An examination of Australian news coverage of Papua New Guinea

This thesis examines Australian news coverage of Papua New Guinea, a country with which Australia shares geographic proximity and strong historical ties. Specifically, this study examines the coverage of PNG by The Australian and The Sydney Morning Herald newspapers from January 01 until June 30, 2010. This work aims to demonstrate that PNG is a neglected news region. This neglect – in terms of quality reporting – has produced a limited and fragmentary portrayal of PNG in the Australian media. In this context, this study observes that the majority of news stories about PNG tend to lack analysis and contextual background. By examining the process of news framing and news values, this thesis suggests that the disproportionate emphasis on events associated with crime, chaos, disaster, and corruption has constructed PNG as a fragile, suffering and dependent society. The key methodologies used in this thesis are content analysis, and indepth interviews with a selected number of Australian journalists currently or previously based in PNG. The thesis forms part of a much broader examination of the changing trends in international news coverage of developing countries, particularly the Asia-Pacific

Solvation of alkane and alcohol molecules. Energy contributions

In this work we conduct a systematic ab initio study of the solvation of small alkane, monoalcohol and diol molecules, in polar solvents with different properties. A choice of basis set suitable for the type of compounds under study is presented. The various components of the solvent–solute interaction and the cavitation energy are treated individually and their variation with chain length and introduction of hydroxy groups assessed. The use of solute molecules in which controlled changes are imposed allows for an estimation of the relative contributions, thus eliminating accidental error cancellation.Fundacão para a Ciência e Tecnologia SAPIENS POCTI/35415/QUI/200

Conformational study of erythritol and threitol in the gas state by density functional theory calculations

Density functional theory calculations using the B3LYP functional and the 6-311++G(d,p) basis set were carried out on the isolated molecules of erythritol and L-threitol. For the meso isomer, a relatively large number of conformers have to be considered to describe the gas state structure. The lowest energy conformer is characterized by the establishment of a strong intramolecular H-bond between the two terminal hydroxyl groups, giving rise to a seven-membered ring and two additional weaker H-bonds between vicinal OH groups. In the case of L-threitol, two conformers are predominant in the gas state, and both are stabilized by the formation of a cyclic system of four intramolecular hydrogen bonds involving all OH groups. The conformational stability in both diastereomers is discussed in terms of the electronic energy and of the Gibbs energy. The weighted mean enthalpy of both diastereomers in the gas state at 298.15 K was obtained from the thermodynamic data and Boltzmann populations of the low-energy conformers.http://www.sciencedirect.com/science/article/B6TFF-4F31PT7-3/1/ae9dae05894f1bf2f4865221eb1b29b

Enthalpy of Sublimation in the Study of the Solid State of Organic Compounds. Application to Erythritol and Threitol

The enthalpies of sublimation of erythritol and L-threitol have been determined at 298.15 K by calorimetry. The values obtained for the two diastereomers differ from one another by 17 kJ mol -1 . An interpretation of these results is based on the decomposition of this thermodynamic property in a term coming from the intermolecular interactions of the molecules in the crystal (∆ int H°) and another one related with the conformational change of the molecules on going from the crystal lattice to the most stable forms in the gas phase (∆ conf H°). This last term was calculated from the values of the enthalpy of the molecules in the gas state and of the enthalpy of the isolated molecules with the crystal conformation. Both quantities were obtained by density functional theory (DFT) calculations at the B3LYP/6-311G++(d,p) level of theory. The results obtained in this study show that the most important contribution to the differences observed in the enthalpy of sublimation are the differences in the enthalpy of conformational change (13 kJ mol -1 ) rather than different intermolecular forces exhibited in the solid phase. This is explained by the lower enthalpy of threitol in the gas phase relative to erythritol, which is attributed to the higher strength of the intramolecular hydrogen bonds in the former. The comparison of the calculated infrared spectra obtained for the two compounds in the gas phase supports this interpretation

Nonlinear regression in parameter estimation from polarographic signals

In this work we describe a detailed treatment of polarographic data curves, including error analysis, by means of nonlinear least-squares in its standard form (or resorting to the errors in variables model). Error estimates for the related parameters are additionally verified by Monte-Carlo simulation and resampling techniques.http://www.sciencedirect.com/science/article/B6TFV-40T9HTX-13/1/f6e264fb725bc85b9d54f33786bbaf7

Maximum likelihood estimation with nonlinear regression in polarographic and potentiometric studies

In this work we review some aspects of maximum likelihood nonlinear modeling in polarographic and potentiometric techniques. Different algorithms, namely the Levenberg-Marquardt and the "error-in-variables" methods in parametric and Monte-Carlo nonparametric estimation are used. Conclusions are drawn upon the influence of experimental errors and error correlation, introduced via statistical weighting, in the accuracy and precision of the estimated parameters. Several of the tested alternatives, including regression on the signal variable alone with a global error weighting function, are shown to provide adequate representation of the experimental data.http://www.sciencedirect.com/science/article/B6TF4-42MN77N-G/1/41f1ab649732a741006ed3b32e9ea5d

Molecular structure of mono- and 1,2-aminoderivatives of cyclohexane: Steric strain effects as determining factors

The conformational study of cyclohexylamine and 1,2-cyclohexylamine derivatives was performed. The potential energy surface of every compound was calculated at B3LYP/6-31G(d) and the conformational energy minima were further optimized at B3LYP/aug-cc-pVDZ level of theory. The geometrical parameters and the electronic energy of each conformer were determined. The internal energy, enthalpy, entropy, Gibbs energy and the relative weight of each conformer in the structure of the respective isomer were calculated at 298.15 K. The steric hindrances in the crowded molecules resulting from the replacement of hydrogens of cyclohexane by amine groups are pointed out by short non-bonded H  H distances and by the consequent bond and dihedral angles distortions relatively to the cyclohexane structure.http://www.sciencedirect.com/science/article/B6TGT-4M40020-2/1/0ae6e9744a075380d2df6ddfef6e7bd