Dynamic NMR line-shape analysis demonstrates that the villin headpiece subdomain folds on the microsecond time scale

There is considerable interest in small proteins that fold very rapidly. These proteins have become attractive targets for both theoretical and computational studies. The independently folded 36-residue villin headpiece subdomain has been the subject of a number of such studies and is predicted to fold quickly. We demonstrate using dynamic NMR line-shape analysis that the protein folds on the time scale of 10 mus. Folding rates were directly estimated between 56 and 78 degrees C using resolved protein resonances from three different residues at both 500 and 700 MHz. The rates estimated using different residues and different field strengths agree well with each other. The estimated folding rate lies between 0.5 and 2.0 x 105 s-1 over this temperature range. The folding rate depends only weakly on temperature.     

Synthesis of Bioactive Organic-Inorganic Hybrids with γ-Methacryloxypropyltrimethoxysilane

Bioactive organic-inorganic hybrids were synthesized through sol-gel processing starting from -methacryloxypropyltrimethoxysilane. NMR-spectroscopic studies showed the presence of silanol groups (Si–OH) and Si–O–Si bonds. In vitro tests of the hybrids for bioactivity with a simulated body fluid (Kokubo solution) indicated that only calcium-containing hybrids could form apatite on their surfaces. Thus the presence of calcium ions was no less important to deposit apatite than the formation of silanol groups or Si–O–Si bonds.     

Some Geometry of the Cone of Nonnegative Definite Matrices and Weights of Associated X2 Distribution

Consider the test problem about matrix normal mean M with the null hypothesis M = O against the alternative that M is nonnegative definite. In our previous paper (Kuriki (1993, Ann. Statist., 21, 1379–1384)), the null distribution of the likelihood ratio statistic has been given in the form of a finite mixture of ² distributions referred to as X² distribution. In this paper, we investigate differential-geometric structure such as second fundamental form and volume element of the boundary of the cone formed by real nonnegative definite matrices, and give a geometric derivation of this null distribution by virtue of the general theory on the X² distribution for piecewise smooth convex cone alternatives developed by Takemura and Kuriki (1997, Ann. Statist., 25, 2368–2387).     

Influence of intramolecular vibrations in charge redistribution at the pentacene-graphite interface

We have investigated the relation between the intramolecular vibrational modes of pentacene and the charge redistribution at the pentacene-graphite interface by using high-resolution electron-energy-loss-spectroscopy. The three main vibrational peaks shift to lower energies as the pentacene film thickness decreases. In order to discuss this energy shift, we have calculated the vibrational energies of a free pentacene molecule by changing its charge state. We have also calculated the vibrational energies of a pentacene molecule adsorbed on a graphite sheet by changing the pentacene-graphite distance. Taking the experimental and calculation results into account, we conclude that the observed energy shifts result from an intramolecular charge redistribution. The present results indicate that the effect of an intramolecular charge redistribution is essential to discuss the origin of an energy shift observed in a vibrational study of an organic molecule/substrate interface.     

High-Quality Protein Crystal Growth of Mouse Lipocalin-Type Prostaglandin D Synthase in Microgravity

Lipocalin-type prostaglandin (PG) D synthase (L-PGDS) catalyzes the isomerization of PGH(2) to PGD(2) and is involved in the regulation of pain and of nonrapid eye movement sleep and the differentiation of male genital organs and adipocytes, etc. L-PGDS is secreted into various body fluids and binds various lipophilic compounds with high affinities, acting also as an extracellular transporter. Mouse L-PGDS with a C65A mutation was previously crystallized with citrate or malonate as a precipitant, and the X-ray crystallographic structure was determined at 2.0 ? resolution. To obtain high-quality crystals, we tried, unsuccessfully, to crystallize the C65A mutant in microgravity under the same conditions used in the previous study. After further purifying the protein and changing the precipitant to polyethylene glycol (PEG) 8000, high-quality crystals were grown in microgravity. The precipitant solution was 40% (w/v) PEG 8000, 100 mM sodium chloride, and 100 mM HEPES-NaOH (pH 7.0). Crystals grew on board the International Space Station for 11 weeks in 2007, yielding single crystals of the wild-type L-PGDS and the C65A mutant, both of which diffracted at around 1.0 ? resolution. The crystal quality was markedly improved through the use of a high-viscosity precipitant solution in microgravity, in combination with the use of a highly purified protein.     

Zirconium-catalyzed chemoselective methylalumination of ethers, amines, and sulfides bearing two terminal alkenyl groups

Chemoselectivity in the methylalumination reaction of unsymmetrical ethers, amines, and sulfides bearing two different terminal alkenyl groups, a 13-tetradecenyl group and an allyl, 4-pentenyl or 6-heptenyl group was examined. The methylalumination of the allyl derivatives proceeded with complete chemoselectivity to afford only the 13-tetradecenyl-monomethylated products. In the methylalumination reactions of the 4-pentenyl and the 6-heptenyl derivatives, in addition to the 13-tetradecenyl-monomethylated products, and dimethylated products were also obtained. However, as in the case of the allyl derivatives, monomethylation to the shorter 4-pentenyl or 6-heptenyl group was not observed, except in the case of 6-heptenyl 13-tetradecenyl amine. The unique selectivity was rationalized upon how readily the intramolecular ligand exchange reaction between intermediate zirconocenium-alkene and zirconocenium-heteroatom complexes could occur.     

Magnetically recoverable osmium catalysts for dihydroxylation of olefins

We prepared magnetically recoverable osmium catalysts by use of magnetite, quaternary ammonium salts, and potassium osmate(VI), and applied them to the dihydroxylation of olefins. By employing 2 mol% of the magnetic osmium catalyst, the dihydroxylation reaction proceeded smoothly to provide the corresponding vicinal diol in a good chemical yield. The osmium catalyst was readily recovered by use of an external magnet, and was reused repeatedly.     

Effect of Photo-Induced Periodic Gain Structure on Oscillation Power and Tunability in Polymer Dye Laser

Pumping dye-doped organic polymer by interference pattern of a frequency-doubled Nd:YAG 532 nm laser to induce a periodic gain-structure and confining it within a stable optical resonator, the oscillation output can be effectively enhanced in comparison with either that of uniform irradiation, i.e., pumping, or of distributed feedback (DFB) operation, and the oscillation wavelength becomes tunable by adjusting the period of the interference pattern. Using Rhodamine-B as a dopant over the range from 200 to 1000 ppm, the oscillation output was enhanced by - 10 dB, which was larger than the output of the uniform irradiation and was - 30% greater than the DFB scheme. Moreover, changing the period of the interference pattern by adjusting the setting angle of the Koster prism enables us to vary the oscillation wavelength around 600 nm.