Flexible host frameworks with diverse cavities in inclusion crystals of bile acids and their derivatives

We have systematically investigated structures and properties of inclusion crystals of bile acids and their derivatives. These steroidal compounds form diverse host frameworks having zero‐, one‐ and two‐dimensional cavities, causing various inclusion behaviors towards many organic compounds. The diverse host frameworks exhibit the following guest‐dependent flexibility. First, the frameworks mainly depend on the included guests in size and shape. The size‐dependence is quantitatively estimated by the parameter PCcavity, which is the volume ratio of a guest molecule to a host cavity. The resulting values of PCcavity lie in the range of 42–76%. Second, each of the host frameworks has its own range of the values. Some guests can employ two different frameworks with the boundary values, explaining formation of polymorphic crystals. Third, the host frameworks are selected by host–guest interactions through weak hydrogen bonds, such as NH/π and CH/O. The weak hydrogen bonds play an important role for various selective inclusion processes. Fourth, the host frameworks are dynamically exchangeable, resulting in intercalation and polymerization in the cavities. These static and dynamic structures of the frameworks demonstrate great potential of crystalline organic inclusion compounds as functional materials. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 124–135; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20171     

Electron transport membrane: Preparation of polypeptide membrane with spacers between the polymer matrix and viologen moiety and their application to an electron transfer reaction

Polypeptide membranes with several lengths of spacers [? (CH₂)_n? ; n = 3, 6, 12] between the polymer matrix and viologen moiety as a functional group were prepared. Reduction of K₃Fe(CN)₆ with Na₂S₂O₄ across the obtained membrane in aqueous media were carried out and reduction rate of K₃Fe(CN)₆ across the membrane of n = 6 was faster than that of n = 3. However, the reduction of the membrane (n = 12) did not proceed chemically and electrochemically at all.     

Electro-optic response of cubic liquid crystal compounds in Kerr cell geometry

We present the results of our investigations on the electro-optic response of the cubic phase liquid crystal compounds 1,2-bis-[4-n-octyloxy-benzoyl]-hydrazine (BABH8) and 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC16) in Kerr cell geometry. The AC electric field response in the BABH8 cubic phase was found to be as small as that of the isotropic phase, even though there was a response in the adjacent smectic C (SmC) phase. The response in the SmC phase means that the BABH8 molecule itself has an electric field coupling ability, but this ability is strongly inactivated in the cubic phase. This inactivity to the AC fields was also found in the cubic phase of ANBC16. This behaviour could be explained by the small structural unit size of the cubic phase.     

Pipette tip biosensors for bacterial double-stranded DNA using bioluminescence induced by zinc finger luciferase

The authors describe a pipette type of biosensor for detecting target genes and using a zinc finger protein fused to luciferase (ZF luciferase). The ZF protein binds to a specific DNA sequence, and the target double-stranded (ds) DNA can be detected by monitoring the enzymatic activity of ZF luciferase. A small avidin-immobilized reaction plate is placed on a plastic pipette tip (referred to as Biologi tip). The dsDNA detection procedures are carried out by using a programmable dispensing robot equipped with a photodetector. These procedures include (a) the aspiration of an analyte to capture the biotinylated target dsDNA (a product of a polymerase chain reaction) on the small reaction plate inside the pipette tip, (b) the introduction of ZF luciferase and luciferin into the pipette tip, and (c) migration of the pipette tip to the detection port to measure bioluminescence on the small reaction plate. The emission originating from luciferase activity is observed on the reaction plate containing immobilized biotin-tagged target dsDNA, whereas plates containing non-target or biotinylated single-stranded DNA only do not yield a signal. The intensity of emission increases proportionally to the concentration of dsDNA, and the detection limit of the target dsDNA is as low as 62 pM. An actual genomic DNA sample from Escherichia coli O157 was successfully detected by this automatic analyzer using the Biologi tip equipped with a reaction plate. This indicates that this system has a large potential for practical applications, including in particular point-of-care analyses in hygiene control, food safety testing, and clinical diagnosis.

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Graphical abstract A pipette-type biosensor was developed to detect target genes using a luciferase-fused zinc finger protein, where a small NeutrAvidin-immobilized reaction plate was placed on the tip, and the biotinylated target double-stranded DNA was detected by monitoring the bound luciferase activity.

     

Hydrogen Peroxide Formation by Electric Discharge with Fine Bubbles

Pulsed discharge plasma is typical oxidation technology for disposing organic compounds in aqueous solutions. When this electrical discharge plasma was applied in water, it may produce hydrogen peroxide (H₂O₂) without any catalyst or chemical agent. In order to increase H₂O₂ production by electrical discharge plasma in water, fine bubbles were introduced into the electrical discharge plasma in this experiment. Bipolar pulsed voltages were applied to cylindrical electrodes in the water while Ar or O₂ bubbles were introduced, generating a pulsed discharge plasma. The introduction of the bubbles seemed to enhance the dissociation of water molecules and increased H₂O₂ formation, especially with O₂ bubbling. Dissolved oxygen in the water contributed to H₂O₂ formation by pulsed discharge plasma with the bubbles, while dissociation of water molecules was the cause of H₂O₂ formation by pulsed discharge plasma without bubbles. More H₂O₂ was formed by pulsed discharge plasma with O₂ bubbles, because the amount of dissolved oxygen in the water increased upon bubbling with O₂.     

Preparation of a cycloheptane ring from a 1,2-diketone with high stereoselectivity

Treatment of 1,6-dialkylhexa-1,5-diene-3,4-diones with bis(iodozincio)methane gave zinc alkoxides of cis-5,6-dialkylcyclohepta-3,7-diene-1,3-diol in good yields at room temperature. The reaction proceeded with high stereospecificity. Bis(iodozincio)methane converted the diketone into the cis-divinylcyclopropane-1,2-diol stereoselectively; this diol transformed into the corresponding cycloheptane derivative stereospecifically via Cope rearrangement.     

Potent 2,2-diphenyl-1-picrylhydrazyl radical-scavenging activity of novel antioxidants, double-stranded tyrosine residues conjugating pyrocatechol

New potent antioxidants conjugating the catechol (=pyrocatechol; pyrCat) group to two N-termini of modified double-stranded tyrosine residues were synthesized and showed radical scavenging activity with 2,2-diphenyl-1-picrylhydrazyl radical (DPPH radical, DPPH˙) as a free radical model, second-order rate constants for the DPPH˙ scavenging reaction, and the results from electron spin resonance (ESR) studies. It was found that the tyrosine (Tyr) residue and pyrCat containing new antioxidants developed in the study have about 3-20 times more potent antioxidative activity than Trolox, pyrCat, and L-ascorbic acid (VC). In order to elucidate the relationship between antioxidant activity and the molecular orbital states, and to design potent antioxidants we present an interesting approach using an absolute hardness (η)-absolute electronegativity (χ) diagram based on chemical hardness. It was shown that quantum chemicals were required to develop potent antioxidants.     

Correlating flame geometry in opposed-flow flame spread over thin fuels

Numerical analysis and scale analysis are combined in a novel manner in this work to develop closed-form expressions for flame geometry in opposed-flow flame spread over condensed fuels. A scale analysis is used to relate different geometric attributes to appropriate non-dimensional parameters. A comprehensive numerical model is then used to generate a large set of numerical data for flame height, flame length, and pyrolysis length as functions of different fuel and oxidizer parameters for flame spread in the thermal, kinetic, and radiative regimes. The numerical data is then correlated to scaled expressions and the unknown coefficients are numerically determined. It is shown that flame length, flame height, and pyrolysis length can be expressed in terms of the preheat length in different regimes of flame spread. An experimental approach is outlined to measure the preheat length necessary for accurately predicting the flame structure. Experimental images obtained from interferometry in two different regimes – downward spreading configuration and quiescent microgravity environment – are consistent with the proposed flame height correlation.     

Superconducting characteristics and microstructure of polycrystalline Zn-doped In2O3 films

In order to investigate the relation among the superconducting transition T_c, carrier density n, resistivity ρ and the microstructure in the polycrystalline (In₂O₃)_1?x–(ZnO)_x films, we prepared specimen films by post annealing of amorphous films with x = 0.025 at various annealing temperature T_a and for annealing time t_a = 1 h and 4 h. As for microstructures, we have investigated the distribution of elements by scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). We have found followings: (1) The annealed films clearly show the superconductivity of which T_c depends on T_a, t_a and n. This indicates that the superconductivity is determined by the combination of crystallinity and carrier density. (2) The data on STEM–EELS spectra mapping of indium plasmon indicate that droplets of the pure indium phase exist inside a film, where the distribution of these droplets dispersed. Therefore, it seems that droplets do not form an electrical conducting path, that is, it is possible that observed superconductivity is due to intrinsic characteristic of polycrystalline (In₂O₃)_1?x–(ZnO)_x films.