Development of a new traceless aniline linker for solid-phase synthesis of azomethines. Application to parallel synthesis of a rod-shaped liquid crystalline library

A new traceless linker was developed to synthesize a library of 42 compounds possessing an azomethine linkage using combinatorial solid-phase parallel synthesis. The loading of the substrates on a solid support and cleavage from the solid support were performed by an imine synthesis and by imine-exchanged process under mild conditions, respectively. Thioesters with a hydroxy group on the central core exhibited liquid crystalline properties with the widest transition temperatures in the library.     

Sugar-sensitive thin films composed of concanavalin A and sugar-bearing polymers.

Layered thin films composed of concanavalin A (Con A) and sugar-bearing polymers were prepared by a layer-by-layer deposition of Con A and the polymer on a solid surface. The sugar-induced disintegration was studied. Con A-polymer layered films could be successfully prepared using a maltose-bearing polymer (PV-MA), while melibiose- and glucose-bearing polymers (PV-MEA and PV-G) did not afford a layered film, due to a weak affinity of PV-MEA and PV-G to Con A. The Con A/PV-MA layered film was stable in pH 7 and 8 solutions, while in a pH 6 medium the film was slightly unstable. The Con A/PV-MA film was disintegrated upon the addition of sugars in solution owing to a preferential binding of the sugars to the binding site of Con A in the film. The disintegration rate was dependent on the type of sugar and its concentration. The Con A/PV-MA film was disintegrated rapidly upon the addition of methyl alpha-D-mannopyranoside, while the rate was slower upon the addition of the same concentration of D-mannose, D-glucose and methyl alpha-D-glucopyranoside. The present system may be useful for constructing sensitive devices that can release a drug or other functional molecules in response to sugars.     

Topological Landau-Ginzburg theory with a rational potential and the dispersionless KP hierarchy

Based on the dispersionless KP (dKP) theory, we study a topological Landau-Ginzburg (LG) theory characterized by a rational potential. Writing the dKP hierarchy in a general form treating all the primaries in an equal basis, we find that the hierarchy naturally includes the dispersionless (continuous) limit of Toda hierarchy and its generalizations having a finite number of primaries. Several flat solutions of the topological LG theory are obtained in this formulation, and are identified with those discussed by Dubrovin. We explicitly construct gravitational descendants for all the primary fields. Giving a residue formulae for the 3-point functions of the fields, we show that these 3-point functions satisfy the topological recursion relation. The string equation is obtained as the generalized hodograph solutions of the dKP hierarchy, which show that all the gravitational effects to the constitutive equations (2-point functions) can be renormalized into the coupling constants in the small phase space. Supported in part by NSF grant DMS-9403597.     

Structural property and function of D-erythro asymmetric chain sphingomyelins as studied by microcalorimetry and electron microscopy

D-erythro sphingomyelines (SM) having a defined acyl chain were synthesized with sphingosylphosphorylcholine as a starting material, and both a structural property and its relating phase transition phenomenon were compared between a symmetric chain length SM (palmitoyl-SM: C16-SM) and asymmetric chain length SMs (behenoyl-SM: C22-SM, lignoceryl-SM: C24-SM). Furthermore, effect of increasing a content of asymmetric chain SMs in the mixture systems of C22-SM/C16-SM, and C24-SM/C16-SM was investigated. The present calorimetric and electron microscopic studies revealed that (1) The main transition enthalpy is smaller for the asymmetric chain SMs than for the symmetric chain SM by about 3 kJ mol⁻¹, although the acyl chain length is longer for the former than for latter; (2) Relatively small size vesicles (100∼200 nm diameters) surrounded by one or more lamellae are observed for the asymmetric chain SMs, in contrast to large multilamellar vesicles (1500∼2500 nm diameters) having at least fifteen stained lamellae for the symmetric chain SM and (3) The coexisting asymmetric chain SMs cause the decrease in size and multiplicity for the MLV of the symmetric chain SM, simultaneously with a decrease in the main transition enthalpy.     

Structure and properties of a styrene–butadiene–styrene block copolymer

Electron-microscopic texture and physical properties of a styrene–butadiene–styrene (SBS) block copolymer obtained by casting from toluene, carbon tetrachloride, ethyl acetate, and methyl ethyl ketone are discussed. Two peaks are observed in the mechanical loss (tan delta;) curve at ?70 and 100°C which are attributed to segmental motion of polybutadiene and polystyrene, respectively. The polybutadiene peak heights are in the order of solubility in the solvent used; the polystyrene peak heights are in converse order. In addition to these peaks, a third peak is observed at 10°C for specimens cast from ethyl acetate or methyl ethyl ketone. A transition corresponding to this peak is also noticed in thermal analysis. It is proposed that aggregation of styrene blocks is relatively incomplete in specimens cast from solution in poor solvents.     

Explicit integration of the full symmetric Toda hierarchy and the sorting property

We give an explicit formula for the solution to the initial-value problem of the full symmetric Toda hierarchy. The formula is obtained by the orthogonalization procedure of Szegö, and is also interpreted as a consequence of the QR factorization method of Symes. The sorting property of the dynamics is also proved for the case of a generic symmetric matrix in the sense described in the text, and generalizations of tridagonal formulae are given for the case of matrices with 2M+1 nonzero diagonals.     

An X-ray diffraction study of anharmonic thermal vibrations in the ionic conductor,barium chloride fluoride (BaClF)

Integrated intensities of X-ray reflections from a barium chloride fluoride single crystal were measured at 24, 180, 289, 402, 467 and 610°C. The intensities were used for the determination of the anharmonic potential parameters up to the third order. Harmonic potential parameters for each ion were obtained from the temperature dependence of thermal parameters, and anharmonic potential parameters were determined by the least-squares procedures, utilizing the temperature factor formalism based on the cumulant expansion. As a result, it has been found that the Ba²⁺ and Cl^? ions show an anharmonicity, while no significant anharmonic effect was detected for the F^? ion. From the potential calculated around the Cl^? and F^? ions, it was found that both Cl^? and F^? ions diffuse more easily within the (001) plane than along the c axis.     

Structure and synthesis of unsaturaded trihydroxy c18 fatty : Acids in rice plants suffering from rice blast disease

Structural elucidation including the absolute configuration was carried out on the trihydroxy C₁₈ -fatty acids isolated from rice plant, Sasanishiki suffered from rice blast disease.     

Postbuckling behavior of circular cylindrical shells under compression

Applying the Galerkin procedure to the Donnell basic equations, reasonably accurate solutions are obtained for the postbuckling behavior of clamped circular cylindrical shells under axial compression. To make a distinct comparison with the previous experimental results, calculations are carried out for shells with the same elastic and geometric parameters and the relations between the waveform, axial shortening and maximum deflections with applied loads are clarified. The results here obtained are found to be in reasonable agreement with experimental ones throughout the regions with fairly large deformations.