Mechanism of the base-assisted displacement of chloride by alcohol in sulfinyl derivatives

A computational study with density functional theory (DFT) is carried out on the reaction between methyl sulfinyl chloride (MSC) and methanol in the presence of trimethylamine, a process which is a general model for two different methods used in practice for the obtention of chiral sulfoxides through dynamic kinetic resolution. Two mechanistic options are considered: in one of them, chloride is initially displaced by the base (ion pair mechanism), whereas in the other, chloride stays bound to sulfur until its final displacement by methoxy (neutral mechanism). In both cases, the approach of the alcohol to sulfur is coupled with a hydrogen transfer from methanol to the oxo group of MSC in a single concerted transition state. The presence of a trimethylamine molecule facilitates substantially the reaction by reducing the nucleophilic substitution barrier by more than 10 kcal/mol through the formation of a N-H bond with the hydrogen atom being transferred. The neutral mechanism presents a free energy barrier lower than the ion pair alternative and is thus preferred.     

Monitoring of chicken meat freshness by means of a colorimetric sensor array

A new optoelectronic nose to monitor chicken meat ageing has been developed. It is based on 16 pigments prepared by the incorporation of different dyes (pH indicators, Lewis acids, hydrogen-bonding derivatives, selective probes and natural dyes) into inorganic materials (UVM-7, silica and alumina). The colour changes of the sensor array were characteristic of chicken ageing in a modified packaging atmosphere (30% CO(2)-70% N(2)). The chromogenic array data were processed with qualitative (PCA) and quantitative (PLS) tools. The PCA statistical analysis showed a high degree of dispersion, with nine dimensions required to explain 95% of variance. Despite this high dimensionality, a tridimensional representation of the three principal components was able to differentiate ageing with 2-day intervals. Moreover, the PLS statistical analysis allows the creation of a model to correlate the chromogenic data with chicken meat ageing. The model offers a PLS prediction model for ageing with values of 0.9937, 0.0389 and 0.994 for the slope, the intercept and the regression coefficient, respectively, and is in agreement with the perfect fit between the predicted and measured values observed. The results suggest the feasibility of this system to help develop optoelectronic noses that monitor food freshness.     

Copper(I) complexes with bipyridyl and phosphine ligands: a systematic study

Phosphorescent copper(I) complexes carrying 2,2'-bipyridyl derivatives and phosphine ligands have been prepared and fully characterised. The role of the bipyridyl as well as the phosphine ligands in defining the optical, as well as the chemical properties of the complexes, are discussed. The light emission of these complexes is investigated as a function of the molecular geometry: rigid complexes with restricted freedom to rearrange in the excited state are found to show a quantum yield of phosphorescence one order of magnitude higher than those complexes with no steric constraint. The complexes have been extruded in a polymer matrix as a proof of principle of their processability.     

Emission and strain in InGaAs/GaAs quantum wells with InAs quantum dots obtained at different temperatures

The photoluminescence (PL), its temperature dependence and X ray diffraction (XRD) have been studied in the symmetric In_0.15Ga_0.85As/GaAs quantum wells (QWs) with embedded InAs quantum dots (QDs), obtained with the variation of QD growth temperatures (470–535 °C). The increase of QD growth temperatures is accompanied by the enlargement of QD lateral sizes (from 12 up to 28 nm) and by the shift non monotonously of PL peak positions. The fitting procedure has been applied for the analysis of the temperature dependence of PL peaks. The obtained fitting parameters testify that in studied QD structures the process of In/Ga interdiffusion between QDs and capping/buffer layers takes place partially. However this process cannot explain the difference in PL peak positions.     

Multicore, tapered optical fiber for nonlinear pulse reshaping and saturable absorption

We present a new method to create a coupled waveguide array via tapering a seven-core telecommunications fiber. The fiber based waveguide array is demonstrated to exhibit the novel physics associated with coupled waveguide arrays, such as discrete diffraction and discrete self-focusing. The saturable absorber characteristics of the device are characterized and an autocorrelation measurement reveals significant single-pass pulse reshaping.     

Hopf bifurcations to quasi-periodic solutions for the two-dimensional plane Poiseuille flow

This paper studies various Hopf bifurcations in the two-dimensional plane Poiseuille problem. For several values of the wavenumber α, we obtain the branch of periodic flows which are born at the Hopf bifurcation of the laminar flow. It is known that, taking α ≈ 1, the branch of periodic solutions has several Hopf bifurcations to quasi-periodic orbits. For the first bifurcation, calculations from other authors seem to indicate that the bifurcating quasi-periodic flows are stable and subcritical with respect to the Reynolds number, Re. By improving the precision of previous works we find that the bifurcating flows are unstable and supercritical with respect to Re. We have also analysed the second Hopf bifurcation of periodic orbits for several α, to find again quasi-periodic solutions with increasing Re. In this case the bifurcated solutions are stable to superharmonic disturbances for Re up to another new Hopf bifurcation to a family of stable 3-tori. The proposed numerical scheme is based on a full numerical integration of the Navier-Stokes equations, together with a division by 3 of their total dimension, and the use of a pseudo-Newton method on suitable Poincaré sections. The most intensive part of the computations has been performed in parallel. We believe that this methodology can also be applied to similar problems.     

Multistability annihilation in the Hénon map through parameters modulation

We consider a situation in which the two parameters of a Hénon map are modulated by the output of another Hénon map. Two cases are considered. Firstly, we investigate the behavior of the Hénon map when its parameters are modulated by another Hénon map, this last working in a high dissipative regime. Secondly, we use a Hénon map working in a low dissipative regime as the modulation. We show that, regardless of the considered case, multistability can be suppressed by the modulation.     

Integrating Hydrogeochemical and Geophysical Data for Testing a Finite Volume Based Numerical Model for Saltwater Intrusion

In this paper, hydrogeological and geophysical data are used to validate a numerical model developed to predict seawater intrusion into coastal aquifers. The cell-centered finite volume method is adopted here to solve the set of coupled partial differential equations describing the motion of saltwater and freshwater separated by a sharp interface. These equations are based on the Dupuit approximation and are obtained from integration of 3D flow equations for fresh and salt water zones over the vertical dimension. In order to have flexibility upon complex configurations domain, non structured grid meshing is utilized. To approximate the diffusion fluxes, Green-Gauss type reconstruction, based on diamond-cell and least squares interpolation, is performed. The model is first validated using academic test case studies with known closed form solutions. The mathematical model has been calibrated using hydrogeochemical and geophysical data. The geophysical method applied in this study has been a frequency domain electromagnetic method. In this method the apparent electrical conductivity is measured by induction using two separate hand-held transmitter and receiver coils. During the operation the transmitter coil is energized by a low frequency alternating current that radiates an electromagnetic field and the receiver coil detects the resulting field. Taking into account the relationship between the bulk conductivity of the subsoil and the conductivity of groundwater, EM soundings have been interpreted to provide complementary information to hydrogeochemical data to outline the fresh–saltwater interface. This methodology has been applied to the case of saltwater intrusion into the Llobregat delta aquifer, near Barcelona, Spain.     

An Approach to Minimize Tumour Proliferation by Reducing the Formation of Components for Cell Membrane

Isoprenoids are natural compounds essential for a great number of cellular functions. One of them is farnesol (FOH), which can reduce cell proliferation, but its low solubility in aqueous solvents limits its possible clinical use as a pharmacological tool. One alternative is the use of cyclodextrins (CDs) which house hydrophobic molecules forming inclusion complexes. To assess FOH potential application in anticancer treatments, Sulfobutylated β-cyclodextrin Sodium Salt (SBE-β-CD) was selected, due to it has high solubility, approbation by the FDA, and numerous studies that ensure its safety to be administered parenterally or orally without nephrotoxicity associated. The therapeutic action of farnesol and complex were studied in different carcinoma cells, compared with a normal cell line. Farnesol showed selectivity, affecting the viability of colon and liver cancer cells more than in breast cancer cells and fibroblasts. All cells suffered apoptosis after being treated with 150 μM of free FOH, but the complex reduced their cell viability between 50 and 75%. Similar results were obtained for both types of isomers, and the addition of phosphatidylcholine reverses this effect. Finally, cell cycle analysis corroborates the action of FOH as inducer of a G0/G1 phase; when the cells were treated using the complex form, this viability was reduced, reaching 50% in the case of colon and liver, 60% in fibroblasts, and only 75% in breast cancer.