Measurement of prompt J/psi and beauty hadron production cross sections at mid-rapidity in pp collisions at root s=7 TeV

The ALICE experiment at the LHC has studied J/psi production at mid-rapidity in pp collisions at root s = 7 TeV through its electron pair decay on a data sample corresponding to an integrated luminosity L-int = 5.6 nb(-1). The fraction of J/psi from the decay of long-lived beauty hadrons was determined for J/psi candidates with transverse momentum p(t) > 1,3 GeV/c and rapidity vertical bar y vertical bar < 0.9. The cross section for prompt J/psi mesons, i.e. directly produced J/psi and prompt decays of heavier charmonium states such as the psi(2S) and chi(c) resonances, is sigma(prompt J/psi) (p(t) > 1.3 GeV/c, vertical bar y vertical bar < 0.9) = 8.3 +/- 0.8(stat.) +/- 1.1 (syst.)(-1.4)(+1.5) (syst. pol.) mu b. The cross section for the production of b-hadrons decaying to J/psi with p(t) > 1.3 GeV/c and vertical bar y vertical bar < 0.9 is a sigma(J/psi <- hB) (p(t) > 1.3 GeV/c, vertical bar y vertical bar < 0.9) = 1.46 +/- 0.38 (stat.)(-0.32)(+0.26) (syst.) mu b. The results are compared to QCD model predictions. The shape of the p(t) and y distributions of b-quarks predicted by perturbative QCD model calculations are used to extrapolate the measured cross section to derive the b (b) over bar pair total cross section and d sigma/dy at mid-rapidity.

Leg and arm lactate and substrate kinetics during exercise

[EN] To study the role of muscle mass and muscle activity on lactate and energy kinetics during exercise, whole body and limb lactate, glucose, and fatty acid fluxes were determined in six elite cross-country skiers during roller-skiing for 40 min with the diagonal stride (Continuous Arm + Leg) followed by 10 min of double poling and diagonal stride at 72-76% maximal O(2) uptake. A high lactate appearance rate (R(a), 184 +/- 17 micromol x kg(-1) x min(-1)) but a low arterial lactate concentration ( approximately 2.5 mmol/l) were observed during Continuous Arm + Leg despite a substantial net lactate release by the arm of approximately 2.1 mmol/min, which was balanced by a similar net lactate uptake by the leg. Whole body and limb lactate oxidation during Continuous Arm + Leg was approximately 45% at rest and approximately 95% of disappearance rate and limb lactate uptake, respectively. Limb lactate kinetics changed multiple times when exercise mode was changed. Whole body glucose and glycerol turnover was unchanged during the different skiing modes; however, limb net glucose uptake changed severalfold. In conclusion, the arterial lactate concentration can be maintained at a relatively low level despite high lactate R(a) during exercise with a large muscle mass because of the large capacity of active skeletal muscle to take up lactate, which is tightly correlated with lactate delivery. The limb lactate uptake during exercise is oxidized at rates far above resting oxygen consumption, implying that lactate uptake and subsequent oxidation are also dependent on an elevated metabolic rate. The relative contribution of whole body and limb lactate oxidation is between 20 and 30% of total carbohydrate oxidation at rest and during exercise under the various conditions. Skeletal muscle can change its limb net glucose uptake severalfold within minutes, causing a redistribution of the available glucose because whole body glucose turnover was unchanged.

Conformation and Stereodynamic of Hindered Aromatic System

The preparation of conformationally hindered molecules and their study by DNMR and computational methods are my thesis’s core. In the first chapter, the conformations and the stereodynamics of symmetrically ortho-disubstituted aryl carbinols and aryl ethers are described. In the second chapter, the structures of axially chiral atropisomers of hindered biphenyl carbinols are studied. In the third chapter, the steric barriers and the -barrier of 1,8-di-aylbiphenylenes are determined. Interesting atropisomers are found in the cases of arylanthrones, arylanthraquinones and arylanthracenes and are reported in the fourth chapter. By the combined use of dynamic NMR, ECD spectroscopy and DFT computations, the conformations and the absolute configurations of 2-Naphthylalkylsulfoxides are studied in the fifth chapter. In the last chapter, a new synthetic route to ,’-arylated secondary or tertiary alcohols by lithiated O-benzyl-carbamates carrying an N-aryl substituent and DFT calculations to determinate the cyclic intermediate are reported. This work was done in the research group of Prof. Jonathan Clayden, at the University of Manchester.

Il ruolo della grande distribuzione nello sviluppo locale. Un'indagine sul contesto italiano

Supermarkets and hypermarkets still represent a relatively new retailing format in Italy and in its Southern area in particular, where they were introduced decades later than in other Western countries, such as France and the UK in Europe, and the US in America. Nowadays, these retailers have become large organisations potentially capable of influencing local development from an economic, social and urban perspective. The literature concerned with their effects on the local economy, in particular, has focused on labour markets, price dynamics, inter-type competition, instead the impact on macroeconomic factors such as GDP, value added and investments in specific sectors, as agriculture, industry and services. This study tries to fill this gap by empirically investigating associations between key characteristics of these retailers and specific macroeconomic factors.

Coupled-Cluster-Berechnungen von Parametern der Kernspin-Resonanz-Spektroskopie

Coupled-Cluster-Berechnungen von Parametern derKernspin-Resonanz-Spektroskopie Dissertationsschrift von Alexander A.Auer, Mainz 2002 Im Rahmen einer Studie der Berechnung von 13C-Verschiebungenwerdendie Einfluesse von Elektronenkorrelation, Basissatz,Gleichgewichtsgeometrie sowie Schwingungs- und Rotationseffekten separat betrachtet.Dabei zeigt sich, dass dieCoupled-Cluster-Singles-Doubles-Methode mitstoerungstheoretischer Behandlung der Dreifachanregungen(CCSD(T)) mit entsprechend grossen Basissaetzen bei Beruecksichtigung derNullpunktsschwingungseffekte Ergebnisse mit ca. 1 ppm Abweichung zum Experiment liefert. Eine Analyse der Elektronenkorrelationseffekte beiCoupled-Cluster- (CC-) Berechnungen von indirekten Spin-Spin-Kopplungskonstanten zeigt, dassCC-Methoden mit Hartree-Fock-Orbitalrelaxation zur Berechnung derKopplungskonstanten ungeeignet sind. Eine Loesung ist die Verwendung unrelaxierter CC-Methoden,in denendie HF-Orbitalrelaxation aus der Berechnung der gestoertenWellenfunktion ausgeschlossen wird. Full-Configuration-Interaction-Berechnungen fuer Borhydridzeigen,dass auf CC-Singles-Doubles-Niveau (CCSD) 94% und aufCC-Singles-Doubles-Triples-Niveau (CCSDT) 99% der Korrelationseffekte beschrieben werden. Weiterhin istdie Beruecksichtigung der Nullpunktsschwingung sowie die Wahl eines ausreichend grossen Basissatzes wichtig. Auf Grundlage der vorangegangenen Studien werden im letztenTeil zwei Beispiele zur Anwendung hochgenauer Berechnungen vonNMR-Parametern vorgestellt.Im Rahmen einer Studie der Spin-Spin-Kopplungskonstanten vonCyclopentan wird eine Karplus-Beziehungzwischen den Kopplungskonstanten und der Konformation desMolekuels aufgestellt, desweiteren werden die NMR-Parameter von Methylidinphosphanuntersucht.

Einfluss von oxidativem Stress auf die DNA-Reparatur in Säugerzellen

Gegenstand dieser Arbeit war es, das Zusammenspiel zwischen DNA-Reparatur und zellulärem anitoxidativen Abwehrsystem in Melanomzellen und gesunden Hautfibroblasten näher zu untersuchen. Dabei konnte gezeigt werden, dass die dominierenden DNA-Läsionen im Falle einer Bestrahlung mit sichtbarem Licht (400 – 800 nm) Fpg-sensitive Läsionen, zu denen die Basenmodifikation 7,8-Dihydro-8-oxoguanin (8-oxoG) gehört, und im Falle der UVA-Bestrahlung Cyclobutan-Pyrimidindimere (CPDs) sind. Sowohl Melanomzellen als auch Hautfibroblasten waren problemlos in der Lage, die durch sichtbares Licht und UVA-Strahlung induzierten oxidativen DNA-Modifikationen zu reparieren. Jedoch reagierten Melanomzellen in einer adaptiven Antwort mit einer Erhöhung ihres Glutathion-Gehalts auf ein Maximum (nach circa 10 - 14 h) nach Bestrahlung mit sichtbarem Licht, wohingegen die Hautfibroblasten einen massiven Einbruch direkt nach Bestrahlung und eine extrem lange Erholungsphase über 48 h aufzuweisen hatten. Die darauffolgende Untersuchung der DNA-Reparaturkapazität der Zellen unter Bedingungen von oxidativem Stress mit vorangegangener Depletion intrazellulären Glutathions zeigten eine dramatische, nahezu vollständige Hemmung der Reparatur durch UVA- bzw. Sonnenlicht-induzierter Fpg-sensitiver DNA-Modifikationen (8-oxoG) - sowohl in Melanomzellen als auch in Hautfibroblasten. Dieser Effekt ließ sich durch den Zusatz von Dithiothreitol (DTT), nach erfolgter Bestrahlung der Glutathion-depletierten Zellen, wieder komplett revertieren. Diese Ergebnisse weisen darauf hin, dass an der Reparatur ein redoxempfindliches Protein oder zellulärer Cofaktor beteiligt sein muß. Zudem konnte durch Untersuchungen der Nukleotidexzisionsreparatur (NER) und der Einzelstrangbruchreparatur nach dem gleichen Versuchsdesign gezeigt werden, dass es sich hierbei sehr wahrscheinlich um einen für die Basenexzisionsreparatur (BER) von 7,8-dihydro-8-oxo-guanine (8-oxoG) exklusiven Effekt handelte. Zwei der wichtigsten Reparaturproteine der BER, nämlich hOGG1 und APE1, wurden anschließend auf ihre Funktionsfähigkeit hin untersucht, da es naheliegend war, dass der Reparaturhemmung ein Funktionsverlust eines dieser beiden Enzyme zugrunde liegen könnte. Im Falle des APE1-Proteins konnte dies ausgeschlossen werden, da mit Hilfe der Alkalischen Elution die volle Funktionsfähigkeit für die Reparatur von AP-Läsionen nachgewiesen werden konnte. Interessanterweise zeigte aber das hOGG1-Protein eine zwischen der dritten und vierten Stunde nach Bestrahlung Glutathion-depletierter Zellen stark abfallende Aktivität der 8-oxoG-Glykosylasefunktion. Die Western-Blot-Analyse ergab allerdings keinen Hinweis auf eine Proteinoxidation von hOGG1. Möglicherweise wird nicht hOGG1 selbst, wohl aber ein anderes, für eine konzertierte Abfolge der einzelnen Reparaturschritte entscheidend notwendiges Protein innerhalb der Zelle durch ROS leicht oxidiert. In jedem Fall bleibt festzustellen, dass Glutathion eine wichtige Aufgabe hinsichtlich einer voll funktionsfähigen Basenexzisionreparatur zuzukommen scheint. Die Ergebnisse unterstreichen die mögliche Bedeutung von oxidativem Stress für die Entstehung von Krebs durch Sonnenlicht, insbesondere durch UVA, da die durch die Strahlung (und eventuell auftretende Entzündung) gebildeten ROS nicht nur DNA-Schäden induzieren, sondern auch ihre Reparatur verhindern können.

Edizione commentata della Cronaca di Venezia di Giovanni Tiepolo (XVI-XVII sec.)

Il seguente studio propone l'esame di una cronaca veneziana del XVI secolo, inedita, dalle origini al 1538/39, che parte della tradizione manoscritta attribuisce al Patriarca di Venezia Giovanni Tiepolo (1619-1631), parte ad Agostino degli Agostini, (1530-1574), un patrizio veneziano il cui nome è legato essenzialmente ad una cronaca dal 421 al 1570. Indipendentemente da chi sia il primitivo autore, la cronaca, di discreto pregio per la storia interna e il funzionamento delle istituzioni veneziane, presenta elementi di spiccata originalità dal punto di vista compositivo e formale che la pongono in una prospettiva storiografica alternativa al dualismo tra la storiografia ufficiale promossa per pubblico decreto e l'iniziativa privata dei diaria del XV-XVI. La cronaca veneziana, abbandonata per formule più sofisticate e innovative di diffusione dell'informazione pubblica, sopravvive, formalmente immutata nella sua arcaicità, rinnovandosi nella tendenza a creare compendi ricchi di documenti e di elenchi, destinati ad aiutare la nobiltà ad orientarsi nel mondo socio-politico contemporaneo. Si consuma così il divorzio fra l'informazione tecnico-politica utile al patriziato nello svolgimento del suo lavoro e la storiografia pubblica che, di fronte alle varie esigenze e ai diversi generi letterari, sceglie ideologicamente di abbracciare il genere delle laus civitatis e della storiografia laudativa ed encomiastica. In questo contesto si inserisce la Cronaca esemplata dal Patriarca Giovanni Tiepolo, chiaro esempio di un tentativo di razionalizzazione dell'informazione in cui le notizie e gli elementi non ritenuti immediatamente utili come le lunghe liste dei 41 elettori, le promissioni ducali, nonchè singoli episodi ed eventi trattati, trovano una collocazione esterna alla cronaca, in quello che Reines definisce l'ormai nascente archivio politico del XVI secolo.

Raccontare gli Antichi: le "Imagini" di Vincenzo Cartari

Con le "Imagini degli dei degli antichi", pubblicate a Venezia nel 1556 e poi in più edizioni arricchite e illustrate, l’impegnato gentiluomo estense Vincenzo Cartari realizza il primo, fortunatissimo manuale mitografico italiano in lingua volgare, diffuso e tradotto in tutta l’Europa moderna. Cartari rimodula, secondo accenti divulgativi ma fedeli, fonti latine tradizionali: come le ricche "Genealogie deorum gentilium" di Giovanni Boccaccio, l’appena precedente "De deis gentium varia et multiplex historia" di Lilio Gregorio Giraldi, i curiosi "Fasti" ovidiani, da lui stesso commentati e tradotti. Soprattutto, però, introduce il patrimonio millenario di favole ed esegesi classiche, di aperture egiziane, mediorientali, sassoni, a una chiave di lettura inedita, agile e vitalissima: l’ecfrasi. Le divinità e i loro cortei di creature minori, aneddoti leggendari e attributi identificativi si susseguono secondo un taglio iconico e selettivo. Sfilano, in trionfi intrisi di raffinato petrarchismo neoplatonico e di emblematica picta poesis rinascimentale, soltanto gli aspetti figurabili e distintivi dei personaggi mitici: perché siano «raccontate interamente» tutte le cose attinenti alle figure antiche, «con le imagini quasi di tutti i dei, e le ragioni perché fossero così dipinti». Così, le "Imagini" incontrano il favore di lettori colti e cortigiani eleganti, di pittori e ceramisti, di poeti e artigiani. Allestiscono una sorta di «manuale d’uso» pronto all’inchiostro del poeta o al pennello dell’artista, una suggestiva raccolta di «libretti figurativi» ripresi tanto dalla maniera di Paolo Veronese o di Giorgio Vasari, quanto dal classicismo dei Carracci e di Nicolas Poussin. Si rivelano, infine, summa erudita capace di attirare appunti e revisioni: l’antiquario padovano Lorenzo Pignoria, nel 1615 e di nuovo nel 1626, vi aggiunge appendici archeologiche e comparatistiche, interessate al remoto regno dei faraoni quanto agli esotici idoli orientali e dei Nuovi Mondi.

Development, characterization, and application of flowing atmospheric-pressure afterglow ionization for mass spectrometric analysis of ambient organic aerosols

Addressing current limitations of state-of-the-art instrumentation in aerosol research, the aim of this work was to explore and assess the applicability of a novel soft ionization technique, namely flowing atmospheric-pressure afterglow (FAPA), for the mass spectrometric analysis of airborne particulate organic matter. Among other soft ionization methods, the FAPA ionization technique was developed in the last decade during the advent of ambient desorption/ionization mass spectrometry (ADI–MS). Based on a helium glow discharge plasma at atmospheric-pressure, excited helium species and primary reagent ions are generated which exit the discharge region through a capillary electrode, forming the so-called afterglow region where desorption and ionization of the analytes occurs. Commonly, fragmentation of the analytes during ionization is reported to occur only to a minimum extent, predominantly resulting in the formation of quasimolecular ions, i.e. [M+H]+ and [M–H]– in the positive and the negative ion mode, respectively. Thus, identification and detection of signals and their corresponding compounds is facilitated in the acquired mass spectra. The focus of the first part of this study lies on the application, characterization and assessment of FAPA–MS in the offline mode, i.e. desorption and ionization of the analytes from surfaces. Experiments in both positive and negative ion mode revealed ionization patterns for a variety of compound classes comprising alkanes, alcohols, aldehydes, ketones, carboxylic acids, organic peroxides, and alkaloids. Besides the always emphasized detection of quasimolecular ions, a broad range of signals for adducts and losses was found. Additionally, the capabilities and limitations of the technique were studied in three proof-of-principle applications. In general, the method showed to be best suited for polar analytes with high volatilities and low molecular weights, ideally containing nitrogen- and/or oxygen functionalities. However, for compounds with low vapor pressures, containing long carbon chains and/or high molecular weights, desorption and ionization is in direct competition with oxidation of the analytes, leading to the formation of adducts and oxidation products which impede a clear signal assignment in the acquired mass spectra. Nonetheless, FAPA–MS showed to be capable of detecting and identifying common limonene oxidation products in secondary OA (SOA) particles on a filter sample and, thus, is considered a suitable method for offline analysis of OA particles. In the second as well as the subsequent parts, FAPA–MS was applied online, i.e. for real time analysis of OA particles suspended in air. Therefore, the acronym AeroFAPA–MS (i.e. Aerosol FAPA–MS) was chosen to refer to this method. After optimization and characterization, the method was used to measure a range of model compounds and to evaluate typical ionization patterns in the positive and the negative ion mode. In addition, results from laboratory studies as well as from a field campaign in Central Europe (F–BEACh 2014) are presented and discussed. During the F–BEACh campaign AeroFAPA–MS was used in combination with complementary MS techniques, giving a comprehensive characterization of the sampled OA particles. For example, several common SOA marker compounds were identified in real time by MSn experiments, indicating that photochemically aged SOA particles were present during the campaign period. Moreover, AeroFAPA–MS was capable of detecting highly oxidized sulfur-containing compounds in the particle phase, presenting the first real-time measurements of this compound class. Further comparisons with data from other aerosol and gas-phase measurements suggest that both particulate sulfate as well as highly oxidized peroxyradicals in the gas phase might play a role during formation of these species. Besides applying AeroFAPA–MS for the analysis of aerosol particles, desorption processes of particles in the afterglow region were investigated in order to gain a more detailed understanding of the method. While during the previous measurements aerosol particles were pre-evaporated prior to AeroFAPA–MS analysis, in this part no external heat source was applied. Particle size distribution measurements before and after the AeroFAPA source revealed that only an interfacial layer of OA particles is desorbed and, thus, chemically characterized. For particles with initial diameters of 112 nm, desorption radii of 2.5–36.6 nm were found at discharge currents of 15–55 mA from these measurements. In addition, the method was applied for the analysis of laboratory-generated core-shell particles in a proof-of-principle study. As expected, predominantly compounds residing in the shell of the particles were desorbed and ionized with increasing probing depths, suggesting that AeroFAPA–MS might represent a promising technique for depth profiling of OA particles in future studies.