Five novel flavonoids from Wasabia japonica

From the fresh leaves of Wasabia japonica Matsum., five novel flavonoids 1-5, isovitexin derivatives having a trans-sinapoyl group at C-7, were isolated together with five known flavonoids, and their structures were elucidated on the basis of their spectroscopic data (NMR, MS, UV, and IR) and chemical evidence.     

Large-scale separation of metallic and semiconducting single-walled carbon nanotubes

In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way.     

Soluble polymer-supported catalysts containing pendant quaternary onium salts for the addition reaction of oxiranes with carbon dioxide

The addition reaction of oxiranes ( 15a-d ) with carbon dioxide (CO₂) was carried out using 1 mol % of soluble polymer-supported quaternary onium salts as catalysts under atmospheric pressure. The reaction of 15a-d with CO₂ proceeded very smoothly to give the corresponding five-membered cyclic carbonates ( 16a-d ) in high yields at 90-100°C. The catalytic activity of the soluble polymer-supported quaternary onium salts was strongly affected by the following factors: kind of reaction solvent, degree of introduction of the pendant onium salt residues in the polymer chain, and type of alkyl group on the onium salts due to the balance between lipophilicity and steric hindrance of the onium salt residue. Furthermore, these soluble polymer-supported quaternary onium salts were found ordinarily to have higher catalytic activity than low molecular weight quaternary onium salts under the same reaction conditions. It was also found that the rate of reaction was proportional both to catalyst concentration and to oxirane concentration. © 1995 John Wiley & Sons, Inc.     

A study of Feynman integrals by micro-differential equations

We use the holonomic character of Feynman integrals to describe their singularity structure explicitly in some simple cases. The results in §1 show that under moderate conditions Feynman amplitudes can be locally expressed essentially in terms of Legendre functions near the points where two positive- Landau-Nakanishi surfaces meet. Related topics such as hierarchical principle in perturbation theory are also discussed in terms of holonomic systems involved. In §4 we use the concrete expressions for Feynman amplitudes obtained in §1 to discuss the validity of Sato's conjecture.Supported in part by NSF MCS 75-2333Supported in part by NSF GP 36269     

Effect of molecular dynamics and modulated structure on H NMR spectrum studied in [Mg(H2O)6][SiF6]

The spectrum of magnetic resonance is typically affected by a modulated structure in an incommensurate phase, resulting in the broadened spectrum characterized by ‘edge singularities’. We demonstrate that the modulated structure in the crystal where molecular motion exists is responsible for the narrowing of the spectrum in the fast motional region by means of the simulation of ²H NMR spectrum of [Mg(H₂O)₆][SiF₆]. The program developed by combining the theories of phase solitons in the incommensurate phase and motional change of ²H NMR spectrum was used for the simulation. We obtained a good agreement between the theoretical ²H NMR spectrum and experimental one for [Mg(H₂O)₆][SiF₆].     

Synthesis and DNA binding properties of iminodiacetic acid-linked polyamides: characterization of cooperative extended 2:1 side-by-side parallel binding

A series of iminodiacetic acid (IDA)-linked polyamides (DpPyPyPy-IDA-PyPyPyDp) were prepared and constitute polyamides joined head-to-head by a functionalizable five-atom linker. It was found that the IDA linker exerts a unique influence over the DNA binding conformation differing from both the beta-alanine (extended) or gamma-aminobutyric acid (hairpin) linkers, resulting in cooperative parallel side-by-side 2:1 binding in an extended conformation most likely with a staggered versus stacked alignment. A generalized variant of a fluorescent intercalator displacement (FID) assay conducted on a series of hairpin deoxyoligonucleotides containing a systematically varied A/T-rich binding-site size was used to distinguish between the binding modes of the IDA-linked polyamides.     

Electrochemically driven clathration/declathration of ferrocene and its derivatives by a nanometer-sized coordination cage

The electrochemical, NMR, and crystallographic studies clearly indicate that the clathration and declathration of ferrocene and its derivatives in a self-assmbled Pd(II)-linked nanometer-sized cage can be controlled by the oxidation state of the guest. Namely, the guests are clathrated when they are reduced but declathrated when they are oxidized. The process is rapid on the NMR time scale but slow on the CV time scale.     

Direct synthesis of hetero-biaryl compounds containing an unprotected NH2 group via Suzuki-Miyaura reaction

Hetero-biaryl compounds were prepared via the Suzuki-Miyaura coupling reaction of hetero-aryl moieties containing an unprotected NH₂ group and arylboronic acids. D-t-BPF was found to be an efficient ligand for the cross-coupling of NH₂-unprotected hetero-aryl chlorides with phenylboronic acid.     

Fluoride-induced chemiluminescent decomposition of dioxetanes bearing a siloxyaryl moiety to produce an alkyl aryl ketone as an emitter

Tetrabutylammonium fluoride induces the decomposition of 1-tert-butyl-4,4-dimethyl-5-(3-siloxyphenyl)-2,6,7-trioxabicyclo[3.2.0]heptane (4a) in DMSO to form an oxyanion of aromatic ketone (14a) as an emitter with high singlet-chemiexcitation yield comparable with that for a chemically initiated electron exchange luminescence (CIEEL) active dioxetane producing an oxyanion of aromatic ester as an emitter. A 7-siloxynaphthalen-2-yl analog (4b) was found on similar treatment to emit light with the maximum wavelength the longest among CIEEL-active dioxetanes hitherto known.     

Efficient copper-catalyzed coupling of aryl iodides and thiobenzoic acid

A highly efficient copper-catalyzed coupling reaction of aryl iodides and thiobenzoic acid, using 10 mol % of copper iodide, 20 mol % of 1,10-phenanthroline, and ⁱPr₂NEt in toluene, was developed. This methodology is applicable to a variety of aryl iodides.