Pyridoxamine,a scavenger agent of carbohydrates

Pyridoxamine has been found to inhibit protein glycation and to avoid the formation of advanced glycation end‐products (AGEs). One of the mechanisms by which pyridoxamine can inhibit glycation involves the scavenger of carbonyl groups with glycation capacity. In this work, we conducted a kinetic study of the reactions of pyridoxamine with various carbohydrates under physiological pH and temperature. The reactions involving hexoses were found to give a tricyclic compound ( 5 ) in addition to pyridoxal and pyridoxine. Such a tricyclic compound inhibits the Amadori rearrangement and the formation of other carbonyl compounds with glycating properties. The reactions involving pentoses gave compound 7 and pyridoxal—by transamination of the Schiff base. The transamination reaction enhances the inhibitory action of pyridoxamine. The formation rate constants for the Schiff base, k₃, were found to be similar to those for the reactions of D ‐glucose with amino acids, which suggests competition between pyridoxamine and terminal amino residues in proteins for glycating sites in sugars. These constants are dependent on the electrophilic character of the carbonyl carbon in the carbohydrate. © 2007 Wiley Periodicals, Inc. 39: 154–167, 2007     

Energy spectrum of a relativistic two-dimensional hydrogen-like atom in a constant magnetic field of arbitrary strength

We compute, via a variational mixed-base method, the energy spectrum of a two-dimensional relativistic atom in the presence of a constant magnetic field of arbitrary strength. The results are compared to those obtained in the non-relativistic and spinless case. We find that the relativistic spectrum does not present s states.     

Quantum relativistic investigation about the coordination and bonding effects of different ligands on uranyl complexes

The coordination and bonding effects of equatorial ligands such as fluoride (F⁻), chloride (Cl⁻), cyanide (CN⁻), isocyanide (NC⁻), and carbonate (CO₃⁻²) on uranyl dication (UO₂²⁺) has been studied using relativistic density functional theory. The ZORA Hamiltonian was applied for the inclusion of relativistic effects taking into account all the electrons for the optimization and the explicit inclusion of spin–orbit coupling effects. Geometry optimizations including the counterions and frequencies analysis were carried out with PW91 and PBE functional. Solvents effects were considered by using the conductor like screening model (COSMO) for water and acetonitrile. The Time-Dependent Density Functional Theory (TDDFT) was used to calculate the excitation energies with GGA SAOP functional and the electronic transitions were analyzed using double group irreducible representations. The theoretical results are in a good agreement with experimental IR, Raman and EXAFS spectra and previous theoretical results. New information about the effect of different (donor and acceptors) ligands on the bonding of uranyl ion and on the electronic transitions involved in these complexes is provided with a possible impact on the understanding of the uranyl coordination chemistry.     

Local search and genetic algorithm for the job shop scheduling problem with sequence dependent setup times

The Job Shop Scheduling Problem (JSP) is an example of a combinatorial optimization problem that has interested researchers for several decades. In this paper we confront an extension of this problem called JSP with Sequence Dependent Setup Times (SDST-JSP). The approach extends a genetic algorithm and a local search method that demonstrated to be efficient in solving the JSP. For local search, we have formalized neighborhood structures that generalize three well-know structures defined for the JSP. We have conducted an experimental study across conventional benchmark instances showing that the genetic algorithm exploited in combination with the local search, considering all three neighborhoods at the same time, provides the best results. Moreover, this approach outperforms the current state-of-the-art methods.     

Optimal Design in Conductivity Under Locally Constrained Heat Flux

This paper addresses the relaxation of an optimal design problem in conductivity under a point-wise constraint on the heat flux. By using a variational approach, developed by the authors in a previous work, we obtained a complete relaxation, involving the explicit computation of constrained quasiconvex envelopes. This relaxed formulation turns out to be very simple in the remarkable compliance case, for which numerical simulations are performed. Those simulations show that our approach and results are interesting from a theoretical point of view as well as from a practical perspective. The emphasis of our work is placed on the local constraint on the heat flux, which seems to be a new ingredient for this kind of optimal design problems.     

DSC study of precipitation processes in Cu-Co-Si alloys

Using differential scanning calorimetry (DSC) the precipitation processes of supersaturated solid solutions of three Cu-Co-Si alloys containing the same atomic cobalt content were investigated. Thermoanalytical and previous studies, reveal that the decomposition begins with cobalt clustering which initiates the precipitation of the Co₂Si stoichiometric particles, which in turn dissolves after further heating. Volume fractions are unequivocally determined by the amount of cobalt present in these alloys. It is infered that surplus silicon atoms retained in the solution increase the reaction rate and dispersity of precipitate structure. Kinetic parameters were obtained by a convolution method based in the Mehl-Johnson-Avrami (MJA) formalism. The lower activation energy associated with cobalt clustering is attributed to the contribution of quenched-in vacancies. Superimposed to the MJA formalism and adaptative spherical diffusion model was used for Co₂Si precipitation with particle size as a disposable parameter. This model further confirmed that as silicon content increases particle dispersity becomes more pronounced. Such results are also infered from a three dimensional diffusion dissolution model previously developed which adjusts quite well to such process in the present cases. Age hardening experiments are in line with all previous results obtained. This revised version was published online in August 2006 with corrections to the Cover Date.     

Laplace-transformed diagonal Dyson correction to quasiparticle energies in periodic systems

We present a method to self-consistently evaluate quasiparticle energies of periodic systems within the diagonal approximation for solving Dyson's equation. Our method is based on the Laplace transform of the second-order M?ller-Plesset perturbation (MP2) theory kernel in the atomic basis formulation. The overhead computational cost of evaluating the fully self-consistent diagonal correction over the MP2 band energy calculation is negligible. We present numerical benchmark results for the band structure of trans-polyacetylene and compare it with MP2 and other approaches.     

(2S,RS)‐6‐Phenyl‐1‐(p‐tolyl­sulfinyl)­hexa‐3(E),5(E)‐dien‐2‐ol

The mol­ecule of the title compound, C₁₉H₂₀O₂S, corresponds to a chiral sulfinyldienol with two stereogenic centres, viz. the C atom susbtituted by the hydr­oxy group and the sulfinyl S atom. The mol­ecule displays a V‐shape in the solid state. The dihedral angle defined by the least‐squares planes of the aromatic rings is 72.9 (1)°. The packing pattern exhibits the following inter­molecular hydrogen bonds: one O—H⋯O [H⋯O = 1.98 Å, O⋯O = 2.785 (4) Å and O—H⋯O = 166°] and two C—H⋯O [H⋯O = 2.58 and 2.60 Å, C⋯O = 3.527 (5) and 3.347 (5) Å, and C—H⋯O = 164 and 134°]. These define a chain along b.