Termotectônica por traços de fissão em apatitas dos altos estrutrais de Pitanga, Pau d'Álho e Jibóia - centro do Estado de São Paulo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structure and absolute configuration of diterpenoids from hymenaea stigonocarpa

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Constraining the absolute neutrino mass scale and Majorana CP violating phases by future 0νββ decay experiments

Assuming that neutrinos are Majorana particles, in a three-generation framework, current and future neutrino oscillation experiments can determine six out of the nine parameters which fully describe the structure of the neutrino mass matrix. We try to clarify the interplay among the remaining parameters, the absolute neutrino mass scale and two CP violating Majorana phases, and how they can be accessed by future neutrinoless double beta (0vυββ) decay experiments, for the normal as well as for the inverted order of the neutrino mass spectrum. Assuming the oscillation parameters to be in the range presently allowed by atmospheric, solar, reactor, and accelerator neutrino experiments, we quantitatively estimate the bounds on m 0, the lightest neutrino mass, that can be inferred if the next generation 0υββ decay experiments can probe the effective Majorana mass (m ee) down to ∼1 meV. In this context we conclude that in the case that neutrinos are Majorana particles, (a) if m 0≳300 meV, i.e., within the range directly attainable by future laboratory experiments as well as astrophysical observations, then m ee≳30 meV must be observed, (b) if m 0 ≤ 300 meV, results from future 0υββ decay experiments combined with stringent bounds on the neutrino oscillation parameters, especially the solar ones, will place much stronger limits on the allowed values of m 0 than these direct experiments. For instance, if a positive signal is observed around m ee = 10 meV, we estimate 3≲m 0/meV≲65 at 95% C.L.; on the other hand, if no signal is observed down to m ee = 10 meV, then m 0≲55 meV at 95% C.L.

Validation of absolute quantitative real-time PCR for the diagnosis of streptococcus agalactiae in fish

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

VCD to determine absolute configuration of natural product molecules: secolignans from Peperomia blanda

The absolute configuration and solution-state conformers of three peperomin-type secolignans isolated from Peperomia blanda (Piperaceae) are unambiguously determined by using vibrational circular dichroism (VCD) spectroscopy associated with density functional theory (DFT) calculations. Advantages of VCD over the electronic form of CD for the analysis of diastereomers are also discussed. This work extends our growing knowledge about secondary metabolites within the Piperaceae family species while providing a definitive and straightforward method to assess the absolute stereochemistry of secolignans.

Further monoterpene chromane esters from Peperomia obtusifolia: VCD determination of the absolute configuration of a new diastereomeric mixture

A reinvestigation of the monoterpene chromane ester enriched fraction from Peperomia obtusifolia using chiral chromatography led to the identification of a minor peak, which was elucidated by NMR and HRMS as fenchyl-3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3 ''-methyl-2 ''-butenyl)-2-(4'-methyl-1',3'-pentadienyl)-2H-1-benzopyran-6-carboxylate, the same structure assigned to two other fenchyl esters described previously, pointing out a stereoisomeric relationship among them. Further NMR analysis revealed that it was actually a mixture of two compounds, whose absolute configurations were determined by VCD measurements. Although, almost no vibrational transitions could be assigned to the chiral chromane, the experimental VCD spectrum was largely opposite to that obtained for the average experimental VCD [(2S,1'''R,2'''R,4'''S + 2R,1'''R,2'''R,4'''S)/2] for fenchol derivatives. These results allowed us to assign the putative compounds as a racemic mixture of the chiral chromane esterified with the monoterpene (1S,2S,4R)fenchol, which had not been identified in our early work. (C) 2012 Elsevier Ltd. All rights reserved.

Procedures of quality control and data analysis of multi-site ground-based observations for the absolute flux calibration of Gaia

The Gaia space mission is a major project for the European astronomical community. As challenging as it is, the processing and analysis of the huge data-flow incoming from Gaia is the subject of thorough study and preparatory work by the DPAC (Data Processing and Analysis Consortium), in charge of all aspects of the Gaia data reduction. This PhD Thesis was carried out in the framework of the DPAC, within the team based in Bologna. The task of the Bologna team is to define the calibration model and to build a grid of spectro-photometric standard stars (SPSS) suitable for the absolute flux calibration of the Gaia G-band photometry and the BP/RP spectrophotometry. Such a flux calibration can be performed by repeatedly observing each SPSS during the life-time of the Gaia mission and by comparing the observed Gaia spectra to the spectra obtained by our ground-based observations. Due to both the different observing sites involved and the huge amount of frames expected (≃100000), it is essential to maintain the maximum homogeneity in data quality, acquisition and treatment, and a particular care has to be used to test the capabilities of each telescope/instrument combination (through the “instrument familiarization plan”), to devise methods to keep under control, and eventually to correct for, the typical instrumental effects that can affect the high precision required for the Gaia SPSS grid (a few % with respect to Vega). I contributed to the ground-based survey of Gaia SPSS in many respects: with the observations, the instrument familiarization plan, the data reduction and analysis activities (both photometry and spectroscopy), and to the maintenance of the data archives. However, the field I was personally responsible for was photometry and in particular relative photometry for the production of short-term light curves. In this context I defined and tested a semi-automated pipeline which allows for the pre-reduction of imaging SPSS data and the production of aperture photometry catalogues ready to be used for further analysis. A series of semi-automated quality control criteria are included in the pipeline at various levels, from pre-reduction, to aperture photometry, to light curves production and analysis.

Qualitative and absolute quantitative studies of the cell-nanoparticle interaction

This thesis focused on the polymer’s influence on the interaction of polymeric NPs with epithelial cells. Furthermore, the measurement of single submicron nanoparticles in a commercially available flow cytometer was established, to provide a new method in the toolbox for nanoparticle-cell studies. This gave way to develop a routine for the absolute quantification of intracellular NPs via flow cytometry. rnThe cellular uptake of poly(methyl methacrylate) (PMMA), polystyrene (PS) and poly(L-lactide) (PLLA) nanoparticles was investigated via flow cytometry. PLLA-NPs were internalized the most efficiently. But upon co-incubation of PS and PLLA particles with cells, the two particles mutually influenced their uptake, slightly shifting the relative uptake efficiencies. This phenomenon should be based on specific properties of the different polymer materials. The findings indicated a competition (which is strongly influenced by properties of the respective polymeric material) for the uptake into the cells, allegedly due to competition for specific coatings with serum components that enhances the NPs’ cellular uptake. The fluorescence of single 150 nm particles was determined with a benchtop cytometer, breaching the machine’s detection limit but yielding precise NP fluorescence standardization factors. Up to now, these standardization factors are mostly determined by spectroscopic analysis of the particles’ dye content. Finally a flow cytometric routine for absolute particle counting in cells was devised. This quantitation revealed a low uptake efficiency for un-functionalized PMMA NPs of less than 150 NPs (approx. 0,001 % of added) per cell.rn

Absolute Hodge cycles and Deligne's principle b

I cicli di Hodge assoluti sono stati utilizzati da Deligne per dividere la congettura di Hodge in due sotto-congetture. La prima dice che tutte le classi di Hodge su una varietà complessa proiettiva liscia sono assolute, la seconda che le classi assolute sono algebriche. Deligne ha dato risposta affermativa alla prima sottocongettura nel caso delle varietà abeliane. La dimostrazione si basa su due teoremi, conosciuti rispettivamente come Principio A e Principio B. In questo lavoro vengono presentate la teoria delle classi di Hodge assolute e la dimostrazione del Principio B.

Atropisomeric xanthines: Synthesis, stereodynamics and absolute configuration

During the thesis period a new class of atropisomeric xanthine derivatives has been studied. We decided to focus our attention on these purine bases because of their various biological activities, that could play an important role in the discovery of new bioactive atropisomers. The synthesized compounds bear an Aryl-N chiral axis in position 1 of the xanthine scaffold, around which the rotation is prevented by the presence of bulky ortho substituents. Through a retro synthetic analysis we synthesized three atropisomeric structures bearing in position 1 of the purine scaffold respectively an o-tolyl, o-nitrophenyl and a 1-naphthyl group. The conformational studies by DFT simulations showed that the interconversion energy barrier between the two available skewed conformations is higher enough to obtain thermally stable atropisomers. After the separation of the atropisomers, the experimental energy of interconversion was investigated by means of kinetic studies following the thermal racemization process using an enantioselective HPLC column. The absolute configuration of each atropisomer was assigned by experimental ECD analysis and TD-DFT simulations of the ECD spectra.

Right ventricular absolute myocardial blood flow in complex congenital heart disease

A consequence in patients with d-transposition of the great arteries (d-TGA) and tetralogy of Fallot (TOF) is right ventricular hypertrophy (RVH) and right ventricular failure. Myocardial contrast echocardiography (MCE) permits the determination of the myocardial microvascular density reflected by the relative myocardial blood volume (rBV; ml/ml). This study was conducted to elucidate the relationship between RVH and myocardial microvascular changes by quantitative MCE in patients with d-TGA and TOF.

Absolute pKa Determinations for Substituted Phenols

The CBS-QB3 method was used to calculate the gas-phase free energy difference between 20 phenols and their respective anions, and the CPCM continuum solvation method was applied to calculate the free energy differences of solvation for the phenols and their anions. The CPCM solvation calculations were performed on both gas-phase and solvent-phase optimized structures. Absolute pKa calculations with solvated phase optimized structures for the CPCM calculations yielded standard deviations and root-mean-square errors of less than 0.4 pKa unit. This study is the most accurate absolute determination of the pKa values of phenols, and is among the most accurate of any such calculations for any group of compounds. The ability to make accurate predictions of pKa values using a coherent, well-defined approach, without external approximations or fitting to experimental data, is of general importance to the chemical community. The solvated phase optimized structures of the anions are absolutely critical to obtain this level of accuracy, and yield a more realistic charge separation between the negatively charged oxygen and the ring system of the phenoxide anions.