence of the Mandatoriccio complex. After reaching the peak-pressure condition (≈4 kbar), the upper crust experienced a period of deformation quiescence marked by the static overgrowths of S2 by Almandine-rich-garnet rims and by porphyroblasts of biotite and staurolite. Probably, this metamorphic phase is related to isotherms relaxation after the thickening episode recorder by the Rb/Sr isotopic system (326 ± 6 Ma isochron age). The post-collisional period was mainly characterised by decompression with increasing temperature. This stage is documented by the andalusite+biotite coronas overgrown on staurolite porphyroblasts and represents a critical point of the metamorphic history, since metamorphic rocks begin to record a significant thermal perturbation. Peak-temperature conditions (≈620 °C) were reached at the end of this stage. They are well constrained by some reaction textures and mineral assemblages observed almost exclusively within paragneisses. The later appearance of fibrolitic sillimanite documents a small excursion of the P-T path across the And-Sil boundary due to the heating. Stephanian U-Pb ages of monazite crystals from the paragneiss, can be related to this heating phase. Similar monazite U-Pb ages from the micaschist combined with the lack of fibrolitic sillimanite suggest that, during the same thermal perturbation, micaschists recorded temperatures slightly lower than those reached by paragneisses. The metamorphic history ended with the crystallisation of cordierite mainly at the expense of andalusite. Consequently, the Ms+Bt+St+And+Sill+Crd mineral assemblage observed in the paragneisses is the result of a polyphasic evolution and is characterised by the metastable persistence of the staurolite in the stability fields of the cordierite. Geologic, geochronologic and petrographic data suggest that the thermal peak recorded by the intermediate/upper crust could be strictly connected with the emplacement of large amounts of granitoid magmas in the middle crust. Probably, the lithospheric extension in the relatively heated crust favoured ascent and emplacement of granitoids and further exhumation of metamorphic rocks. After a comparison among the tectono-metamorphic evolutions of the different Hercynian crustal levels exposed in Sila, it is concluded that the intermediate/upper crustal level offers the possibility to reconstruct a more detailed tectono-metamorphic history. The P-T paths proposed for the lower crustal levels probably underestimate the amount of the decompression. Apart from these considerations, the comparative analysis indicates that P-T paths at various crustal levels in the Sila cross section are well compatible with a unique geologic scenario, characterized by post-collisional extensional tectonics and magmas ascent.

108 Sn studied with intermediate-energy Coulomb excitation

In dieser Arbeit wurde der instabile, Neutronenarme Kern 108Sn mit Hilfe der Coulomb-Anregung bei intermediaeren Energien in inverser Kinematik studiert. Diese Methode wurde bisher zur Untersuchung der ersten angeregten 2+ Zustaende und deren E2 Zerfallsraten in Kernen mit Kernladungszahl Z< 30 angewendet. 108Sn ist somit der Kern mit der groeßten Kernladungszahl, bei dem diese Studien bisher stattfanden. Das Ziel dieses Experiments war die Messung der unbekannten reduzierten Uebergangswahrscheinlichkeit B(E2,0+ -> 2+). Der B(E2)-Wert von 0.230(57) e2b2 wurde relativ zu dem bekannten Wert des Isotops 112Sn bestimmt. Das Experiment wurde an der GSI Darmstadt mit Hilfe des RISING Detektors und des Fragmentseperators (FRS) durchgefuehrt. Sekundaere Strahlen (108Sn, 112Sn) mit einer Energie von ca. 150 MeV pro Nukleon wurden auf ein 386 mg/cm2 dickes 197Au Target geschossen. Die Projektilfragmente wurden mit Hilfe des Fragmentseparators selektiert und identifiziert. Zur Selektion des Reaktionskanals und zur Bestimmung des Winkels der gestreuten Fragmente wurde das Teilchenteleskop CATE, das sich hinter dem Target befand, verwendet. Gammastrahlung, die in Koinzidenz mit den Projektilrestkernen emittiert wurde, wurde in den Germanium-Cluster Detektoren des RISING Detektors nachgewiesen. Der gemessene B(E2,0+ -> 2+)-Wert von 108Sn ist in Uebereinstimmung mit neueren Schalenmodellrechnungen, die auf realistischen effektiven Wechselwirkungen basieren und im Rahmen eines verallgemeinerten Seniorit¨ats-Schemas erklaert werden.

Untersuchung von organischen Spurengasen und sekundärem organischem Aerosol in der Atmosphäre mittels PTR-MS

In dieser Arbeit wurden die OH-Radikalausbeuten beider Doppelbindungen von alpha-Phellandren, alpha-Terpinen, Limonen und Terpinolen bei der Ozonolyse getrennt voneinander bestimmt. Dabei wurde sich die hohe zeitliche Auflösung des PTR-MS zunutze gemacht. Es wurden die OH-Radikale mittels Cyclohexan abgefangen und aus dem daraus gebildeten Cyclohexanon die OH-Radikalausbeute berechnet. Dadurch konnten zum ersten Mal die OH-Radikalausbeuten der langsamer reagierenden Doppelbindung bestimmt werden. Es ergaben sich für alpha-Phellandren 8%11% (±3%), alpha-Terpinen 12%14% (±4%), Limonen 7%10% (±3%) und für Terpinolen 39%48% (±14%). Desweiteren wurde eine theoretische Diskussion über den Reaktionsmechanismus der Ozonolyse und dem daraus gebildetem Criegee-Intermediat durchgeführt. Dadurch konnten die OH-Radikalausbeuten erklärt werden und eine Voraussage über die OH-Radikalausbeute bei anderen Verbindungen ist mit diesen Überlegungen möglich. In einer Messkampagne in Paris konnten verschiedene VOCs und andere atmosphärisch relevante Komponenten wie Ozon, CO, NO2 und NO gemessen werden. Aus diesen Daten wurde zum einen ein Datenpaket in Igor gefertigt, welches die Interpretation der Daten erleichtern sollte. Zum anderen wurden die Daten mit einem PMF-Model analysiert.Durch die Analyse verschiedener Komponenten konnte die Frage beantwortet werden, ob die Lösungsmittelindustrie in und um Paris einen großen Einfluss auf die Konzentrationen gewisser Komponenten in der Luft hat. Über die Korrelation von Benzol und Toluol mit schwarzem Kohlenstoff und den typischen Tagesverlauf mit zwei Konzentrationsmaxima dieser Komponenten konnte gezeigt werden, dass als Hauptquelle diese beiden Stoffe nur der Straßenverkehr infrage kommt. Desweiteren konnte gezeigt werden, dass die Luftmassen die Paris erreichen einen großen Einfluss auf die Konzentration gewisser Komponenten in der Luft haben. Dadurch konnte gut zwischen lokalen Quellen und weit transportierten VOCs unterschieden werden. Schließlich konnten über das PFM-Model ein Großteil der in Paris gemessenen Substanzen in sieben unterschiedliche Quellen eingeteilt werden und deren prozentualer Einfluss während ozeanischer Luftmassen und kontinentalen Luftmassen bestimmt werden. Um Bestandteile von organischem Aerosol mithilfe eines PTR-MS und dessen schonender Ionisationstechnik detektieren zu können, wurde erfolgreich ein Einlass für das PTR-MS entwickelt der es ermöglicht neben den Messungen von VOCs in der Gasphase auch organisches Aerosol zu sammeln, desorbieren und zu detektieren. Zu Testen des neuen Einlasses wurden verschiedene Laborexperimente durchgeführt und es wurde eine Messkampagne in Cabauw (nahe Utrecht, NL) durchgeführt. Die Labortests des neuen Einlasses zeigen, dass es möglich ist organisches Aerosol und VOCs (Aerosol Precurser) in der Gasphase mit einem einzelnen Instrument zu messen. Dazu wurden in einer Smog Chamber Isopren, alpha-Pinen, Limonen und beta-Caryophyllen jeweils mit Ozon zur Reaktion gebracht. Die Messungen in der Gasphase zeigten, dass verschiedene Komponenten wie gewohnt mit hoher Zeitauflösung durch das PTR-MS detektiert werden konnten. Die Messungen des Aerosols zeigten, dass es möglich ist, viele der aus den Reaktionen bekannten Produkte direkt oder mit geringer Fragmentation zu detektieren. Die Messkampagne in Cabauw zeigte, dass es mit diesem Einlass möglich ist über einen langen Zeitraum Aerosol und VOCs mit nur einem Instrument zu messen. Die Gasphasenmessungen sind unbeeinflusst von den Modifikationen, die an dem PTR-MS und der Driftröhre vorgenommen werden mussten um Aerosol detektieren zu können. Desweiteren konnte gezeigt werden, dass sich natürliches organisches Aerosol von Aerosol aus einer Smog Chamber im Dampfdruck unterscheidet. Deswegen muss man vorsichtig sein, falls man diese zwei Aerosolarten miteinander vergleichen will.

First measurements of the aSPECT spectrometer

The aSPECT spectrometer has been constructed to measure, with high precision, the integral proton spectrum of the free neutron decay. From this spectrum the neutrino electron angular correlation coefficient a can be inferred. The coefficient a is involved in several Standard Model tests, like the unitarity test of the Cabibbo-Kobayashi-Maskawa quark mixing matrix. aSPECT has been designed to determine the coefficient a with an accuracy better than 3×10−4, that is, one order of magnitude better than the best current accuracy. First measurements with neutron beam with the aSPECT spectrometer were performed in the Forschungsneutronenquelle Heinz Maier-Leibnitz, in Munich. A study of the data taken in this period is presented in this thesis, demonstrating the proof of principle of the spectrometer. However, the observation of situation and time-dependent background instabilities impedes the report of a new value of the coefficient a. A thorough data analysis is carried out to identify sources of these background instabilities in order to improve the aSPECT experiment for future beam times. The investigation indicates that trapped particles are most likely the reason for the background problems. Furthermore, it has been observed that measurements containing less trapped particles provide a-values closer to the currently Particle Data Group value. Based on this findings, different measures are proposed to eliminate potential traps in the spectrometer. Indeed, with the proposed modifications realized for the following beam-times, the observed background instabilities were greatly reduced.

New and More Sustainable Processes for the Synthesis of Phenolics: 2-phenoxyethanol and hydroxytyrosol

The research work has dealt with the study of new catalytic processes for the synthesis of fine chemicals belonging to the class of phenolics, namely 2-phenoxyethanol and hydroxytyrosol. The two synthetic procedures investigated have the advantages of being much closer to the Green Chemistry principles than those currently used industrially. In both cases, the challenge was that of finding catalysts and methods which led to the production of less waste, and used less hazardous chemicals, safer solvents, and reusable heterogeneous catalysts. In the case of 2-phenoxyethanol, the process investigated involves the use of ethylene carbonate (EC) as the reactant for phenol O-hydroxyethylation, in place of ethylene oxide. Besides being a safer reactant, the major advantage of using EC in the new synthesis is the better selectivity to the desired product achieved. Moreover, the solid catalyst based on Na-mordenite was fully recyclable. The reaction mechanism and the effect of the Si/Al ratio in the mordenite were investigated. In the case of hydroxytyrosol, which is one of the most powerful natural antioxidants, a new synthetic procedure was investigated; in fact, the method currently employed, the hydrolysis of oleuropein, an ester extracted from the waste water processing of the olive, makes use of large amounts of organic solvents (hexane, ethyl acetate), and involves several expensive steps of purification. The synthesis procedure set up involves first the reaction between catechol and 2,2-dimethoxyacetaldehyde, followed by the one-pot reduction of the intermediate to give the desired product. Both steps were optimized, in terms of catalyst used, and of reaction conditions, that allowed to reach ca 70% yield in each step. The reaction mechanism was investigated and elucidated. During a 3-month period spent at the University of Valencia (with Prof. A. Corma’s group), a process for the production of diesel additives (2,5-bis(propoxymethyl)furan) from fructose has been investigated.

Structural characterization of intermediate and metastable phases by electron microscopy

Structure characterization of nanocrystalline intermediates and metastable phases is of primary importance for a deep understanding of synthetic processes undergoing solid-to-solid state phase transitions. Understanding the evolution from the first nucleation stage to the final synthetic product supports not only the optimization of existing processes, but might assist in tailoring new synthetic paths. A systematic investigation of intermediates and metastable phases is hampered because it is impossible to produce large crystals and only in few cases a pure synthetic product can be obtained. Structure investigation by X-ray powder diffraction methods is still challenging on nanoscale, especially when the sample is polyphasic. Electron diffraction has the advantage to collect data from single nanoscopic crystals, but is limited by data incompleteness, dynamical effects and fast deterioration of the sample under the electron beam. Automated diffraction tomography (ADT), a recently developed technique, making possible to collect more complete three-dimensional electron diffraction data and to reduce at the same time dynamical scattering and beam damage, thus allowing to investigate even beam sensitive materials (f.e. hydrated phases and organics). At present, ADT is the only technique able to deliver complete three-dimensional structural information from single nanoscopic grains, independently from other surrounding phases. Thus, ADT is an ideal technique for the study of on-going processes where different phases exist at the same time and undergo several structural transitions. In this study ADT was used as the main technique for structural characterization for three different systems and combined subsequently with other techniques, among which high-resolution transmission electron microscopy (HRTEM), cryo-TEM imaging, X-ray powder diffraction (XRPD) and energy disperse X-ray spectroscopy (EDX).rnAs possible laser host materials, i.e. materials with a broad band emission in the near-infrared region, two unknown phases were investigated in the ternary oxide system M2O-Al2O3-WO3 (M = K, Na). Both phases exhibit low purity as well as non-homogeneous size distribution and particle morphology. The structures solved by ADT are also affected by pseudo-symmetry. rnSodium titanate nanotubes and nanowires are both intermediate products in the synthesis of TiO2 nanorods which are used as additives to colloidal TiO2 film for improving efficiency of dye-sensitized solar cells (DSSC). The structural transition from nantubes to nanowires was investigated in a step by step time-resolved study. Nanowires were discovered to consist of a hitherto unknown phase of sodium titanate. This new phase, typically affected by pervasive defects like mutual layer shift, was structurally determined ab-initio on the basis of ADT data. rnThe third system is related with calcium carbonate nucleation and early crystallization. The first part of this study is dedicated to the extensive investigations of calcium carbonate formation in a step by step analysis, up to the appearance of crystalline individua. The second part is dedicated to the structure determination by ADT of the first-to-form anhydrated phase of CaCO3: vaterite. An exhaustive structure analysis of vaterite had previously been hampered by diffuse scattering, extra periodicities and fast deterioration of the material under electron irradiation. rn

Anthropology in the twenty-first century : a view of, and from, Germany

The article explores the developments in German-language anthropology in the past decades, focussing on the period after the 1970s. It argues that the recent history of German-language Ethnologie (social and cultural anthropology) is one of catching-up modernization. German-speaking anthropologists are increasingly involved in, and contribute to, broader theoretical debates, publish in English and in international journals, and are actively engaged in international academic networks. The paper discusses how and under what conditions of knowledge production these transformations have taken place. It analyses the changing institutional environment in which German anthropologists have worked and work today, as well as the theoretical impulses from within and outside the discipline that have given rise to the contemporary orientation of German-language anthropology as an anthropology of the 'present'. Finally, and beyond the focus on Germany, the article offers some ideas on the future of anthropology as a symmetrical social science, characterized by a continued strong reliance on field work and a high level of 'worldliness', a basic attitude of systematically shifting perspectives, the critical reflection of the social and political embeddedness of knowledge production, and an engagement with social theory across disciplinary boundaries.