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.

U-Pb zircon in situ dating with LA-MC-ICP-MS using a mixed detector configuration

The LA-MC-ICP-MS method applied to U-Pb in situ dating is still rapidly evolving due to improvements in both lasers and ICP-MS. To test the validity and reproducibility of the method, 5 different zircon samples, including the standard Temora-2, ranging in age between 2.2 Ga and 246 Ma, were dated using both LA-MC-ICP-MS and SHRIMP. The selected zircons were dated by SHRIMP and, after gentle polishing, the laser spot was driven to the same site or on the same zircon phase with a 213 nm laser microprobe coupled to a multi-collector mixed system. The data were collected with a routine spot size of 25 μm and, in some cases, of 15 and 40 μm. A careful cross-calibration using a diluted U-Th-Pb solution to calculate the Faraday reading to counting rate conversion factors and the highly suitable GJ-1 standard zircon for external calibrations were of paramount importance for obtaining reliable results. All age results were concordant within the experimental errors. The assigned age errors using the LA-MC-ICP-MS technique were, in most cases, higher than those obtained by SHRIMP, but if we are not faced with a high resolution stratigraphy, the laser technique has certain advantages.

Structural stability of flexible lines in catenary configuration under torsion

Catenary risers can present during installation a very low tension close to seabed, which combined with torsion moment can lead to a structural instability, resulting in a loop. This is undesirable once it is possible that the loop turns into a kink, creating damage. This work presents a numerical methodology to analyze the conditions of loop formation in catenary risers. Stability criteria were applied to finite element models, including geometric nonlinearities and contact constraint due to riser-seabed interaction. The classical Greenhill's formula was used to predict the phenomenon and parametric analysis shows a “universal plot” able to predict instability in catenaries using a simple equation that can be applied for typical risers installation conditions and, generically, for catenary lines under torsion.

Gold ion implantation into alumina using an “inverted ion source” configuration.

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is injected into a space held at high negative potential, allowing considerable savings both economically and technologically. We used an “inverted ion implanter” of this kind to carry out implantation of gold into alumina, with Au ion energy 40 keV and dose (3–9) × 1016 cm−2. Resistivity was measured in situ as a function of dose and compared with predictions of a model based on percolation theory, in which electron transport in the composite is explained by conduction through a random resistor network formed by Au nanoparticles. Excellent agreement is found between the experimental results and the theory.

Polyphase drive systems configuration aiming EMI mitigation

Topologies of motor drive systems are studied, aiming the reduction of common-mode (CM) currents. Initially, the aspects concerning the CM currents circulation are analysed. The reason of common-mode voltages generation, the circulating paths for the resulting CM currents and their effects are discussed. Then, a non-conventional drive system configuration is proposed in order to reduce the CM currents and their effects. This configuration comprehends a non-conventional inverter module wired to a motor with an unusual connection. The cables arrangement differs from the standard solution, too. The proposed topology is compared with other ones, like the active circuit for common-mode voltages compensation. The contribution of the configuration to the reduction of CM voltages and currents and their related interferences are evaluated, based on numerical simulations. Some results are presented and discussed regarding the suitability of the proposed configuration as a potential solution to reduce the CM currents effects, when the state of art and implementation cost of drives are taken into account.

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.

Stress free configuration of the human eye

Numerical simulations of eye globes often rely on topographies that have been measured in vivo using devices such as the Pentacam or OCT. The topographies, which represent the form of the already stressed eye under the existing intraocular pressure, introduce approximations in the analysis. The accuracy of the simulations could be improved if either the stress state of the eye under the effect of intraocular pressure is determined, or the stress-free form of the eye estimated prior to conducting the analysis. This study reviews earlier attempts to address this problem and assesses the performance of an iterative technique proposed by Pandolfi and Holzapfel [1], which is both simple to implement and promises high accuracy in estimating the eye's stress-free form. A parametric study has been conducted and demonstrated reliance of the error level on the level of flexibility of the eye model, especially in the cornea region. However, in all cases considered 3-4 analysis iterations were sufficient to produce a stress-free form with average errors in node location <10(-6)mm and a maximal error <10(-4)mm. This error level, which is similar to what has been achieved with other methods and orders of magnitude lower than the accuracy of current clinical topography systems, justifies the use of the technique as a pre-processing step in ocular numerical simulations.

Fixed block configuration GDDs with block size 6 and (3, r)-regular graphs

Chapter 1 is used to introduce the basic tools and mechanics used within this thesis. Most of the definitions used in the thesis will be defined, and we provide a basic survey of topics in graph theory and design theory pertinent to the topics studied in this thesis. In Chapter 2, we are concerned with the study of fixed block configuration group divisible designs, GDD(n; m; k; λ1; λ2). We study those GDDs in which each block has configuration (s; t), that is, GDDs in which each block has exactly s points from one of the two groups and t points from the other. Chapter 2 begins with an overview of previous results and constructions for small group size and block sizes 3, 4 and 5. Chapter 2 is largely devoted to presenting constructions and results about GDDs with two groups and block size 6. We show the necessary conditions are sufficient for the existence of GDD(n, 2, 6; λ1, λ2) with fixed block configuration (3; 3). For configuration (1; 5), we give minimal or nearminimal index constructions for all group sizes n ≥ 5 except n = 10, 15, 160, or 190. For configuration (2, 4), we provide constructions for several families ofGDD(n, 2, 6; λ1, λ2)s. Chapter 3 addresses characterizing (3, r)-regular graphs. We begin with providing previous results on the well studied class of (2, r)-regular graphs and some results on the structure of large (t; r)-regular graphs. In Chapter 3, we completely characterize all (3, 1)-regular and (3, 2)-regular graphs, as well has sharpen existing bounds on the order of large (3, r)- regular graphs of a certain form for r ≥ 3. Finally, the appendix gives computational data resulting from Sage and C programs used to generate (3, 3)-regular graphs on less than 10 vertices.