High alpha/beta-anomer selectivity in molecular recognition of carbohydrates by artificial receptors

[structure: see text] New effective, acyclic, pyridine-based receptors 1-3 show remarkable alpha/beta binding selectivity in the recognition of monosaccharides. They are able to participate in cooperative and bidentate hydrogen bonds with sugar hydroxyls as well as in CH-pi interactions with CH's of sugar molecules.     

Macroscopic evidence of soliton formation in multiterawatt laser-plasma interaction

A novel physical phenomenon has been observed following the interaction of an intense (10(19) W/cm(2)) laser pulse with an underdense plasma. Long-lived, macroscopic bubblelike structures have been detected through the deflection that the associated electric charge separation causes in a proton probe beam. These structures are interpreted as the remnants of a cloud of relativistic solitons generated in the plasma by the ultraintense laser pulse. This interpretation is supported by an analytical study of the soliton cloud evolution, by particle-in-cell simulations, and by a reconstruction of the proton-beam deflection.     

A class of multidimensional periodic splines

Periodic spline functions are introduced by use of reproducing kernel structure in Hilbert spaces. Minimum properties are described in interpolation and best approximation problems. A numerical method for determining interpolating splines and best approximations is proposed.Dedicated to Prof. Dr. F. Reutter on the occasion of his 70th birthday     

Studies on the Thorpe-Ziegler-reaction. A new synthesis of the pyridine part of thiamine]

Thorpe-Ziegler cyclization of N′-cyano-N-(2-cyanoethyl)-acetamidine ( 5a ) yields 4-amino-2-methyl-1,6-dihydro-5-pyrimidinecarbonitrile ( 8a ). The acetamidine 5a is accessible either from the N-cyanoimidate 1 and β-aminopropionitrile ( 3a ) or the N-cyanoamidine 2 and acrylonitrile ( 4 ). The dihydropyrimidine 8a is easily converted to 4-amino-2-methyl-5-pyrimidine-carbonitrile ( 13 ) by dehydrogenation or to 4-amino-5-aminomethyl-2-methylpyrimidine ( 15 ) by hydrogenation-dehydrogenation. Both products are important intermediates in the synthesis of thiamine.     

Thioformaldehyde S-methylide and thioacetone S-methylide: an ab initio MO study of structure and cycloaddition reactivity

The mechanisms of cycloaddition of thioformaldehyde S-methylide and thioacetone S-methylide, as models for an alkyl-substituted ylide, to thioformaldehyde and thioacetone, as well as to ethene as a model for a C=C double bond have been studied by ab initio calculations. Restricted and unrestricted B3LYP/6-31G* calculations were performed for the geometries of ground states, transition structures, and intermediates. Although basis sets with more polarization functions were tested, the 6-31G* basis set was applied throughout. Single-point CASPT2 calculations are reported for analysis of the unsubstituted system. The stabilities of structures with high biradical character seem to be overestimated by DFT methods in comparison to CASPT2. The general trends of the results are independent of the level of theory. Thioformaldehyde adds to thioformaldehyde S-methylide without activation energy, and the activation energies for two-step biradical pathways to 1,3-dithiolane are low. C,S biradicals are more stable than C,C biradicals. The two-step cycloaddition is not competitive with the concerted cycloaddition. Methyl substitution in the 1,3-dipole and the dipolarophile does not change the mechanistic relationships. TSs for the concerted formation of the regioisomeric cycloadducts of thioacetone Smethylide and thioacetone were located. Concerted addition remains the preferred reaction. The reactivity of the C=S double bond is high relative to that of the C=C double bond.     

Multiscale analysis and simulation of a reaction–diffusion problem with transmission conditions

This paper considers a transmission problem for partial differential equations obtained in the recent paper [M. Neuss-Radu, W. Jäger, Effective transmission conditions for reaction-diffusion processes in domains separated by an interface, SIAM J. Math. Anal. 39 (2007) 687–720] as the effective system modeling a reaction–diffusion process in two domains separated by a membrane. For the analysis of this problem an appropriate function space, which includes the coupling conditions for the concentrations on the interface, is introduced. The transmission conditions for the flux are included in the variational formulation with respect to this function space.The solution of the transmission problem is approximated by using the Galerkin method. Numerically the problem is reduced to a system of ordinary differential equations, where the coupling of the micro- and macro-variables leads to a special structure, distinguishing the variables relevant for the transmission. Results of numerical simulations are illustrating the effect of the microscopic process in the membrane on the macroscopic reaction–diffusion process in the bulk domains.