Absolute stereostructure of Andirolides A-G from the flower of Carapa guianensis (Meliaceae)

A new gedunin, three new mexicanolides and three new phragmalin-type limonoids named Andirolides A (1), B (2), C (3), D (4), E (5), F (6), and G (7) were isolated from oil of the flower of Carapa guianensis Aublet (Meliaceae). Their absolute stereostructures were determined by 2D NMR and CD spectra, and single-crystal X-ray analysis, and all compounds were confirmed to have the C-17βH configuration. Considering the similarity in CD spectra between Andirolide G (7) and the xyloccensins reported by Wu, we concluded that the structures of xyloccensins should be revised so as to have the absolute configuration of 17R.     

Hydroxylated terphenylphosphine ligands for palladium-catalyzed ortho-selective cross-coupling of dibromophenols, dibromoanilines, and their congeners with Grignard reagents

p-Terphenylphosphines bearing one or two hydroxy groups were used as ligands to palladium in the cross-coupling of dibromophenols, dibromoanilines, and their congeners with Grignard reagents. High ortho-selectivity that cannot be achieved using other phosphine ligands was observed. ortho-Preference was also observed in competitive cross-coupling reactions of two substrates. A significant effect of the concentration of the Grignard reagent on the ortho-selectivity was observed, when the hydroxylated terphenylphosphines were used. Kinetic studies on this effect showed that high concentrations of the Grignard reagent retard the cross-coupling reaction only at the para-position, but not at the ortho-position.     

Cleavage of oligonucleotides containing a P3'→N5' phosphoramidate linkage mediated by single-stranded oligonucleotide templates

Double-stranded DNA (dsDNA) templates can hybridize to and accelerate cleavage of oligonucleotides containing a P3'→N5' phosphoramidate (P-N) linkage. This dsDNA-templated cleavage of P-N linkages could be due to conformational strain placed on the linkage upon triplex formation. To determine whether duplex formation also induced conformational strain, we examined the reactivity of the oligonucleotides with a P-N linkage in the presence of single-stranded templates, and compared these reactions to those with dsDNA templates. P-N oligonucleotides that are cleaved upon duplex formation could be used as probes to detect single-stranded nucleic acids.     

Size and shape of Au nanoparticles formed in ionic liquids by electron beam irradiation

Au nano-particles were synthesized via a reductive reaction in ionic liquid solution containing Au(3+) ions using a low-energy electron irradiation technique. In this study, we focused on how the electron beam conditions (acceleration energy, beam current and irradiation time) and the kinds of ionic liquid affected the size and shape of the prepared Au particles. The sizes of the primary particles increased with higher acceleration energy of the electron beam, whereas they did not depend so much on the beam current. Although the amount of secondary particles increased with longer irradiation time, the sizes of the primary particles remained constant. The anion of the ionic liquid strongly affected the size and shape of the primary particles, which was due to the different local structure of the ionic liquid around the Au particles. When the thickness of the ionic liquid layer was smaller than the penetration length of the electron beam, the formation of secondary particles was suppressed. The present results gave an important knowledge for controlling the size and shape of the metal particles, which is important for application of various catalyst or devices.     

Benzyl radical addition reaction through the homolytic cleavage of a benzylic C-H bond

Direct generation of a benzyl radical by C-H bond activation of toluenes and the addition reaction of the resulting radical to an electron deficient olefin were developed. The reaction of dimethyl fumarate with toluene in the presence of Et(3)B as a radical initiator at reflux afforded 2-benzylsuccinic acid dimethyl ester in good yield.     

Bridged nucleic acid conjugates at 6'-thiol: synthesis, hybridization properties and nuclease resistances

The bridged nucleic acid (BNA) containing a thiol at the 6'-position in the bridged structure was synthesized from the disulfide-type BNA and conjugated with various functional molecules via the thioether or the disulfide linkage post-synthetically and efficiently in solution phase. The disulfide-linked conjugate was cleaved under reductive conditions derived from glutathione and an oligonucleotide bearing a free thiol was released smoothly. Conjugated functional molecules had great effects on duplex stability with the DNA complement. In contrast, the molecules little influenced the stability with the RNA complement. Moreover, the oligonucleotides with functional groups at the 6'-position had as high or higher resistances against 3'-exonuclease than phosphorothioate oligonucleotide (S-oligo).     

π Back-bonding of iron(II) complexes supported by tris(pyrid-2-ylmethyl)amine and its nitro-substituted derivatives

The electronic and geometric structures of a series of iron(II) complexes supported by tetradentate tris(pyrid-2-ylmethyl)amine-type ligands with different numbers of 4-nitropyridine groups, [(PyCH(2))(3-n)(4-NO(2)PyCH(2))(n)N] (n = 0-3), were examined by X-ray absorption fine-structure and variable-temperature (1)H NMR spectroscopies and theoretical calculations to reveal how the low-spin state is stabilized through π back-bonding interactions between iron(II) and 4-nitropyridine donor group(s).     

A novel bifunctional protein supramolecule for construction of carbon nanotube-titanium hybrid material

Carbon nanotube-TiO(2) hybrid materials with many nano-scale cavities were realized using a bifunctional protein supramolecule possessing carbonaceous material-binding peptides and Ti-binding peptides. The obtained structure was confirmed to consist of a central nanotube, surrounding proteins, and a swathing titanium-layer. All processes were carried out at room temperature, using an environmentally friendly method.     

Observation of long-range f-f interactions between two f-electronic systems in quadruple-decker phthalocyanines

Homo and heteronuclear quadruple-decker phthalocyanine tetramers containing Y(3+) and/or magnetically anisotropic lanthanide ions such as Tb(3+), Dy(3+), and Er(3+) have been synthesized, and their magnetic properties have been elucidated, giving clear evidence of the long-range interactions between two f-electronic centers.