Synthesis of 5-Thio-D- Galactopyranose

5-Thio-D-galactopyranose has been synthesized from diacetone galactofuranose in nine steps and 13.4% overall yield. The key step involved a successful conversion of furanosyl 5,6-epoxide with an L-altrose configuration into the corresponding 5,6-thiirane D-galactose derivative, which was hydrolyzed to the target compound.     

The Regio- and Stereoselective Synthesis of Rhamnose-Containing Oligosaccharides Via Sugar-Sugar Orthoester Formation and Rearrangement

ABSTRACT

Convenient regio- and stereoselective syntheses of rhamnose-containing oligosaccharides via sugar-sugar orthoester formation and rearrangement are described. 1→3 Linked rhamno di- and trisaccharides were synthesized effectively using unprotected rhamnose residue as the glycosyl acceptor by this methodology.     

Optical bistability based on surface plasmon coupled between two noble metal films involving Kerr materials

We successfully investigate an optical bistability phenomenon in a layered structure consisting of Kretschmann configuration involving the Kerr-type nonlinear and the silver film. Pure theoretical approaches are employed to investigate that the surface plasmon could easily be coupled and both the reflection and transmission curves versus the incident intensity forms optical bistability. The transmission curves are greatly influenced by the thickness of the second silver film. These results may be useful for designing novel surface plasmon-based optical devices and will be essential for future classical and quantum information processes.     

Immobilized palladium on surface-modified Fe3O4/SiO2 nanoparticles: as a magnetically separable and stable recyclable high-performance catalyst for Suzuki and Heck cross-coupling reactions

A palladium-based catalyst (Fe₃O₄/SiO₂/HPG–OPPh₂–PNP) supported on chlorodiphenylphosphine-functionalized magnetic nanoparticles was successfully prepared from Fe₃O₄/SiO₂ with sequential attachment of glycerol and chlorodiphenylphosphine, followed by treatment of an ethanolic solution of palladium chloride with hydrazine. The as-prepared catalyst was characterized by ICP-AES, FTIR, XRD, SEM, and TEM. The Fe₃O₄/SiO₂/HPG–OPPh₂–PNP was found as a magnetically separable and highly active catalyst for Suzuki coupling reactions of aryl iodides, bromides, and chlorides as well as Heck reactions of aryl iodides and bromides. Under appropriate conditions, all reactions afforded the desired products in moderate to excellent yields. Moreover, this catalyst can be easily recovered by using a magnetic field and directly reused for at least six cycles without significant loss of its activity.     

A new electronically deficient atropisomeric diphosphine ligand (S)-CF3O-BiPhep and its application in asymmetric hydrogenation

A new electronically deficient atropisomeric diphosphine ligand (S)-CF₃O-BiPhep was synthesized from 1-bromo-3-(trifluoromethoxy)benzene in high yield. The key steps included oxidative coupling with anhydrous ferric chloride and optical resolution by (+)-DMTA. The ligand afforded high performance for Ir-catalyzed asymmetric hydrogenation of quinolines with ee up to 92% and TON up to 25,000. It was also successfully applied to the Pd-catalyzed asymmetric hydrogenation of simple indoles with ee up to 87% and Rh-catalyzed asymmetric 1,4-addition of phenylboronic acid to 2-cyclohexenone with 97% ee.     

Why calcium inhibits magnesium-dependent enzyme phosphoserine phosphatase? A theoretical study

Mechanisms for the formation of the Schiff base from acetaldehyde and butylamine, glycine and phosphatidylethanolamine based on Dmol3/DFT calculations were realized. For the case of phosphatidylethanolamine, calculations were done under periodic boundary conditions, in an amine-phospholipid monolayer model with two molecules of phosphatidylethanolamine by cell. All models contained explicit aqueous solvent. In the three cases, a neutral amino group is used to model the nucleophilic attack on the carbonyl group of acetaldehyde, and water molecules form hydrogen bond networks. These networks were involved in the reactions by performing as proton-transfer carriers, important in some steps of reactions, and stabilizing reaction intermediates. In all the studied reactions, they take place in two steps, namely: (1) formation of a carbinolamine and (2) its dehydration to the Schiff base, being the dehydration the rate-determining step of the process, consistent with available experimental evidence for similar reactions. The main difference between the studied reactions is found in the value for relative free energy for the intermediates and transition states in the second step; these values are lower in the cases of glycine and phosphatidylethanolamine in comparison with butylamine, due the influence of their molecular environments. Based on the results, the aminophospholipid surface environment and carboxylic group of glycine may boost Schiff base formation via a neighboring catalyst effect.     

Pattern discrimination and firing behavior of cold receptor model aided with noise

A method for characterizing and identifying firing patterns of neural spike trains is presented. Three characteristic variables defined at sequential moments, including two formal derivatives and the integration of the counting process, are introduced to reflect the temporal patterns of a spike train. This paper also examines how noise interacts with encoding mechanisms of neuronal stimulus in a cold receptor. From ISI series and bifurcation diagrams it is shown that there are considerable differences in interval distributions and impulse patterns caused by purely deterministic simulations and noisy simulations. The ISI-distance can be used as an effective and powerful way to measure the noise effects on spike trains quantitatively. It is found that spike trains observed in cold receptors can be more strongly affected by noise for low temperatures than for high temperatures in some aspects; meanwhile, spike train has greater variability with the noise intensity increasing.