Construction of hydrogen-bonded ternary organic crystals derived from L-tartaric acid and their application to enantioseparation of secondary alcohols

Ternary organic crystals consisting of an L-tartaric acid-derived dicarboxylic acid, a commercially available achiral diamine, and a chiral secondary alcohol have been developed and characterized by X-ray crystallography. 1D, 2D, and 3D hydrogen-bonded supramolecular networks were constructed, depending on the structure of the diamine used. Benzylic and aliphatic secondary alcohols were enantioselectively incorporated into the crystal and were successfully enantioseparated with up to 86 and 79% enantiomeric excess (ee), respectively. Selective incorporation of one enantiomer of 2-butanol, which is a small chiral aliphatic alcohol, was achieved by the cooperative effects of hydrogen bonds, CH···π interactions, and van der Waals interactions between the guest and host molecules, with the aid of two water molecules. The high host potential of the binary supramolecular system is mainly attributed to the skewed conformation of two rigid aromatic groups of tartaric acid derivatives, which prevents dense packing of the molecules and enhances the formation of multicomponent inclusion crystals.     

Intramolecular iodoetherification of ene or diene ketals: facile synthesis of spiroketals

A novel and rapid approach to chiral mono- or di-substituted spiroketals based on remote asymmetric induction by intramolecular iodoetherification of ene or diene ketals has been developed. This strategy concisely offers 5,5- and 5,6-spiroketals including the natural insect pheromone of the wasp.     

Fluorescence studies on phenylene moieties embedded in a framework of periodic mesoporous organosilica

The excited state characteristics of phenylene (Ph)-bridged periodic mesoporous organosilica (PMO) powders with crystal-like and amorphous wall structures are investigated. Crystal-like Ph-PMO has a molecular ordering of the bridging organic moieties with intervals of 0.76 and 0.44 nm parallel and perpendicular to the mesochannel direction, respectively, whereas amorphous Ph-PMO has no molecular-level periodicity in the wall. Fluorescence from the exciton and excimer of the Ph moieties and the defect center in the silicate network were detected at room temperature, but fluorescence from the excimer and the defect center were not detected at 77 K for crystal-like Ph-PMO dispersed in a methanol/ethanol mixed solvent. The decay curve of the exciton fluorescence of crystal-like Ph-PMO at room temperature was analyzed successfully using a one-dimensional diffusion model quenched by the defect center and the excimer site. The results were discussed in comparison with those for the crystal-like biphenylene-bridged PMO reported in the preceding paper (Yamanaka et al., Phys. Chem. Chem. Phys., 2010, 12, 11688-11696). The existence of excited states with various conformations including ground state dimers or aggregates of the Ph moieties was suggested for amorphous Ph-PMO. It was clearly apparent that the differences in the excited state dynamics reflected the differences in the molecular-level structure in the wall.     

Pushing exercise program to correct glottal incompetence

A voice therapy program using pushing exercises to correct glottal incompetence is described. The program utilizes various types of instrumentation to determine whether or not a given patient is likely to benefit from the treatment. The program also provides feedback of target voices. Three cases with incomplete glottal closure and subsequent vocal dysphonia characterized by an asthenic breathy quality are used to illustrate the program. Details of the program, termination criteria, and problems and precautions learned from treating 29 patients over a 3-year period are presented.     

On time-like surfaces of positive constant Gaussian curvature and imaginary principal curvatures

We establish the Bäcklund transformation for the construction of time-like surfaces with positive Gaussian curvature and imaginary principal curvatures. The construction can be realized by algebraic algorithm via Darboux transformations.     

Chemical synthesis and application of C-terminally 5-carboxyfluorescein-labelled thymopentin as a fluorescent probe for thymopoietin receptor.

Thymopentin (TP5) is a synthetic pentapeptide fragment, which corresponds to position 32 - 36 of thymic polypeptide thymopoietin. Thymopoietin and TP5 display a variety of biological functions, including phenotypic differentiation of T cells and the regulation of immune systems. Previous chemical modification experiments suggested that there was an absolute requirement for N-terminal amino acids to maintain the biological activity of TP5. On the basis of this structure-activity relationship, we designed and synthesized the C-terminally 5-carboxyfluorescein-coupled TP5 (TP5-FAM) as a fluorescent probe for thymopoietin receptor. TP5-FAM could bind to the membrane of human lymphoid cell lines, MOLT-4 cells, in which the thymopoietin receptor is expressed. The binding is specific and saturable (K(d) = 33 microM). TP5 and human splenopentin are nearly equipotent inhibitors of TP5-FAM binding to the thymopoietin receptor, but porcine secretin did not show any significant inhibition of TP5-FAM binding to MOLT-4 cells. Thus, TP5-FAM is suggested to be a potent and biologically active ligand that would be useful for studying the binding and functional characteristics of the human thymopoietin receptor.     

Synthetic studies on oligomycins. Enantiospecific synthesis of the oligomycin B spiroketal portion and establishment of the absolute stereochemistry of oligomycin B

The enantiospecific synthesis of the oligomycin B degradation product 2, corresponding to the C19–C34 spiroketal portion, has been achieved by sequential coupling of the C19–C21, C22–C27, and C28–C34 subunits, establishing the absolute stereochemistry of oligomycin B.     

Relation between Hall-magnetohydrodynamics and the kinetic Alfvén wave

Effects of a finite ion temperature on the Hall magnetohydrodynamics (MHD), which breaks down for a finite ion temperature, are clarified in terms of a rigorous three-field kinetic dispersion relation. The MHD mode equation becomes anisotropic with respect to the ion pressure because of the double adiabaticity in ion dynamics.