DFT studies of long-chain FAMEs: theoretical justification for determining chain length and unsaturation from experimental Raman spectra

Density functional calculations, using B3LPY/6-31G(d) methods, have been used to investigate the conformations and vibrational (Raman) spectra of a series of long-chain, saturated fatty acid methyl esters (FAMEs) with the formula CH2nO2 (n = 5-21) and two series of unsaturated FAMEs. The calculations showed that the lowest energy conformer within the saturated FAMEs is the simple (all-trans) structure and, in general, it was possible to reproduce experimental data using calculations on only the all-trans conformer. The only exception was C6H12O2, where a second low-lying conformer had to be included in order to correctly simulate the experimental Raman spectrum. The objective of the work was to provide theoretical justification for the methods that are commonly used to determine the properties of the fats and oils, such as chain length and degree of unsaturation, from experimental Raman data. Here it is shown that the calculations reproduce the trends and calibration curves that are found experimentally and also allow the reasons for the failure of what would appear to be rational measurements to be understood. This work shows that although the assumption that each FAME can simply be treated as a collection of functional groups can be justified in some cases, many of the vibrational modes are complex motions of large sections of the molecules and thus would not be expected to show simple linear trends with changes in structure, such as increasing chain length and/or unsaturation. Simple linear trends obtained from experimental data may thus arise from cancellation of opposing effects, rather than reflecting an underlying simplicity.

Conformations, vibrational frequencies and Raman intensities of short-chain fatty acid methyl esters using DFT with 6-31G(d) and Sadlej pVTZ basis sets

Density functional calculations, using B3LPY/6-31G(d) methods, have been used to investigate the conformations and vibrational (Raman) spectra of three short-chain fatty acid methyl esters (FAMEs) with the formula CnH2nO2 (n = 3-5). In all three FAMEs, the lowest energy conformer has a simple 'all-trans' structure but there are other conformers, with different torsions about the backbone, which lie reasonably close in energy to the global minimum. One result of this is that the solid samples we studied do not appear to consist entirely of the lowest energy conformer. Indeed, to account for the 'extra' bands that were observed in the Raman data but were not predicted for the all-trans conformer, it was necessary to add-in contributions from other conformers before a complete set of vibrational assignments could be made. Provided this was done, the agreement between experimental Raman frequencies and 6-31G(d) values (after scaling) was excellent, RSD = 12.6 cm(-1). However, the agreement between predicted and observed intensities was much less satisfactory. To confirm the validity of the approach followed by the 6-3 1 G(d) basis set, we used a larger basis set, Sadlej pVTZ, and found that these calculations gave accurate Raman intensities and simulated spectra (summed from two different conformers) that were in quantitative agreement with experiment. In addition, the unscaled Sadlej pVTZ, and the scaled 6-3 1 G(d) calculations gave the same vibrational mode assignments for all bands in the experimental data. This work provides the foundation for calculations on longer-chain FAMEs (which are closer to those found as triglycerides in edible fats and oils) because it shows that scaled 6-3 1 G(d) calculations give equally accurate frequency predictions, and the same vibrational mode assignments, as the much more CPU-expensive Sadlej pVTZ basis set calculations.

Calibration of assessment instruments – classification in mathematics at the Universidad Jorge Tadeo Lozano

Item Response Theory, IRT, is a valuable methodology for analyzing the quality of the instruments utilized in assessment of academic achievement. This article presents an implementation of the mentioned theory, particularly of the Rasch model, in order to calibrate items and the instrument used in the classification test for the Basic Mathematics subject at Universidad Jorge Tadeo Lozano. 509 responses chains of students, obtained in the june 2011 application, were analyzed with a set of 45 items, through eight case studies that are showing progressive steps of calibration. Criteria of validity of items and of whole instrument were defined and utilized, to select groups of responses chains and items that were finally used in the determination of parameters which then allowed the classification of assessed students by the test.

Adaptation of a questionnaire to assess the epistemological beliefs of mathematics in secondary school teachers

The objective of the study is to determine the psychometric properties of the Epistemological Beliefs Questionnaire on Mathematics. 171 Secondary School Mathematics Teachers of the Central Region of Cuba participated. The results show acceptable internal consistency. The factorial structure of the scale revealed three major factors, consistent with the Model of the Three Constructs: beliefs about knowledge, about learning and teaching. Irregular levels in the development of the epistemological belief system about mathematics of these teachers were shown, with a tendency among naivety and sophistication poles. In conclusion, the questionnaire is useful for evaluating teacher’s beliefs about mathematics.

Chemistry in the Circumstellar Medium: Unveiling the Dust Formation Zone

The growth of dust grains in the inner regions of late-type stars is shrouded in mystery due to the difficulty of understanding the growth of heterogeneous particles from simple atoms and molecules and the lack of observational data. This article reviews the molecular processes important in circumstellar envelopes and discusses how ALMA might be used to probe the dust formation zone either directly or indirectly.