Synthesis of the Carbohydrate Moiety of Glycoproteins from the Parasite Echinococcus granulosus and Their Antigenicity against Human Sera

Stereocontrolled syntheses of biotin-labeled oligosaccharide portions containing the carbohydrate moiety of glycoprotein from Echinococcus granulosus have been accomplished. Trisaccharide Galβ1-3Galβ1-3GalNAcα1-R (A), tetrasaccharide Galα1-4Galβ1-3Galβ1-3GalNAcα1-R (B), and pentasaccharide Galα1-4Galβ1-3Galβ1-3Galβ1-3GalNAcα1-R (C), (R = biotinylated probe) were synthesized by stepwise condensation and/or block synthesis by the use of 5-(methoxycarbonyl)pentyl 2-azido-4,6-O-benzylidene-2-deoxy-α-d-galactopyranoside as a common glycosyl acceptor. The synthesis of the tetrasaccharide and the pentasaccharide was improved from the viewpoint of reducing the number of synthetic steps and increasing the total yield by changing from stepwise condensation to block synthesis. Moreover, hexasaccharide E, which contains the oligosaccharide sequence which occurs in E. granulosus, was synthesized from trisaccharide D. We examined the antigenicity of these five oligosaccharides by an enzyme-linked immunosorbent assay (ELISA). Although compounds of C–E did not exhibit antigenicity against cystic echinococcosis (CE) patient sera, compounds B, D, and E showed good serodiagnostic potential for alveolar echinococcosis (AE).     

Mechanisms for NH3 decomposition on Si(100)-(2 x 1) surface: a quantum chemical cluster model study

In this paper, we present a detailed mechanism for the complete decomposition of NH3 to NHx(a) (x = 0-2). Our calculations show that the initial decomposition of NH3 to NH2(a) and H(a) is facile, with a transition-state energy 7.4 kcal mol-1 below the vacuum level. Further decomposition to N(a) or recombination-desorption to NH3(g) is hindered by a large barrier of approximately 46 kcal mol-1. There are two plausible NH2 decomposition pathways: 1) NH2(a) insertion into the surface Si-Si dimer bond, and 2) NH2(a) insertion into the Si-Si backbond. We find that pathway (1) leads to the formation of a surface Si = N unit, similar to a terminal Si = Nt pair in silicon nitride, Si3N4, while pathway (2) leads to the formation of a near-planar, subsurface Si3N unit, in analogy to a central nitrogen atom (Nc) bounded to three silicon atoms in the Si3N4 environment. Based on these results, a plausible microscopic mechanism for the nitridation of the Si(100)-(2 x 1) surface by NH3 is proposed.     

Lewis acid promoted cyclization of enyne triesters and diesters

Reactions of enynes with three or two ester groups (1-4) in the presence of halogen-ligand Lewis acids gave cyclized products with halide incorporation (5-8) with high generality. The cyclization process was also analyzed in a theoretical study. Facile isomerization and dehydrohalogenation of five-membered products 5 and 8 by Al(2)O(3) or Et(3)N were also observed; this process introduces conjugated moieties into the products.     

Solid-state thiotropolone: an extremely rapid intramolecular proton transfer

Through variable-temperature solution-state NMR and molten- and solid-state CP/MAS (13)C NMR spectra, thiotropolone is found to exist as two rapidly equilibrated tautomeric structures, thione and enethiol, even in the solid state far below the melting point. The crystal structure shows an almost perpendicular packing, suggesting that the intramolecular hydrogen bond is dominant.     

Selective growth of ag nanowires on Si(111) surfaces by electroless deposition

Electroless deposition of Ag on atomically flat H-terminated Si(111) surfaces in aqueous alkaline solutions containing Ag ions produced two different sizes of Ag nanowires along atomic step edges: (1) a narrow nanowire of 10 nm in width and 0.5 nm in height and (2) a wide nanowire of 35 nm in width and 11 nm in height. The narrow and wide nanowires were formed by immersion in the solutions containing less than 1 ppb and 8 ppm dissolved-oxygen concentrations, respectively. This result indicates that the dissolved oxygen initiates the formation of Ag nucleation sites and that the fabrication method has a possibility of controlling the size of Ag nanowires.     

Dynamic stability of carbonyl ylides

The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.     

Midgap levels of photoexcited conductive polymers. I. A simple description of the midgap levels based on molecular orbital interaction

We studied the midgap levels appearing in the photoexcited conductive polymers such as trans- and cis-polyacetylenes, poly(p-phenylene), polypyrrole, and polyacene based on the molecular orbital analysis. The midgap levels are constructed from the transformation of the highest occupied molecular orbital and the lowest unoccupied molecular orbital of the ground state. As the result of the localization of the wave functions associated with these midgap levels, large polarization is induced between adjacent carbon atoms. Based on the examination of the energy gap between the two midgap levels, the polymers with a nondegenerate ground state such as cis-polyacetylene, poly(p-phenylene), and polypyrrole would show no sizable photoconductivities.