1H-NMR Investigation of the Binding of 2-Methylnaphthalene to α-Cyclodextrin in D2O Solutions

As -cyclodextrin (-CD) was added to D₂Osolutions of 2-methylnaphthalene, its proton signals shifted to lower fieldsat low concentrations of -CD. At 2.0 × 10^-2 moldm^-3 of -CD, however, a reverse, higher-field shift wasobserved for the H-8 signal, indicating the formation of 1 : 1 and 2 : 1-CD–2-methylnaphthalene inclusion complexes. Intrinsic chemicalshift differences of all the protons in 2-methylnaphthalene have beenevaluated for both the 1 : 1 and the 2 : 1-CD–2-methylnaphthalene inclusion complexes. These intrinsicchemical shift differences suggest that the first -CD molecule has noselectivity in accommodating one end of uncomplexed 2-methylnaphthalene;-CD binds to a methyl group, as well as a naphthalene ring-end havingno methyl group, to form the 1 : 1 inclusion complex, resulting in theformation of two kinds of 1 : 1 complexes.     

Salt effect in the base-catalyzed polymerization of unsaturated amide compounds. III. Nature of the polymerization system

Coordination complexes of lithium chloride with polar solvents and monomers were isolated, and their physical properties were studied. The parallel between stabilities of isolated complexes and coordination function in the polymerization system is discussed. The increase of the Q and e values of p-vinylbenzamide (VBA) supports the mechanism of vinyl-type polymerization of VBA in the presence of the salt. The specific solvent effect of dimethyl sulfoxide was determined by measurement of electrical conductivity of a model system.     

A new synthesis of pyrroles by the condensation of cyclopropenes and nitriles mediated by gallium(III) and indium(III) salts

Gallium(III) and indium(III) halides were found to mediate the condensation of cyclopropenes and nitriles to give pyrrole derivatives in moderate yields. When excess nitrile was present, diazepine was also formed.     

Profiling and comprehensive expression analysis of ABC transporter solute-binding proteins of Bacillus subtilis membrane based on a proteomic approach

We analyzed ABC transporter solute-binding proteins (SBPs) of the Bacillus subtilis membrane using a proteomic approach. We prepared a washed cell membrane fraction that was insoluble in 134 mM nondetergent sulfobetaine and then extracted proteins using mixtures of detergents in a stepwise manner. The membrane proteins were resolved by three two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) or two one-dimensional (1-D) PAGE procedures, electroblotted, and digested in the presence of 5% or 80% acetonitrile. Thereafter, matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF MS) identified 637 proteins corresponding to 15.9% of the total cellular proteins. We predicted that among these, 256 were membrane proteins, 101 were lipoproteins or secretory proteins and 280 were soluble proteins containing peripheral proteins that function in both the cytoplasm and the cell membrane such as SecA and FtsY. Among the 637 proteins, we identified 30 SBPs among 38 importers predicted by a bioinformatic search of the genome. We confirmed expression of the genes for the 30 SBPs using DNA microarray analysis. We compared the 2-D gel separation profiles of submembrane fractions solubilized by 1% n-dodecyl-beta-D-maltoside from cells cultured on Luria Bertani (LB), S7, and S7 medium without glutamate as well as DNA microarray data on LB and S7. The results suggested that YcdH, YtmK and YurO are binding proteins for Mn(++), glutamate and glucose, respectively, and that YqiX and YxeM are binding proteins for amino acids (tryptophan in S7 medium).     

Palladium-catalyzed regio- and diastereo-selective allylic alkylation using 2-(diphenylphosphino)benzoic acid: construction of vicinal quaternary and tertiary carbon centers

The palladium-catalyzed regio- and diastereo-selective allylic alkylation of allyl acetates with carbon nucleophiles occurred. The stereochemistry was highly controlled by the palladium catalyst with 2-(diphenylphosphino)benzoic acid as the ligand, and vicinal quaternary and tertiary carbon centers were constructed.     

Polymeric phosphonium salts as a novel class of cationic biocides. V. Synthesis and antibacterial activity of polyesters releasing phosphonium biocides

Polyesters were prepared which retained phosphonium biocides as counter ions of sodium sulfonate moieties incorporated into the polymers, and surface antibacterial activity of the polyester films against Staphylococcus aureus and Escherichia coli was explored. These films exhibited a high surface antibacterial activity against S. aureus and E. coli, particularly against S. aureus, and the activity was affected by the structure and the compositional ratio of the phosphonium salts. Amount of the released phosphonium salts was very small, so that liberation of the phosphonium biocides can be expected to occur over a long period. Morphological changes of the cells of S. aureus and E. coli in contact with the polyester films were evaluated by scanning electron microscopy. It was found that the surface antibacterial activity of the polyester films was rather bacteriostatic than bactericidal as evidenced by no morphological changes of the bacterial cells in contact with the phosphonium biocides © 1993 John Wiley & Sons, Inc.     

Some structural features induced by the space-time metrical fluctuation in the theory of gravitational fields

Under the assumption that the so-called space-time fluctuationy(x) in a classical sense, attached to each point of the gravitational field at some microscopic stage, is summarized as the metrical fluctuation in the formg _λκ (x)=g_λκ (x)·exp2σ(y(x)), some new physical aspects induced by the conformal scalarσ(x) (≡σ(y(x))) are found: By introducing the torsionT _κ ^λμ (x) from a general standpoint, the resulting micro-gravitational field is made to have a conformally non-Riemannian structure, where a special form ofT _κ ^λμ (i.e.,T _κ ^λμ =δ _κ ^λ σ_μ?δ _κ ^μ σ_λ(σ_μ=?σ/?x ^μ)) shows some peculiar features. An averaging process with respect toy is taken into account, by which the spatial structure of the corresponding macro-field is shown, in general, to have a somewhat “non”-Riemannian structure due to the contributions of the torsionT _κ ^λμ .     

The circular dichroism spectra of the β-cyclodextrin complex with azulene

When azulene is included in the cavity of β-cyclodextrin (β-CDx), induced circular dichroism (CD) bands are observed in the corresponding absorption bands of azulene. On the basis of the theoretical conclusions for β-CDx complexes with naphthalene derivatives of Harata and Uedaira, it is concluded from the signs of the CD bands that the first (about 455 to 715 nm), third (about 290 to 305 nm) and fifth (at about 238 nm) absorption bands have the transition dipole moments perpendicular to the long axis and the second 305 to 360 nm), fourth (about 240 to 290 nm) and sixth (shorter than 220 nm) absorption bands have the transition dipole moments parallel to the long axis of azulene. Our assignments are in complete agreement with earlier assignments. Our experimental results do not provide any information regarding two new electronic transitions suggested theoretically by Thulstrup et al.     

Structural colors in nature: the role of regularity and irregularity in the structure.

Coloring in nature mostly comes from the inherent colors of materials, but it sometimes has a purely physical origin, such as diffraction or interference of light. The latter, called structural color or iridescence, has long been a problem of scientific interest. Recently, structural colors have attracted great interest because their applications have been rapidly progressing in many fields related to vision, such as the paint, automobile, cosmetics, and textile industries. As the research progresses, however, it has become clear that these colors are due to the presence of surprisingly minute microstructures, which are hardly attainable even by ultramodern nanotechnology. Fundamentally, most of the structural colors originate from basic optical processes represented by thin-film interference, multilayer interference, a diffraction grating effect, photonic crystals, light scattering, and so on. However, to enhance the perception of the eyes, natural creatures have produced various designs, in the course of evolution, to fulfill simultaneously high reflectivity in a specific wavelength range and the generation of diffusive light in a wide angular range. At a glance, these two characteristics seem to contradict each other in the usual optical sense, but these seemingly conflicting requirements are realized by combining appropriate amounts of regularity and irregularity of the structure. In this Review, we first explain the fundamental optical properties underlying the structural colors, and then survey these mysteries of nature from the viewpoint of regularity and irregularity of the structure. Finally, we propose a general principle of structural colors based on structural hierarchy and show their up-to-date applications.     

Isolation of heptadepsin, a novel bacterial cyclic depsipeptide that inhibits lipopolysaccharide activity

Lipopolysaccharide (LPS) is considered to cause various inflammatory reactions. We searched among microbial secondary metabolites for compounds that could inhibit LPS-stimulated adhesion between human umbilical vein endothelial cells (HUVEC) and human myelocytic cell line HL-60 cells. In the course of our screening, we isolated a novel cyclic depsipeptide, which we named heptadepsin, from the whole culture broth of Paenibacillus sp. The addition of heptadepsin prior to LPS stimulation decreased HL-60 cell-HUVEC adhesion without showing any cytotoxicity. It also inhibited the cellular adhesion induced by lipid A, the active component of LPS, but it did not inhibit TNF-alpha or IL-1beta-induced cell adhesion. The result of surface plasmon resonance (SPR) analysis revealed that heptadepsin interacted with lipid A directly. Thus, heptadepsin, a novel naturally occurring cyclic heptadepsipeptide, was shown to inactivate LPS by direct interaction with LPS.