Rapid method based on reversed-phase high-performance liquid chromatography for purification of human myelin basic protein and its thrombic and endoproteinase Lys-C peptides.

Reversed-phase high-performance liquid chromatography was applied to isolate myelin basic protein from human brain, followed by separation of proteolytic peptides thereof on the same chromatographic system. Brain tissue was delipidated under conditions that keep copurifying proteases inactive. The crude brain protein fraction was applied directly to a C4 column. The homogeneous protein obtained in this way was digested with thrombin and endoproteinase Lys-C in order to produce short defined myelin basic protein peptides. The purified peptides were used to determine the antigen fine specificity of myelin basic protein recognizing T lymphocyte lines isolated from multiple sclerosis patients.     

Chiral ligand-controlled asymmetric conjugate addition of lithium amides to enoates

The external chiral ligand-controlled asymmetric conjugate addition reaction of lithium amides with alpha,beta-unsaturated esters provided beta-amino esters in high yields and high enantioselectivities.     

Copper-catalyzed allylation of carbonyl derivatives using allyl(2-pyridyl)silanes

[reaction: see text] We have developed an efficient copper-catalyzed allylation of carbonyl derivatives using allyl(2-pyridyl)silanes, in which the strong directing effect of the 2-pyridyl group was observed. A useful synthesis and allylation of substituted allyl(2-pyridyl)silanes is also described.     

Coumarin-conjugated cyclodextrins: remarkable enhancement of the chemical-to-light energy transfer efficiency

One or two coumarin units were incorporated to the primary face of γ-cyclodextrin (γ-CD), and the resultant coumarin derivatives were employed to harvest the chemical energy generated in the reaction of bis(trichlorophenyl)oxalate with hydrogen peroxide. In comparison with the coumarin without CD cavity for molecular recognition, the coumarin–CD conjugates demonstrated much higher chemiluminescence inetensity, indicating that the CD moiety remarkably improves the chemical energy transfer.     

Crystal habit of fcc metal particles controlled by electrode potential in solution

The crystal habit of fcc metal particles formed on an amorphous carbon film electrode in solution at different electrode potentials is discussed. The fcc metal particles have different crystallographic habits depending on applied electrode potential; that is, icosahedral and/or decahedral particles are formed at lower potentials, and fcc single-crystalline or polycrystalline particles at higher potentials. It was found that decahedra and icosahedra of Cu-Au alloy particles are formed in the potential region of underpotential deposition (UPD) of Cu at which only fcc Au single-crystalline particles and Au polycrystalline particles appear. This is attributed to the charge transfer from the UPD Cu ions to the Au overlayer of Cu-Au alloy particles. The formation of decahedral and icosahedral Cu-Au alloy particles depends on the composition of the Cu-Au alloy. On the basis of these results it was deduced that the contraction of the surface lattice of the growing particles is responsible for the formation of icosahedral and decahedral particles. Received: 25 February 1997 / Accepted: 21 April 1997     

A novel reaction of allylic alcohols with hexafluoropropene-diethylamine adduct (PPDA) to form 2-fluoro-2-trifluoromethyl-4-alkenamide

Treatment of allylic alcohols with hexafluoropropene-diethylamine adduct (PPDA) afforded N,N-diethyl-2-fluoro-2-trifluoromethyl-4-alkenamides which were formed by the Claisen rearrangement of intermediary 2-alkenyl-1-diethylamino-2,3,3,3-tetrafluoro-1-propenyl ethers. Although (E)-allylic alcohols gave two diastereomeric products in about 1:1 ratio, (Z)-allylic alcohols gave the corresponding product as a single diastereomer.     

Cp/mas 13c nmr and Electron Diffraction Study of Bacterial Cellulose Structure Affected by Cell Wall Polysaccharides

Acetobacter xylinum was cultured in Schramm–Hestrin medium containing pectin (pectin medium), xylan (xylan medium), or glucomannan (mannan medium). X-ray diffractometry revealed that xylan and glucomannan affected the size of the cellulose crystals and their d-spacing values. Solid-state cross polarization magic angle spinning carbon-13 nuclear magnetic resonance spectroscopy indicated that the ratio of cellulose I was reduced by the addition of polysaccharides. These effects were more remarkable on the cellulose in the mannan medium than that in the xylan medium, and were scarcely observed in the pectin medium. Electron diffraction analysis revealed that these effects on hemicelluloses along cellulose microfibrils are continuous in the mannan medium and discontinuous in the xylan medium. These findings suggest that the uronic acid in the polysaccharides prevents interactions with cellulose leading to alterations of the structure of the cellulose crystal.