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.

Cutting edge: Langerin+ dendritic cells in the mesenteric lymph node set the stage for skin and gut immune system cross-talk.

Topical transcutaneous immunization (TCI) presents many clinical advantages, but its underlying mechanism remains unknown. TCI induced Ag-specific IgA Ab-secreting cells expressing CCR9 and CCR10 in the small intestine in a retinoic acid-dependent manner. These intestinal IgA Abs were maintained in Peyer\'s patch-null mice but abolished in the Peyer\'s patch- and lymph node-null mice. The mesenteric lymph node (MLN) was shown to be the site of IgA isotype class switching after TCI. Unexpectedly, langerin(+)CD8alpha(-) dendritic cells emerged in the MLN after TCI; they did not migrate from the skin but rather differentiated rapidly from bone marrow precursors. Depletion of langerin(+) cells impaired intestinal IgA Ab responses after TCI. Taken together, these findings suggest that MLN is indispensable for the induction of intestinal IgA Abs following skin immunization and that cross-talk between the skin and gut immune systems might be mediated by langerin(+) dendritic cells in the MLN.

Multiple Input Governor Control for a Diesel Generating Set

The paper presents a multiple input single output fuzzy logic governor algorithm that can be used to improve the transient response of a diesel generating set, when supplying an islanded load. The proposed governor uses the traditional speed input in addition to voltage and power factor to modify the fuelling requirements during various load disturbances. The use of fuzzy logic control allows the use of PID type structures that can provide variable gain strategies to account for non-linearities in the system. Fuzzy logic also provides a means of processing other input information by linguistic reasoning and a logical control output to aid the governor action during transient disturbance. The test results were obtained using a 50 kVA naturally aspirated diesel generator testing facility. Both real and reactive load tests were conducted. The complex load test results demonstrate that, by using additional inputs to the governor algorithm, enhanced generator transient speed recovery response can be obtained.

Photodissociation of D-3(+) in an intense, femtosecond laser field

H-3(+) is the simplest triatomic molecule and plays an important role in laboratory and astrophysical plasmas. It is very stable both in terms of its electronic and nuclear degrees of freedom but is difficult to study in depth in the laboratory due to its ionic nature. In this communication, experimental results are presented for the strong field dissociation of the isotopic analogue D-3(+), using 30 fs, 800 nm laser pulses with intensities up to 10(16) W cm(-2). By employing a novel experimental set-up, ions were confined in an electrostatic ion trap so that dissociation of the molecule could be studied as it radiatively cools. It was determined that dissociation could only be observed for molecules in ro-vibrational states relatively close to the dissociation limit, while more tightly bound states demonstrated remarkable stability in even the strongest fields.

The Postmodern Non-city in Miquel de Palol’s "El Jardí del Set Crepuscles"

El Jardí del Set Crepuscles –primera novela del escritor y arquitecto catalán Miquel de Palol– nos brinda la oportunidad de reflexionar acerca de la metamorfosis experimentada por la ciudad occidental a principios de los años setenta del siglo pasado. De acuerdo con autores como Henri Lefebvre, David Harvey, Giandomenico Amendola o Edward Soja, el surgimiento de la ciudad posmoderna en el marco de la transición hacia el modo de acumulación postfordista se presenta acompañado por un debilitamiento del tejido social y de la esfera pública y cívica. El objetivo del presente artículo es ilustrar las estrategias narrativas y retóricas con las que el texto de Miquel de Palol representa, y analiza, dicho fenómeno.

Techniques for multiple-set synchronous islanding control

Power system islanding can improve the continuity of power supply. Synchronous islanded operation enables the islanded system to remain in phase with the main power system while not electrically connected, so avoiding out-of-synchronism re-closure. Specific consideration is required for the multiple-set scenario. In this paper a suitable island management system is proposed, with the emphasis being on maximum island flexibility by allowing passive islanding transitions to occur, facilitated by intelligent control. These transitions include: island detection, identification, fragmentation, merging and return-to-mains. It can be challenging to detect these transitions while maintaining syn-chronous islanded operation. The performance of this control system in the presence of a variable wind power in-feed is also examined. A Mathworks SimPowerSystems simulation is used to investigate the performance of the island management system. The benefit and requirements for energy storage, com-munications and distribution system protection for this application are considered.

On the set of hypercyclic vectors for the differentiation

Let D be the differentiation operator Df = f' acting on the Fréchet space H of all entire functions in one variable with the standard (compact-open) topology. It is known since the 1950’s that the set H(D) of hypercyclic vectors for the operator D is non-empty. We treat two questions raised by Aron, Conejero, Peris and Seoane-Sepúlveda whether the set H(D) contains (up to the zero function) a non-trivial subalgebra of H or an infinite-dimensional closed linear subspace of H. In the present article both questions are answered affirmatively.

Order Flow and the Monetary Model of Exchange Rates: Evidence from a Novel Data Set

We propose an exchange rate model that is a hybrid of the conventional specification with monetary fundamentals and the Evans–Lyons microstructure approach. We estimate a model augmented with order flow variables, using a unique data set: almost 100 monthly observations on interdealer order flow on dollar/euro and dollar/yen. The augmented macroeconomic, or “hybrid,” model exhibits greater in-sample stability and out of sample forecasting improvement vis-à-vis the basic macroeconomic and random walk specifications.