Synthesis of (R)-tembamide and (R)-aegeline via asymmetric transfer hydrogenation in water

The synthesis of (R)-tembamide and (R)-aegeline via asymmetric transfer hydrogenation involving enantioenriched monosulfonamide–RhCp¹ complex in aqueous sodium formate as hydride donor is described.     

Isobaric thermal expansivity of the binary system 1-hexanol + n-hexane as a function of temperature and pressure

The isobaric thermal expansivity against temperature and pressure for the system 1-hexanol + n-hexane was directly determined by means of a calorimetric method. From these data, the excess isobaric thermal expansivity is calculated at representative temperatures and pressures. The obtained results for this excess quantity are qualitatively discussed by applying well-known arguments often used for explaining the thermodynamic behavior of alcohol + alkane mixtures. In order to check the consistency of these data with those of literature, the derivative of excess molar volume against temperature and that of excess isobaric molar heat capacity against pressure are calculated and compared with those obtained from literature data. Very good coherence between both data sources is obtained.     

On the Ligand‐to‐Metal Charge‐Transfer Photochemistry of the Copper(II) Complexes of Quercetin and Rutin

In contrast to the UV‐photoinduced ligand photoionization of the flavonoid complexes of Fe^III, redox reactions initiated in ligand‐to‐metal charge‐transfer excited states were observed on irradiation of the quercetin ( 1 ) and rutin ( 2 ) complexes of Cu^II. Solutions of complexes with stoichiometries [Cu^IIL₂] (L=quercetin, rutin) and [Cu^II₂L_n] (n=1, L=quercetin; n=3, L=rutin) were flash‐irradiated at 351 nm. Transient spectra observed in these experiments showed the formation of radical ligands corresponding to the one‐electron oxidation of L and the reduction of Cu^II to Cu^I. The radical ligands remained coordinated to the Cu^I centers, and the substitution reactions replacing them by solvent occurred with lifetimes τ<350 ns. These are lifetimes shorter than the known lifetimes (τ>1 ms) of the quercetin and rutin radical's decay.     

Study of a Tritrophic Food Chain Model with Non-differentiable Functional Response

We study a model of three interacting species in a food chain composed by a prey, an specific predator and a generalist predator. The capture of the prey by the specific predator is modelled as a modified Holling-type II non-differentiable functional response. The other predatory interactions are both modelled as Holling-type I. Moreover, our model follows a Leslie-Gower approach, in which the function that models the growth of each predator is of logistic type, and the corresponding carrying capacities depend on the sizes of their associated available preys. The resulting model has the form of a set of nonlinear ordinary differential equations which includes a non-differentiable term. By means of topological equivalences and suitable changes of parameters, we find that there exists an Allee threshold for the survival of the prey population in the food chain, given, effectively, as a critical level for the generalist predator. The dynamics of the model is studied with analytical and computational tools for bifurcation theory. We present two-parameter bifurcation diagrams that contain both local phenomena (Hopf, saddle-node transcritical, cusp, Bogdanov-Takens bifurcations) and global events (homoclinic and heteroclinic connections). In particular, we find that two types of heteroclinic cycles can be formed, both of them containing connections to the origin. One of these cycles is planar involving the absence of the specific predator. In turn, the other heteroclinic cycle is formed by connections in the full three-dimensional phase space.

     

Design and operation issues using NLP superstructure modeling

Till present, models that determined batch plants configurations in the chemical process industry resorted to models with binary variables to represent the different admissible options. This approach allowed representing the problem in a simple way while considering a significant number of alternatives. Nevertheless, the non-convexity that arises when dealing with detailed models for representing the involved units operation prevents its correct resolution or has a low performance. This work presents a representation of the problem through a superstructure that takes explicitly into account all the alternatives without resorting to binary variables. By using extremely simple modeling, it is possible to manage an appropriate number of options for this type of problems by means of a non-linear programming (NLP) model. Moreover, it is possible to consider duplication in series of production stages, which is an alternative that has not been used till now. This approach is posed for the case of a fermentors network. The solution is reached with very low requirements as regards employed computer time and without the aforementioned difficulties.     

New Materials Derived from Ybco: CrSr2RECu2O8 (RE = La, Pr, Nd, Eu, Gd, Tb, Dy, Y, Ho, Er, Lu)

Eleven new oxides, derived from yttrium barium copper oxide by replacing the square-planar copper [Cu-O4] of the basal plane of the triple perovskite-based structure with octahedral Cr(IV), have been prepared at high pressure and temperature. Their crystal structures have been determined, and their complex microstructure has been established by means of high-resolution electron microscopy and electron diffraction. The materials have a general formula of CrSr2RECu2O8 (RE = La, Pr, Nd, Eu, Gd, Tb, Dy, Y, Ho, Er, and Lu); they are tetragonal, show the symmetry of space group P4/mmm, and do not appear to be superconducting.     

Trace level determination of substance P using capillary electrophoresis and laser-induced fluorescence

An analytical method was developed to determine the undecapetide substance P (SP) based on capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection. SP was derivatized with the fluorogenic reagent 2,3-naphthalenedicarboxaldehyde (NDA) prior to injection into the CE-LIF system. The pre-column derivatization scheme combined with injection enhancement techniques extends the detectability of SP to the subnanomolar level. Limit of detection (LOD) of 100 pM was achieved without pre-concentrating the sample prior to injection. The reproducibility for six different preparations of a standard sample containing 5 nM of SP was 6.8% RSD and that of the CE migration time was 0.08% RSD. The method was used to determine SP in a saliva sample.