A critical evaluation of Raman spectroscopy for the analysis of lipids: fatty acid methyl esters.

The work presented here is aimed at determining the potential and limitations of Raman spectroscopy for fat analysis by carrying out a systematic investigation of C-4-C-24 FAME. These provide a simple, well-characterized set of compounds in which the effect of making incremental changes can be studied over a wide range of chain lengths and degrees of unsaturation. The effect of temperature on the spectra was investigated over much larger ranges than would normally be encountered in real analytical measurements. It was found that for liquid FAME the best internal standard band was the carbonyl stretching vibration nu(C = O), whose position is affected by changes in sample chain length and physical state; in the samples studied here, it was found to lie between 1729 and 1748 cm(-1). Further, molar unsaturation could be correlated with the ratio of the nu(C = O) to either nu(C = C) or delta(H-C = ) with R-2 > 0.995. Chain length was correlated with the delta(CH2)(tw)/nu(C = O) ratio, (where "tw" indicates twisting) but separate plots for odd- and even-numbered carbon chains were necessary to obtain R-2 > 0.99 for liquid samples. Combining the odd- ani even-numbered carbon chain data in a single plot reduced the correlation to R-2 = 0.94-0.96, depending on the band ratios used. For molal unsaturation the band ratio that correlated linearly with unsaturation (R-2 > 0.99) was nu(C = C)/delta(CH2)(SC) (where "sc" indicates scissoring). Other band ratios show much more complex behavior with changes in chemical and physical structure. This complex behavior results from the fact that the bands do not arise from simple vibrations of small, discrete regions of the molecules but are due to complex motions of large sections of the FAME so that making incremental changes in structure does not necessarily lead to simple incremental changes in spectra.

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.

Optical Thomson scatter from laser-ablated plumes

We have obtained density and temperature informations on an expanding KrF laser-ablated magnesium plume via optical Thomson scatter with a frequency doubled Nd:YAG laser. The electron temperature was found to decay with the expected Te t-1 dependence. However, we have found the electron density to have a time dependence ne t-4.95 which can be explained by strong recombination processes. We also observed atomic Raman satellites originating from transitions between the different angular momentum levels of the metastable 3P0 term in Mg I.

Analysis procedure for calculation of electron energy distribution functions from incoherent Thomson scattering spectra

Incoherent Thomson scattering (ITS) provides a nonintrusive diagnostic for the determination of one-dimensional (1D) electron velocity distribution in plasmas. When the ITS spectrum is Gaussian its interpretation as a three-dimensional (3D) Maxwellian velocity distribution is straightforward. For more complex ITS line shapes derivation of the corresponding 3D velocity distribution and electron energy probability distribution function is more difficult. This article reviews current techniques and proposes an approach to making the transformation between a 1D velocity distribution and the corresponding 3D energy distribution. Previous approaches have either transformed the ITS spectra directly from a 1D distribution to a 3D or fitted two Gaussians assuming a Maxwellian or bi-Maxwellian distribution. Here, the measured ITS spectrum transformed into a 1D velocity distribution and the probability of finding a particle with speed within 0 and given value v is calculated. The differentiation of this probability function is shown to be the normalized electron velocity distribution function. (C) 2003 American Institute of Physics.

Thomson scattering system at the Tokyo electron beam ion trap

A Thomson scattering system has been installed at the Tokyo electron beam ion trap for probing characteristics of the electron beam. A YVO4 green laser beam was injected antiparallel to the electron beam. The image of the Thomson scattering light from the electron beam has been observed using a charged-coupled device camera. By using a combination of interference filters, the spectral distribution of the Thomson scattering light has been measured. The Doppler shift observed for the scattered light is consistent with the beam energy. The beam radius dependence was investigated as a function of the beam energy, the beam current, and the magnetic field at the trap region. The variation of the measured beam radius against the beam current and the magnetic field were similar to those in Herrmann's prediction. The beam radius as a function of the beam energy was also similar to Herrmann's prediction but seemed to become larger at low energy. (C) 2002 American Institute of Physics.

James Anderson's Political Economy--His Influence on Smith and Malthus

James Anderson's powerful critique of Adam Smith's position on the corn export bounty was published in 1777. It focuse d on Smith's proposition that the bounty could not lead to increased corn production because it could not increase corn's real price. Smit h's response to the critique is traced in later editions of Wealth of Nations. While Anderson's critique of Smith influenced Thomas Malthu s's writings from 1803 onwards, his theory of differential rent did n ot influence Malthus at this stage. An examination of the evolution o f Malthus's ideas on rent between 1803 and 1815, however, indicates t hat Malthus knew and used Anderson's work on rent.

Prices and Wages in Ireland, 1700-1850

The article presents primary research on rural wages and the prices of agricultural goods and draws conclusions concerning the trend in the living conditions of rural workers in the century before the Great Irish Famine of 1845-1850.

"Irish Perspectives on EC Law by Mary Catherine Lucey and Cathrina Keville (eds.), Dublin, Thomson Round Hall, 2003 (ISBN 1-85800-280-X)"

Book Review

Politics, Patriotism and Women in Ireland, Britain and Colonial America, c.1700-c.1780

The use of the consumer boycott as a political tool is commonly associated with pre-revolutionary colonial America and has been identified by historians as an important means through which American women were politicized. This article argues that from the late seventeenth century, Irish political discourse advocated the non-consumption of imported goods and support for home manufactures by women in ways that were strikingly similar to those used later in North America. In Ireland and, subsequently in the American colonies, the virtuous woman consumer was given an active public role by political and social commentators. Rather than being a “brilliantly original American invention,” as T. H. Breen has argued, the political exploitation of a consumer boycott and the promotion of local industry were among what Bernard Bailyn has described as the “set of ideas, already in scattered ways familiar” to the revolutionary leaders through the Irish experience. The article also argues that a shared colonial environment gave Irish and American women a public patriotic role in the period, c. 1700–1780 that they did not have in the home countries of England and Scotland.