Exceptionally strong Bragg diffraction from a mesoporous silica film pretreated with chlorotrimethylsilane toward application in X-ray optics

Exceptionally strong Bragg diffraction from a mesoporous silica film is achieved by exposing the as-deposited film to vapor of chlorotrimethylsilane (Me(3)SiCl) before extracting the surfactant. The intensity of the X-ray diffraction peak increased 7 times after the surfactant removal and it approached 30% reflectivity. This large increase of diffraction intensity cannot be explained simply by the improved contrast of the electron density, and rearrangement of the pore wall during the Me(3)SiCl vapor treatment is suggested. It is shown by infrared spectroscopy that Me(3)SiCl with a high grafting reactivity effectively caps the silanol groups and prevents the following condensation, which causes the structural degradation. The substitution of the hydrogen atom of hydroxyl groups with trimethylsilyl groups should help the improvement of the structural regularity by reducing the hydrogen bonds in the pore wall. The achieved strong diffraction opens the gate for the application of these regular mesoporous films prepared by a self-assembly process to optical elements in the X-ray region.     

Crystal Structure of Quinine: The Effects of Vinyl and Methoxy Groups on Molecular Assemblies of Cinchona Alkaloids Cannot Be Ignored

Quinine, one of Cinchona alkaloids, has been of great interest from medical, synthetic, and supramolecular viewpoints. However, unaccountably, the guest‐free (GF) crystal of quinine containing no solvent or other molecules has not been reported for nearly three decades, although GF crystals of other Cinchona alkaloids, such as quinidine, cinchonidine, and cinchonine, are already known. In this study, we successfully revealed the crystal structure of quinine, which belongs to the P2₁ space group with the cell parameters of a=6.0587(1), b=19.2492(5), c=22.2824(7) Å, β=92.1646(11)°, and V=2596.83(12) ų. Interestingly, the crystal has three crystallographically independent molecules in the cell (Z′=3) that are connected through a N(quinoline)???H? O hydrogen bond to form a pseudo three‐two‐fold (3₂) double‐helical motif. The helical motif is completely different from those observed in GF crystals of other Cinchona alkaloids. Hierarchical comparison on the crystal structures of a series of Cinchona alkaloids including quinine clearly demonstrated that only small structural differences of a molecule, particularly the position of the vinyl group, cause a significant variety of assembly manner in the crystalline state. There have been no reports systematically demonstrating such steric effect in crystals of Cinchona alkaloids, and, therefore, the present system contributes to the design of desired functional crystal structures.     

Approximate extension property of mappings

The extension problem is to determine the extendability of a mapping defined on a closed subset of a space into a nice space such as a CW complex over the whole space. In this paper, we consider the extension problem when the codomains are general spaces. We take a shape theoretic approach to generalize the extension theory so that the codomains are allowed to be general spaces. We extend the notion of extension type which has been defined for the class of CW complexes and introduce the notion of approximate extension type which is defined for general spaces. We define approximate extension dimension analogously to extension dimension, replacing the class of CW complexes by the class of finitistic separable metrizable spaces. For every metrizable space X, we show the existence of approximate extension dimension of X.     

Bioluminescence color modulation of Vibrio fischeri strain Y1 coupled with alterable levels of endogenous yellow fluorescent protein and its fluorescence imaging

Bioluminescence (BL) (lambda(max) approximately 535 nm) of Vibrio fischeri strain Y1 has been previously characterized in terms of the fluctuation in intracellular levels of yellow fluorescent protein (YFP). In this study fluorescence microscopic analysis has revealed that yellow fluorescence, as well as blue fluorescence attributable to a luciferase intermediate, is localized to the periphery of V. fischeri Y1 cells. This finding indicates that both YFP and the luciferase are present in the vicinity of the cell membrane. By using cyanide to enhance yellow BL, it has been shown that BL modulation is coupled with the fluctuations in the intracellular levels of YFP and the primary emitter. On the basis of the BL characterization, combined with results of a sedimentation experiment, it has been shown that larger cells produce a relatively stronger yellow BL. Two-dimensional gel electrophoresis of cell-protein extracts has shown that the YFP level is more alterable than the luciferase level. It is postulated that the yellow BL modulation takes place in connection with cell growth.     

Supramolecular structure of N,N-Bis(2-hydroxybenzyl)alkylamine: flexible molecular assembly framework for host without guest and host with guest

N,N-Bis(2-hydroxybenzyl)alkylamine derivatives form a cage-like assembly consisting of two molecules via inter- and intramolecular hydrogen bonds. The derivatives exhibit themselves as host to accept copper-ion guests under the double-oxygen-bridged dimeric system. Quantum chemical calculation suggested that the host-guest interaction is based on a charge-transfer coordination. Comparison of the crystal structures before and after complexation clarifies a rare example of a host-guest compound where the hosts maintain their cage framework through the change of hydrogen bonds to coordination bonds.     

IR-extended photoluminescence mapping of single-wall and double-wall carbon nanotubes

A simple and efficient technique is described for measuring photoluminescence (PL) maps of carbon nanotubes (NTs) in the extended IR range (1-2.3 mum). It consists of preparing an NT/surfactant/gelatin film and measuring PL spectra using a combination of a tunable Ti-sapphire laser excitation and FTIR detection. This procedure has been applied to a wide range of single- and double-wall NTs unveiling chirality and diameter distributions that have so far been very difficult to measure. The problems associated with deducing these distributions are discussed by comparing absorption and PL mapping data for NT samples prepared under different conditions.     

Bioactivity and Mechanical Properties of Polydimethylsiloxane (PDMS)-CaO-SiO2 Hybrids with Different PDMS Contents

Silica-titania and titania aerogels were prepared by supercritical drying using different solvents such as low temperature CO₂ (353 K), high temperature CO₂ (553 K), ethanol (553 K) and ethanol with zeolite (553 K) and their efficiencies for the removal of benzene from a synthetic air mixture were investigated. The aerogels obtained showed both large capacities for benzene adsorption and high photocatalytic activity for its decomposition in the adsorbed state. The degree of benzene removal by silica-titania aerogel seemed to depend on the crystallinity of the titania and was in the order low temperature CO₂ < high temperature CO₂ < ethanol = ethanol with zeolite. The amount of CO₂ liberated by the photocatalytic decomposition of benzene also followed the same sequence. Titania aerogels showed the greatest efficiency in the decomposition of benzene, while the amount of CO₂ evolved was lower than those of the silica-titania systems investigated. The adsorption capacity of benzene basically depended on the silica matrix and was not greatly influenced by the difference in the crystallinity of titania.     

Synthesis and biological evaluation of all A-ring stereoisomers of 5,6-trans-2-methyl-1,25-dihydroxyvitamin D(3) and their 20-epimers: possible binding modes of potent A-ring analogues to vitamin D receptor.

BACKGROUND: The secosteroid 1 alpha,25-dihydroxyvitamin D(3) (1) has a wide variety of biological activities, which makes it a promising therapeutic agent for the treatment of cancer, psoriasis and osteoporosis. Insight into the structure-activity relationships of the A-ring of 1 is still needed to assist the development of more potent and selective analogues as candidate chemotherapeutic agents, as well as to define the molecular mode of action. RESULTS: All possible A-ring stereoisomers of 5,6-trans-2-methyl-1,25-dihydroxyvitamin D(3) (6a-h) and their 20-epimers (7a-h) were designed and efficiently synthesized. The dependence of the affinities for vitamin D receptor (VDR) and vitamin D binding protein (DBP), as well as the HL-60 cell differentiation-inducing activity, upon the stereochemistry of the A-ring and at C20 in the side chain was evaluated. CONCLUSIONS: The binding affinities and potency of the 5,6-trans and 5,6-cis analogues were enhanced by a 2-methyl substituent in a certain orientation. Molecular docking studies based upon the X-ray crystal structure of VDR suggested that the axial 2-methyl group would be accommodated in a pocket surrounded by hydrophobic amino acid residues in the ligand binding domain, resulting in enhanced interaction.