A highly regio- and stereoselective formation of bicyclo[4.2.0]oct-5-ene derivatives through thermal intramolecular [2 + 2] cycloaddition of allenes

Thermal [2 + 2] cycloaddition of allenes with an additional multiple bond is described. By simply heating the allenenes or allenynes having a three-atom tether in an appropriate solvent such as dioxane or DMF, the distal double bond of the allenic moiety regioselectively participates in the cycloaddition to form bicyclo[4.2.0]oct-5-ene derivatives in good to excellent yields. In all the reactions of allenenes, the olefin geometry was completely transferred to the cycloadducts. While the reaction of terminal allenes afforded bicyclic cyclobutane derivatives as a single isomer, the cycloaddition of some internal allenes with axial chirality yielded a diastereomeric mixture of cycloadducts. These results are in good accordance with the stepwise mechanism through a biradical intermediate with a coplanar allyl radical.     

InCl3/I2-catalyzed cross-coupling of alkyl trimethylsilyl ethers and allylsilanes via an in situ derived combined Lewis acid of InCl3 and Me3SiI

Direct Csp3-Csp3 coupling of various aliphatic trimethylsilyl ethers and allylsilanes is effectively catalyzed by InCl3 and I2. The transformation is thought to involve an in situ-derived combined Lewis acid of InCl3 and Me3SiI. The reaction can be used for the construction of quaternary-quaternary and quaternary-tertiary carbon-carbon bonds. This system enabled a highly chemoselective coupling to be conducted with a trimethylsilyl ether including an aryl halide moiety. Furthermore, couplings were possible using an alkynyltrimethylsilane and a trimethylsilyl ketene acetal.     

Comparative study of urea and betaine solutions by dielectric spectroscopy: liquid structures of a protein denaturant and stabilizer

We performed dielectric spectroscopy measurements on aqueous solutions of glycine betaine (N,N,N-trimethylglycine), which is known to be a strong stabilizer of globular proteins, over a wide concentration range (3-62 wt %) and compared the results with our previously published data for aqueous solutions of urea, a representative protein denaturant. The hydration number of betaine (9), calculated on the basis of the reduction in the dielectric relaxation strength of bulk water with addition of betaine, is significantly larger than that of urea (2). Furthermore, the dielectric relaxation time increased with betaine concentration, while that remained nearly constant for the urea-water system over a wide concentration range. This difference between urea and betaine is probably related to their opposite effects on the protein stabilization.     

Gold-catalyzed hydroarylation of allenes: a highly regioselective carbon-carbon bond formation producing six-membered rings

Gold-catalyzed intramolecular hydroarylation of allenic anilines and phenols offers an efficient route to dihydroquinoline and chromene derivatives under mild reaction conditions. The hydroarylation takes place at the terminal or central allenic carbon depending on the substrate structure, leading to a highly selective formation of six-membered rings.     

Bifunctional pathways mediated by Pt clusters and Al2O3 in the catalytic combustion of dimethyl ether

Mixtures of Pt clusters dispersed on gamma-Al(2)O(3) and additional gamma-Al(2)O(3) led to much higher DME combustion turnover rates than on the individual components or on Pt clusters supported on non-acidic oxides.     

Soft-to-hard transformation of the mechanical properties of dynamic covalent polymers through component incorporation

The mechanical properties of acylhydrazone dynamic polymers may be converted from soft to hard by the incorporation of rigid monomeric components into the original soft polymer backbone, taking advantage of acylhydrazone bond exchange.     

Time dilation of a bound half-fluxon pair in a long Josephson junction with a ferromagnetic insulator

The fluxon dynamics in a long Josephson junction with a ferromagnetic insulating layer is investigated. It is found that the Josephson phase obeys a double sine-Gordon equation involving a bound pi fluxon solution, and the internal oscillations of the bound pair acting as a clock exhibit Lorentz reductions in their frequencies regarded as a relativistic effect in the time domain, i.e., time dilation. This is the complement to the Lorentz contraction of fluxons with no clock. A possible observation scheme is also discussed.     

Asymmetric Transformation Driven by Confinement and Self-Release in Single-Layered Porous Nanosheets

Reported here is the use of single-layered, chiral porous sheets with induced pore chirality for repeatable asymmetric transformations and self-separation without the need for chiral catalysts or chiral auxiliaries. The asymmetric induction is driven by chiral fixation of absorbed achiral substrates inside the chiral pores for transformation into enantiopure products with enantioselectivities of greater than 99 % ee. When the conversion is completed, the products are spontaneously separated out of the pores, enabling the porous sheets to perform repeated cycles of converting achiral substrates into chiral products for release without compromising pore performance. Confinement of achiral substrates into two-dimensional chiral porous materials provides access to a highly efficient alternative to current asymmetric synthesis methodologies.     

Signal characteristics of FLAIR related to water content: comparison with conventional spin echo imaging in infarcted rat brain

To examine the correlation between tissue water content and signal intensity on fluid-attenuated inversion recovery (FLAIR) images, we analyzed infarcted rat brain, verified the results by theoretical simulation, and compared them with conventional spin-echo images. We produced brain infarction with cavitation in five rats by middle cerebral artery occlusion. After in vivo MRI, histologic sections of the MRI plane were obtained. We measured the signal intensity of regions on FLAIR and spin-echo images, and measured the area of cavitation on histologic sections. We plotted curves of cavity percentage to signal intensity. Theoretical values were calculated using a two-compartment model. On the curve of cavity area to signal intensity, the signal on FLAIR images peaked in tissues with 20% to 30% area of cavitation. On the theoretical curve, the signal on FLAIR images peaked at 90% tissue water content. These results seem to be characteristic of FLAIR.