Nutrients balances and milk fatty acid profile of mid lactation dairy cows supplemented with monensin

The aim of this study was to evaluate the nutrients balance and milk fatty acids profile of dairy cows supplemented with monensin. Twelve Brazilian Holstein dairy cows were distributed into four balanced 3x3 Latin squares, and fed with the following diets: control (C), basal diet without addition of monensin, monensin 24 (M24), addition of 24mg/kg DM of monensin, and monensin 48 (M48), addition of 48mg/kg DM. The experimental diets influenced the efficiency of net energy of lactation utilization. A quadratic effect was observed for the energy balance. It was observed effect of diets on nitrogen balance. It was observed effect of monensin in the milk yield, composition and in the milk fatty acids profile. Monensin in diets of dairy cows in mid lactation, using corn silage, improved the nutrients balance and milk fatty acid profile with 24mg/kg DM.

Bird species diversity in the Atlantic Forest of Brazil is not explained by the Mid-domain Effect

The Atlantic Forest is an excellent case study for the elevational diversity of birds, and some inventories along elevational gradients have been carried out in Brazil. Since none of these studies explain the patterns of species richness with elevation, we herein review all Brazilian studies on bird elevational diversity, and test a geometric constraint null model that predicts a unimodal species-altitude curve, the Mid-domain Effect (MDE). We searched for bird inventories in the literature and also analysed our own survey data using limited-radius point counts along an 800 m elevational gradient in the state of São Paulo, Brazil. We found 10 investigations of elevational diversity of Atlantic Forest birds and identified five different elevational patterns: monotonic decreasing diversity, constant at low elevations, constant at low elevations but increasing towards the middle, and two undescribed patterns for Atlantic Forest birds, trough-shaped and increasing diversity. The average MDE fit was low (r² = 0.31) and none of the MDE predictions were robust across all gradients. Those studies with good MDE model fits had obvious sampling bias. Although it has been proposed that the MDE may be positively associated with the elevational diversity of birds, it does not fit the Brazilian Atlantic Forest bird elevational diversity.

In situ and remote sensing signature of meddies east of the mid-Atlantic ridge

[EN] Mediterranean Water eddies (meddies) are thought to play an important climatic role. Nevertheless, their dynamics are not sufficiently known because of difficulties encountered in their observation. Though propagating below the main thermocline, a number of pieces of evidence of sea surface manifestation of meddies are collected. The present work is based on joint in situ and altimetry data analyses to prove that the meddies can be followed with remote sensing data for long periods of time. The in situ observations are based on data from an oceanographic cruise, which crossed three meddies, and reanalysis of historical data sets, including RAFOS floats paths. Suggested methodology permitted us to obtain uninterrupted tracks for several meddies for a period from several months to more than 2 years. It was found that the dynamically calm region to the north of the Azores current presents favorable conditions for meddy tracking. The meddy surface signal may become shattered and difficult to follow during interaction with a strong dynamic structures (the Azores current/surface vortexes) or peaking topography. Theoretical considerations support the observations and lead to the conclusion that the dynamic signature of meddies at the sea surface is an intrinsic property of meddy dynamics

Lagrangian evolution of a mid ocean anticyclonic eddy

[EN]The lagrangian evolution of 4 months old anticyclonic intrathermocline eddy of the Canary Eddy Corridor is investigated from the trajectories of 5 satellites tracked drifting buoys. Buoys were drogued below and above the Ekman depth at 15 m and 100 m, respectively. One buoy remained inside the eddy during almost 4 months being thus a long lived coherent feature with a life span of at least 8 months. The eddy consisted in a central core rotating in solid body rotation with a rather constant periodicity of 4 days and in an outer ring rotating much more slowly with periodicities between 8 and 12 days…

Studio del copolimero stirene-acrilonitrile mediante spettroscopia IR e correlazione bidimensionale

Lo studio di cambiamenti strutturali inter o intramolecolari nei materiali polimerici può essere effettuato mediante la spettroscopia infrarossa associata a quella di correlazione bidimensionale (2D-COS, two-dimensional correlation spectroscopy). Questa tecnica, applicata a campioni del copolimero stirene-acrilonitrile (SAN) a diversa composizione, consente di interpretare variazioni spettrali riscontrate e l’andamento della temperatura di transizione vetrosa, Tg. L’applicazione della spettroscopia di correlazione bidimensionale (2D-COS) e l’analisi dell’intensità delle bande spettrali in funzione del contenuto di AN nel copolimero SAN, prevedono lo sviluppo di un metodo per correggere gli spettri IR da instabilità dovute alla linea di base e da variazioni derivanti dallo spessore dei film. A tal fine si sottopone lo spettro IR di ogni film di SAN alla correzione della linea di base e successivamente al processo di normalizzazione. La banda di vibrazione sottoposta ad analisi 2D-COS è quella corrispondente allo stretching del gruppo −C≡N in quanto presenta le maggiori variazioni in funzione della composizione del copolimero. La 2D-COS evidenzia che tali variazioni sono attribuibili alla variazione contemporanea di frequenza di assorbimento, larghezza e intensità di banda. A partire da questa osservazione si può dedurre la presenza nel materiale di un’interazione dipolo-dipolo di tipo intra-molecolare tra i gruppi nitrilici.

Il mercato e-MID: intraday e crisi finanziaria

Il lavoro di tesi ha l’obiettivo di dare seguito e profondità alle verifiche già condotte negli anni scorsi da Monticini e Baglioni, da Angelini e da Vento e La Ganga. Nel dettaglio nella serie storica dei tassi scambiati, sul comparto ON, del mercato e-Mid, riscontrano empiricamente che i tassi scambiati nelle prime ore del mattino sono in media superiori rispetto a quelli del pomeriggio. In pratica emerge un costo orario positivo. Il campione è costituito da 196.571 contratti eseguiti tra il 1 gennaio 2007 ed il 31 marzo 2009, sul comparto ON. Le analisi si sono concentrate sull’intensità del reversal patttern, oltre che su base giornaliera anche su base settimanale (day of the week) e su base mensile (month of the year effect). Le medesime analisi sono state condotte sull’ultimo giorno del periodo di mantenimento, e su particolari giorni che hanno scandito la crisi finanziaria. Per osservare la dinamica del reversal pattern prima e durante la crisi, le medesime verifiche sono condotte su tre sub campioni. Il primo considera tutti i contratti dall’inizio e fino all’8 agosto compreso; il secondo da quest’ultimo e fino al 12 settembre 2008 compreso; l’ultimo dal fallimento della Lehman e fino al 31 marzo 2009. I risultati confermano la presenza del reversal, per tutti i giorni e per tutti i mesi. Tuttavia quando il campione è suddiviso, le stime del primo campione, perdono di significatività, in particolare il giovedì ed il mese di febbraio. Sel medesimo periodo di campionamento al fine di verificare se il reversal pattern sia attribuire in parte anche alla liquidità del mercato, si è indagato su tutte le proposte in bid ed in offer, e dei relativi volumi, ovvero sul bid ask spread, il relativo prezzo medio ed i volumi. Anche in questo caso le analisi si sono concentrate oltre che sul campione originario, anche sui tre sub campioni in cui è stato successivamente suddiviso. . Quando infine si analizzano volumi e proposte, si nota innanzitutto che, al mattino, quando i prezzi scambiati sono maggiori il bid ask spread è minimo. Viceversa il pomeriggio quando il BAS è minore. La stessa dinamica si osserva per lo spread effettivo (SE), il quale è pari alla differenza tra prezzo medio delle contrattazioni e prezzo medio delle proposte. Infine i volumi sia delle proposte che delle contrattazioni, sono maggiori al mattino rispetto al pomeriggio e tendono a decrescere con l’intensificarsi della crisi. Inoltre i volumi in bid sono sempre maggiori rispetto a quelli in offer al mattino piuttosto che al pomeriggio.

Cold cloud climatology over Europe and the Mediterranean during the warm season from Meteosat IR imagery

Thermal infrared (IR, 10.5 – 12.5 m) images from the Meteosat Visible and Infrared Imager (MVIRI) of cold cloud episodes (cloud top brightness temperature < 241 K) are used as a proxy of precipitating clouds to derive a warm season (May-August) climatology of their coherency, duration, span, and speed over Europe and the Mediterranean. The analysis focuses over the 30°-54°N, 15°W-40°E domain in May-August 1996-2005. Harmonic analysis using discrete Fourier transforms is applied together with a statistical analysis and an investigation of the diurnal cycle. This study has the objective to make available a set of results on the propagation dynamics of the cloud systems with the aim of assist numerical modellers in improving summer convection parameterization. The zonal propagation of cold cloud systems is accompanied by a weak meridional component confined to narrow latitude belts. The persistence of cold clouds over the area evidences the role of orography, the Pyrenees, the Alps, the Balkans and Anatolia. A diurnal oscillation is found with a maximum marking the initiation of convection in the lee of the mountains and shifting from about 1400 UTC at 40°E to 1800 UTC at 0°. A moderate eastward propagation of the frequency maximum from all mountain chains across the domain exists and the diurnal maxima are completely suppressed west of 5°W. The mean power spectrum of the cold cloud frequency distribution evidences a period of one day all over Europe disappearing over the ocean (west of 10°W). Other maxima are found in correspondence of 6 to 10 days in the longitudes from 15° W to 0° and indicate the activity of the westerlies with frontal passage over the continent. Longer periods activities (from 15 up to 30 days) were stronger around 10° W and from 5° W to 15° E and are likely related to the Madden Julian Oscillation influence. The maxima of the diurnal signal are in phase with the presence of elevated terrain and with land masses. A median zonal phase speed of 16.1 ms-1 is found for all events ≥ 1000 km and ≥ 20 h and a full set of results divided by years and recurrence categories is also presented.

Spektromikroskopische Analyse von Nukleationsdomänen in epitaktischen Diamantschichten auf Ir,SrTiO 3 und von präsolaren SiC-Meteoritenkörnern

Im Rahmen dieser Arbeit wurden zwei verschiedene Systeme untersucht, deren verbindende Gemeinsamkeit in den verwendeten ortsauflösenden, spektroskopischen Messmethoden der Oberflächenanalytik, wie z.B. abbildendes XPS, Röntgennahkanten-Photoemissionsmikroskopie (XANES-PEEM) und Augerspektroskopie (AES) liegt. Im ersten Teil der Arbeit wurden Diamant-Nukleationsdomänen auf Ir/SrTiO3 untersucht und mit vorherrschenden Modellen aus der Literatur verglichen. Die Nukleationsdomänen, wie sie im Mikrowellen-induzierten CVD Prozess unter Verwendung der BEN Prozedur (bias-enhanced nucleation) entstehen, bilden die „Startschicht“ für ein heteroepitaktisches Wachstum einer hoch orientierten Diamantschicht. Sie entwickeln sich aber unter Bedingungen, unter denen 3D-Diamant abgetragen und weggeätzt wird. Mittels XANES-PEEM Messungen konnte erstmals die lokale Bindungsumgebung des Kohlenstoffs in den Nukleationsdomänen ortsaufgelöst aufgezeigt werden und aus AES Messungen ließ sich die Schichtdicke der Nukleationsdomänen abschätzen. Es zeigte sich, dass die Nukleationsdomänen Bereiche mit etwa 1 nm Dicke darstellen, in denen der Übergang von eine sp2-koordinierte amorphen Kohlenstoff- zu einer Diamantschicht mit hohem sp3 Anteil abläuft. Zur Erklärung des Nukleationsprozesses wurde auf das „Clustermodell“ von Lifshitz et al. zurückgegriffen, welches um einen wesentlichen Aspekt erweitert wurde. Die Stabilität der Nukleationsdomänen gegen die Ätzwirkung des Nukleationsprozesses auf Volumendiamant wird durch eine starke Wechselwirkung zwischen dem Diamant und dem Iridiumsubstrat erklärt, wobei die Dicke von etwa 1 nm als Maß für die Ausdehnung dieses Wechselwirkungsbereichs angesehen wird. Der zweite Teil der Arbeit beschäftigt sich mit der Charakterisierung präsolarer SiC-Körner und darin eingeschlossener Spurenelemente. Neben den Hauptelementen Si und C wurden auch Spinelle wie Chromit (FeCr2O4), Korund (Al2O3) und auch verschiedene Spurenelemente (z. B. Al, Ba und Y) nachgewiesen. Ferner wurden XPS-Linien bei Energien nachgewiesen, welche sich den Seltenen Erden Erbium, Thulium und Dysprosium zuordnen lassen. Aufgrund von Abweichungen zur Literatur bzgl. der ausgeprägten Intensität der XPS-Linien, wurde als alternative Erklärungsmöglichkeit für verschiedene Signale der Nachweis von stark schwefelhaltigen Körnern (z.B. so genannte „Fremdlinge“) mit Aufladungen von mehreren Volt diskutiert. Es zeigt sich, dass abbildendes XPS und XANES-PEEM Methoden zur leistungsfähigen chemischen Charakterisierung von SiC-Körnern und anderer solarer und präsolarer Materie im Größenbereich bis herab zu 100 – 200 nm Durchmesser (z.B. als Grundlage für eine spätere massenspektrometrische Isotopenanalyse)darstellen.

The role of the West African Monsoon in the tropical to mid-latitudes climate

The interaction between atmosphere–land–ocean–biosphere systems plays a prominent role on the atmospheric dynamics and on the convective rainfall distribution over the West Africa monsoon area during the boreal summer. In particular, the initialization of convective systems in the Sub – Sahelian region has been directly linked to soil moisture heterogeneities identified as the major triggering, development and propagation of convective systems. The present study aims at investigating African monsoon large scale convective dynamics and rainfall diurnal cycle through an exploration of the hypothesis behind the mechanisms of a monsoon phenomenon as an emergence of a collective dynamics of many propagating convective systems. Such hypothesis is based on the existence of an internal self – regulation mechanism among the various components. To achieve these results a multiple analysis was performed based on remote sensed rainfall dataset, and global and regional modelling data for a period of 5 seasons: 2004 - 2008. Satellite rainfall data and convective occurrence variability were studied for assessing typical spatio – temporal signatures and characteristics with an emphasis to the diurnal cycle footprint. A global model and regional model simulation datasets, specifically developed for this analysis and based on Regional Atmospheric Modelling System – RAMS, have been analysed. Results from numerical model datasets highlight the evidence of a synchronization between the destabilization of the convective boundary layer and rainfall occurrence due to the solar radiation forcing through the latent heat release. This supports the conclusion that the studied interacting systems are associated with a process of mutual adjustment of rhythms. Furthermore, this rainfall internal coherence was studied in relation to the West African Heat Low pressure system, which has a prominent role in the large scale summer variability over the Mediterranean area since it is acting as one of dynamic link between sub tropical and midlatitudes variability.

Sintesi e caratterizzazione di complessi misti Ir(iii)-Eu(iii) per l'emissione di luce bianca

Diodi organici emettitori di luce bianca (WOLEDs) sono dei dispositivi promettenti per la realizzazione di sorgenti luminose a basso consumo di energia, in quanto essi combinano un’alta efficienza e bassi costi di produzione con l’interessante caratteristica di poter produrre grandi superfici che emettono luce bianca di buona qualità. Tuttavia, la durata, le prestazioni e i costi devono ancora essere ottimizzati affinché i WOLEDs possano diventare commercialmente competitivi con le altre più comuni fonti di illuminazione; in particolare è necessario migliorare la stabilità e l’efficienza degli emettitori. Nella presente tesi viene trattata la sintesi di molecole organometalliche a singolo componente per ottenere un’elettroluminescenza di un bianco più puro possibile. In particolare l’attenzione è stata rivolta all’ottenimento di complessi eterometallici Ir-Eu. Sono stati sintetizzati tre diversi dimeri di Ir (III), con sistemi fenilpiridinici variamente fluorurati come leganti; a secondo del tipo di legante si hanno delle variazioni delle proprietà fotofisiche del complesso di Ir (III) successivamente prodotto. In seguito sono stati sintetizzati leganti bifunzionali contenenti un’unità isocianuro (in grado di coordinare selettivamente l’Iridio) e un gruppo acetilacetonato (in grado di coordinare selettivamente l’Europio). Tali leganti sono stati poi impiegati per formare il complesso di Eu (III). Infine, la reazione tra i dimeri di Ir (III) e il complesso di Eu (III) ha portato alla formazione dei complessi eterometallici Ir-Eu, che sono stati poi caratterizzati sia strutturalmente che fotofisicamente. Grazie ai due diversi centri emissivi presenti nella stessa molecola si è ottenuta una complessiva luce bianca.

Solubility and permeability as in vitro predictors for in vivo performance of fenofibrate IR solid dosage forms

This current work focused on the simulation of in vivo dissolution and permeation in order to be able to predict the in vivo performance of orally administered fenofibrate immediate release formulations. Therefore, the effects of the formulation surfactants on in vivo solubility and permeation of fenofibrate under physiologically relevant excipient concentrations were emphasized.rnIt was shown that the surfactant sodium dodecyl sulfate (SDS) may decrease rather than increase the solubility of fenofibrate in vivo. This was related to the interference of SDS with the vesicular system of the biorelevant medium, FaSSIFmod, and therefore its solubilization capacity. rnMoreover, in vitro permeation studies revealed that SDS concentrations inversely correlated with fenofibrate permeability. Through combination of the observed permeation and solubility data a good in vitro/in vivo correlation regarding Cmax values in humans could be established for five fenofibrate formulations which were based on the same manufacturing technique.rnBesides the experimental part, the major characteristics and their potential implementation in a dissolution/permeation device were discussed based on the promising realization of the in vitro solubility and permeation methods. rn

Enantioselective synthesis of Equol with Ir-BARF and labelling with deuterium

In this project we researched and optimized an new synthetic route for R-Equol, a molecule that is attracting increasing interest for the medicine because of its phytoestrogenic properties and the chemoprevention of breast cancer. To reach this objective we start, from smaller building blocks, with the synthesis of Daidzein followed by a chemoselective borane reduction to obtain an olefin that will be hydrogenated enantioselectively with a commercial Ir-BARF catalyst. The increasing success of these catalysts even with this genre of substrates has already given good results with different catalysts in both e.e. and yield. For further researches we deuterate the Equol in the aliphatic O-ring and attempt a secondary synthetic route with an hydrogenation using QN-modified Pd.