Influence of Polarity and Activation Energy in Microwave–Assisted Organic Synthesis (MAOS)

The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol⁻¹ and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.     

Pseudo-Strong Regularity Around a Set

A generalization of strong regularity around a vertex subset C of a graph Γ, which makes sense even if Γis non-regular, is studied. Such a structure appears, together with a kind of distance-regularity around C , when an spectral bound concerning the so-called predistance polynomial of C is attained. As a main consequence of these results, it is shown that a regular (connected) graph Γwith d + 1 distinct eigenvalues is distance-regular, and its distance- d graph Γ d is strongly regular with parameters a = c , if and only if the number of vertices at distance d from each vertex satisfies an expression which depends only on the order of Γand the different eigenvalues of Γ.     

A system of parabolic equations in nonequilibrium thermodynamics including thermal and electrical effects

The time-dependent equations for a charged gas or fluid consisting of several components, exposed to an electric field, are considered. These equations form a system of strongly coupled, quasilinear parabolic equations which in some situations can be derived from the Boltzmann equation. The model uses the duality between the thermodynamic fluxes and the thermodynamic forces. Physically motivated mixed Dirichlet-Neumann boundary conditions and initial conditions are prescribed.The existence of weak solutions is proven. The key of the proof is (i) a transformation of the problem by using the entropic variables, or electro-chemical potentials, which symmetrizes the equations, and (ii) a priori estimates obtained by using the entropy function. Finally, the entropy inequality is employed to show the convergence of the solutions to the thermal equilibrium state as the time tends to infinity.     

A Nonlinear Drift - Diffusion System with Electric Convection Arising in Electrophoretic and Semiconductor Modeling

A multi-dimensional transient drift-diffusion model for (at most) three charged particles, consisting of the continuity equations for the concentrations of the species and the Poisson equation for the electric potential, is considered. The diffusion terms depend on the concentrations. Such a system arises in electrophoretic modeling of three species (neutrally, positively and negatively charged) and in semiconductor theory for two species (positively charged holes and negatively charged electrons). Diffusion terms of degenerate type are also possible in semiconductor modeling. For the initial boundary value problem with mixed Dirichlet - Neumann boundary conditions and general reaction rates, a global existence result is proved. Uniqueness of solutions follows in the Dirichlet boundary case if the diffusion terms are uniformly parabolic or if the initial and boundary densities are strictly positive. Finally, we prove that solutions exist which are positive uniformly in time and globally bounded if the reaction rates satisfy appropriate growth conditions.     

HPLC study of starch hydrolysis products obtained with α-amylase from bacillus amyloliquefaciens and bacillus licheniformis

Two bacterial α-amylases from new industrial strains were studied: α-amylase fromBacillus amyloliquefaciens CCM 3502 (Czechoslovak) and thermostable α-amylase fromBacillus licheniformis 44MB82 (Bulgarian). The thermostable enzyme hydrolyzed starch mainly to dextrins, and after 1 h, 30% of the products were oligosaccharides. TheB. amyloliquefaciens enzyme produced more maltooligosaccharides than the first enzyme (B. licheniformis). Within 1 h, up to 80% of the substrate were hydrolyzed, giving different spectrum of oligosaccharides in comparison with the thermostable one.     

Some characterisations of supported algebras

We give several equivalent characterisations of left (and hence, by duality, also of right) supported algebras. These characterisations are in terms of properties of the left and the right parts of the module category, or in terms of the classes L₀ and R₀ which consist respectively of the predecessors of the projective modules, and of the successors of the injective modules.     

Stereoselectivity in the intermolecular Pauson-Khand reaction of electron-deficient terminal alkynes

A family of terminal alkyne dicobalthexacarbonyl complexes bearing groups with a range of electron-withdrawing abilities has been synthesized. After submitting these complexes to the intermolecular Pauson-Khand reaction with norbornadiene, electron-deficient substrates afforded up to 26% of the unexpected endo-cyclopentenone.     

Group algebras of Kleinian type and groups of units

The algebras of Kleinian type are finite-dimensional semisimple rational algebras A such that the group of units of an order in A is commensurable with a direct product of Kleinian groups. We classify the Schur algebras of Kleinian type and the group algebras of Kleinian type. As an application, we characterize the group rings RG, with R an order in a number field and G a finite group, such that the group of units of RG is virtually a direct product of free-by-free groups.     

Coupling leads to chaos

The main goal of this paper is to prove analytically the existence of strange attractors in a family of vector fields consisting of two Brusselators linearly coupled by diffusion. We will show that such a family contains a generic unfolding of a 4-dimensional nilpotent singularity of codimension 4. On the other hand, we will prove that in any generic unfolding Xμ of an n-dimensional nilpotent singularity of codimension n there are bifurcation curves of (n−1)-dimensional nilpotent singularities of codimension n−1 which are in turn generically unfolded by Xμ. Arguments conclude recalling that any generic unfolding of the 3-dimensional nilpotent singularity of codimension 3 exhibits strange attractors.     

The ionization constants of alpha-alanine in NaCl at 25 degrees. Effect of the ionic strength based on three models

In the present work we obtained the experimental pKs of the amino acid alpha-alanine in NaCl at 25 degrees and different ionic strengths. The equilibrium constants have been potentiometrically determined with a commercial glass electrode and the results analysed through three models: two directly based on the Pitzer and Scatchard approaches to the ion specific interaction theory and the other based on a simpler modification of the Debye-Hückel equation. The three models fit the data reasonably well and the extrapolated pK values obtained show a good agreement. The goodness of the ridge regression method cannot be probed in this case.