Control Mechanism for cis Double‐Bond Formation by Polyunsaturated Fatty‐Acid Synthases

Polyunsaturated fatty acids (PUFAs) such as docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and arachidonic acid (ARA) are essential fatty acids for humans. Some microorganisms biosynthesize these PUFAs through PUFA synthases composed of four subunits with multiple catalytic domains. These PUFA synthases each create a specific PUFA without undesirable byproducts, even though the multiple catalytic domains in each large subunit are very similar. However, the detailed biosynthetic pathways and mechanisms for controlling final‐product profiles are still obscure. In this study, the FabA‐type dehydratase domain (DH_FabA) in the C‐subunit and the polyketide synthase‐type dehydratase domain (DH_PKS) in the B‐subunit of ARA synthase were revealed to be essential for ARA biosynthesis by in vivo gene exchange assays. Furthermore, in vitro analysis with truncated recombinant enzymes and C₄‐ to C₈‐acyl ACP substrates showed that ARA and EPA synthases utilized two types of DH domains, DH_PKS and DH_FabA, depending on the carbon‐chain length, to introduce either saturation or cis double bonds to growing acyl chains.     

Molecular Recognition of Medium-size Lactones by Enclathration of Cholic Acid

Abstract

Molecular recognitions of medium size lactones by enclathration of cholic acid (CA) are described. Size and location of the substituents on the lactone rings play an important role for enclathration. Lactones within the limited steric dimensions are included in CA, and larger or smaller ones are not included to give guest-free crystals of CA. Moreover, CA partially separates one enantiomer from racemic lactones by recystallization. X-ray crystallographic studies reveal that all included lactones form the β-trans type bilayer structure having a pentagonal void channel with a side pocket. The cross-sections illustrate that the lactone rings are incorporated in the center of the channel and that the substituents of the guests are fixed in the side pockets. The asymmetric channel enables CA to discriminate size and chirality of medium size lactones.     

XAFS study of copper and silver nanoparticles in glazes of medieval middle-east lustreware (10th–13th century)

It has recently been shown that lustre decoration of medieval and Renaissance pottery consists of silver and copper nanoparticles dispersed in the glassy matrix of the ceramic glaze. Here the findings of an X-ray absorption fine structure (XAFS) study on lustred glazes of shards belonging to 10th and 13rd century pottery from the National Museum of Iran are reported. Absorption spectra in the visible range have been also measured in order to investigate the relations between colour and glaze composition. Gold colour is mainly due to Ag nanoparticles, though Ag⁺, Cu⁺ and Cu²⁺ ions can be also dispersed within the glassy matrix, with different ratios. Red colour is mainly due to Cu nanoparticles, although some Ag nanoparticles, Ag⁺ and Cu⁺ ions can be present. The achievement of metallic Cu and the absence of Cu²⁺ indicate a higher reduction of copper in red lustre. These findings are in substantial agreement with previous results on Italian Renaissance pottery. In spite of the large heterogeneity of cases, the presence of copper and silver ions in the glaze confirms that lustre formation is mediated by a copper- and silver-alkali ion exchange, followed by nucleation and growth of metal nanoparticles.     

Organic intercalation material: reversible change in interlayer distances by guest release and insertion in sandwich-type inclusion crystals of cholic acid

Cholic acid (CA) forms inclusion crystals that have a sandwich-type lamellar structure constructed by the alternative stacking of host bilayers and guest layers. Five disubstituted benzenes, o-toluidine, m-fluoroaniline, o-chlorotoluene, o-bromotoluene, and indene, are accommodated in the two-dimensional void space between the host bilayers at 1:2 host-guest stoichiometries. Thermal gravimetric analysis of the inclusion crystals revealed that all the guest molecules, except o-toluidine, are released in two separate steps, indicating the formation of intermediate crystals after the first guest release. Adequate heat treatment of the four inclusion crystals induces release of half or three quarters of the guest molecules. X-ray diffraction patterns of the intermediate crystals revealed that the crystals have a bilayer structure the same as those of the common CA inclusion crystals. They have one-dimensional cavities, in which the guest molecules are included at a 1:1 or 2:1 host-guest stoichiometry. These facts indicate that the host bilayers move 1.6-4.5 A perpendicular to the layer direction by desorption of the guest molecules. Furthermore, a reverse structural change is also achieved by absorption of the guest molecules to regenerate the starting sandwich-type inclusion crystals. This reversible change in the host bilayer by the guest sorption and desorption is a novel example of organic intercalation materials.     

Face-selective decoration of an organic single crystal toward photochemical devices

Face-selective decoration of a single crystal constructed from 1-pyrenemethylammonium chloride by an anionic porphyrin dye is reported. CLSM observations indicated that the {001} face of the single crystal was selectively coated by the anionic porphyrin (TPPS). This novel achievement could be the first step for preparation of multi-component composite materials mediated by anisotropy of organic single crystals toward photochemical devices.     

Phase-matched SHG in periodically poled LiNbO3 waveguides: A novel configuration

We present a feasiblity study of a new method for enhancing the continuously phase matched second harmonic generation in 2D PPLN optical waveguides fabricated using the off-center Czochralski technique and proton-exchange. We show that a periodic variation of the nonlinear coefficient along the transverse coordinate permits for efficient energetic exchanges.     

Structural and physical properties of cobalt nanocluster composite glasses

Composite systems with metallic nanoparticles embedded in dielectrics present peculiar physical properties which are attractive in several application fields. In the case of transition elements, the magnetic properties of the metal clusters embedded in a dielectric matrix mainly depend on the particle size and structure. In this work, silica films containing cobalt atoms were synthesized by RF magnetron co-sputtering deposition technique, with cobalt concentration of a few atomic percent. X-ray diffraction and transmission electron microscopy showed the presence of hcp cobalt nanoclusters in the as-deposited sample with the highest cobalt concentration. After deposition, thermal treatments were performed to promote cobalt compounds or nanoparticle formation. The thermal treatments were able to change the oxidation state of cobalt atoms, as well as the structure of metallic cobalt nanoclusters (from hcp to fcc), their final size depending on both the preparation parameters and the subsequent annealing atmospheres.     

Au-Cu nanoparticles in silica glass as composite material for photonic applications

In the framework of metal nanocluster composite glasses for photonic application, (gold + copper)-containing silica films were synthesized by radiofrequency co-sputtering deposition technique by varying the Au/Cu ratio. To obtain the formation of metallic (alloy) nanoclusters, the deposited samples were annealed in reducing atmosphere at 900 °C. The linear and nonlinear optical properties of the composite glasses were investigated. In particular, the nonlinear ultrafast optical response was measured by means of the Z-scan technique at a wavelength of 527 nm with single 6 ps pulse configuration. Significant refractive and absorptive effects were observed in all the annealed samples. The two main figures of merit related to the performance of materials for optical switching device application were evaluated for all samples, showing interesting values for the Cu-rich composites.     

Organic layered crystals with adjustable interlayer distances of 1-naphthylmethylammonium n-alkanoates and isomerism of hydrogen-bond networks by steric dimension

A series of 1-naphthylmethylammonium n-alkanoates from acetate to triacontanoate produce isomorphic layered structures in the crystalline state. The interlayer distances, d-spacings, are proportional to the lengths of the alkyl chains. This is attributed to synergic intermolecular interactions; pi-pi and CH-pi interactions of the naphthalene rings between the cations, hydrophobic interactions of the alkyl chains, and two-dimensional hydrogen-bond networks between the primary ammonium cations and the carboxylate anions. Salts made from carboxylic acids wider than 5.5 A in the cross sections produce another columnar structure with a one-dimensional ladder-type hydrogen-bond network. Steric parameters of the acid components provide an explanation for the isomerism of the hydrogen-bond network.