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.

Impacts of climate change on species, populations and communities: palaeobiogeographical insights and frontiers

Understanding climate change and its potential impact on species, populations and communities is one of the most pressing questions of twenty-fi rst-century conservation planning. Palaeobiogeographers working on Cenozoic fossil records and other lines of evidence are producing important insights into the dynamic nature of climate and the equally dynamic response of species, populations and communities. Climatic variations ranging in length from multimillennia to decades run throughout the palaeo-records of the Quaternary and earlier Cenozoic and have been shown to have had impacts ranging from changes in the genetic structure and morphology of individual species, population sizes and distributions, community composition to large-scale bio-diversity gradients. The biogeographical impacts of climate change may be due directly to the effects of alterations in temperature and moisture on species, or they may arise due to changes in factors such as disturbance regimes. Much of the recent progress in the application of palaeobiogegraphy to issues of climate change and its impacts can be attributed to developments along a number of still advancing methodological frontiers. These include increasingly finely resolved chronological resolution, more refi ned atmosphere-biosphere modelling, new biological and chemical techniques in reconstructing past species distributions and past climates, the development of large and readily accessible geo-referenced databases of biogeographical and climatic information, and new approaches in fossil morphological analysis and new molecular DNA techniques.

Self-affine crossover length in a layered silicate deposit

Self-affine dehydrated colloidal deposits on fresh mica surfaces of the synthetic layered silicate 2:1 smectite clay laponite have been studied by means of atomic force microscopy (AFM). AFM images of these prepared assemblies of sol and gel aggregates have been analyzed both by means of standard AFM Fourier software and a wavelet method. The deposited surfaces show a persistence to antipersistent crossover with a clay concentration dependent crossover length. It is concluded that the crossover length is associated with aggregate size, and further that the persistent roughness at small length scales signals near compact clusters of fractal dimension three, whereas the antipersistent roughness at large length scales signals a sedimentation process.

Optimum decision delay of the finite-length DFE

This letter investigates the optimum decision delay and tap-length of the finite-length decision feedback equalizer. First we show that, if the feedback filter (FBF) length N-b is equal to or larger than the channel memory upsilon and the decision delay Delta is smaller than the feedforward filter (FFF) length N-f, then only the first Delta + 1 elements of the FFF can be nonzero. Based on this result we prove that the maximum effective FBF length is equal to the channel memory upsilon, and if N-b greater than or equal to upsilon and N-f is long enough, the optimum decision delay that minimizes the MMSE is N-f - 1.