Amphezonol A, a novel polyhydroxyl metabolite from marine dinoflagellate Amphidinium sp.

Amphezonol A (1), a novel polyhydroxyl linear carbon-chain metabolite, has been isolated from the cultured marine dinoflagellate Amphidinium sp., which was isolated from an Okinawan marine acoel flatworm Amphiscolops sp. The structure of 1 was elucidated by detailed analyses of 2D NMR spectra. Amphezonol A (1) possesses one tetrahydrofuran ring, two tetrahydropyran rings, and twenty-one hydroxyl groups on C₆₀-linear aliphatic chain with one exo-methylene and one methyl branch. Amphezonol A (1) exhibited a modest inhibitory activity against DNA polymerase α.     

A note on the momentum distribution function for an electron gas

The one-electron momentum distribution function $\text{〈a}{}_{\mathrm{k\sigma }}{}^2\text{a}{}_{\mathrm{k\sigma }}\text{〉}$ for an electron gas is investigated by a diagrammatic analysis of perturbation theory. It is shown that $\text{〈a}{}_{\mathrm{k\sigma }}{}^2\text{a}{}_{\mathrm{k\sigma }}\text{〉}$ has the following exact asymptotic form for large k (k ? p_F; p_F, the Fermi momentum): $\text{〈a}{}_{\mathrm{k\sigma }}{}^2\text{a}{}_{\mathrm{k\sigma }}\text{〉 =}\text{4}\text{9}\text{(}\text{αr}{}_{\mathrm{s}}\text{π}\text{)}{}^2\text{×(}\text{p}{}_{\mathrm{<mtext>F</mtext>}}{}^8\text{k}{}^8\text{) g?(0) + ?}$, where g?(0) is the zero-distance value of the spin-up-spin-down pair correlation function. The physical implications of the above asymptotic form are discussed.     

Synthesis and properties of 1-Benzothiopyrano[2,3-d]-pyrimidine-2,4-(3H)diones (10-thia-5-deazaflavins)

Treatment of 6-arylthiouracils with the Vilsmeier reagent (dimethylformamide-phosphorus oxychloride) gave the corresponding 6-arylthio-5-formyluracils, which could alternatively be prepared by the condensation of 6-chloro-5-formyluracils with thiophenols. Dehydrative cyclization of the above 5-formyluracils with polyphosphoric acid gave 1-benzothiopyrano[2,3-d]pyrimidine-2,4-(3H)diones (10-thia-5-deazaflavins). These 10-thia-5-deazaflavins oxidized alcohols to give the corresponding carbonyl compounds with the aid of strong base, and they were hydrogenated to 1,5-dihydro-10-thia-5-deazaflavins. Treatment of 10-thia-5-deazaflavins with concentrated aqueous potassium hydroxide led to the exclusive formation of 1,5-dihydro-10-thia-5-deazaflavins and 1,5-dihydro-10-thia-5-deazaflavin-5-ones via intermolecular oxidation-reduction (disproportionation) between initially formed 1,5-dihydro-5-hydroxy-10-thia-5-deazaflavins and unchanged 10-thia-5-deazaflavins.     

Studies on iron(III) complex with 5,6-diamino-1,3-dimethyluracil

Reaction of 5,6-diamino-1,3-dimethyluracil (DDU) with iron(III) ion gave a fine blue colouration due to the formation of Fe[(DDU—H)₃]·2HClO₄. An oxidation product (7), C₁₂H₁₂N₆O₄, was also isolated from the reaction mixture.     

A new strategy for the selective determination of D-amino acids: enzymatic and chemical modifications for pre-column derivatization

A new strategy for the selective determination of D-amino acids (DAAs) employing a pre-column derivatization was designed with concepts based on both enzymatic and chemical modifications. Selective determination of DAAs was accomplished by following: DAA was enzymatically modified with D-amino acid oxidase (DAAO: EC 1.4.3.3) to form an alpha-keto acid. Subsequently, resulting alpha-keto acid was detected by high-performance liquid chromatography (HPLC) after chemical modification with o-phenylenediamine (PDA) in the presence of 2-mercaptoethanol (2ME) to give the corresponding quinoxalinol derivative (PDA-alpha-keto acid derivative). After optimizing the pre-column derivatization and HPLC separation, five peaks corresponding to DAAs (D-alanine, D-leucine, D-methionine, D-phenylalanine, D-valine (as the standard mixture of DAAs in this paper) were separately eluted and monitored by means of a conventional HPLC system with a gradient elution on octadecyl silica gel (ODS) column and a fluorescence detector (Ex.: 341 nm, Em.: 413 nm), respectively. It was confirmed that the present method was incapable of detecting L-amino acids (LAA) when a sample solution consisting of both LAAs and DAAs was examined. The linearity of the peak-area responses to their concentration range of DAAs from 10 to 500 microM is 0.994-1.000, and their detection limits were 0.2-1 microM (signal/noise = 3). When this method was applied to a methanolic extract of short-necked clams, Ruditapes philippinarum (in Japanese, Asari), a big peak, corresponding to D-alanine was detected, corresponding to 2.9 mg/g D-alanine. In this paper, we present an example of pre-column derivatization method that was newly configured to take into account both the biological and chemical properties of the substances in question.     

Clustering of Ti on a C60 surface and its effect on hydrogen storage

Recent efforts in finding materials suitable for storing hydrogen with large gravimetric density have focused attention on carbon-based nanostructures. Unfortunately, pure carbon nanotubes and fullerenes are unsuitable as hydrogen storage materials because of the weak bonding of the hydrogen molecules to the carbon frame. It has been shown very recently that coating of carbon nanostructures with isolated transition metal atoms such as Sc and Ti can increase the binding energy of hydrogen and lead to high storage capacity (up to 8 wt % hydrogen, which is 1.6 times the U.S. Department of Energy target set for 2005). This prediction has led to a great deal of excitement in the fuel cell community [see The Fuel Cell Review, http://fcr.iop.org/articles/features/2/7/4]. However, this prediction depends on the assumption that the metal atoms coated on the fullerene surface will remain isolated. Using first-principles calculations based on density functional theory, we show that Ti atoms would prefer to cluster on the C60 surface, which can significantly alter the nature of hydrogen bonding, thus affecting not only the amount of stored hydrogen but also their thermodynamics and kinetics.     

Thorium encapsulated caged clusters of germanium: Th@Ge(n), n = 16, 18, and 20

We report from ab initio calculations that thorium encapsulation can be used to stabilize highly symmetric cages of germanium with 16 and 20 atoms. The lowest energy structures of these clusters are different from the recently found silicon fullerenes and are similar to clusters found in bulk metallic alloys. The binding energies of these clusters are higher compared with the values for the elemental germanium clusters of comparable sizes, and this suggests a strong possibility of their experimental realization in large quantities. Also, Th@Ge(16) has a large highest occupied-lowest unoccupied molecular orbital (HOMO-LUMO) gap of 1.72 eV that makes it interesting for optoelectronic applications.