A novel antivirally active fucan sulfate derived from an edible brown alga, Sargassum horneri

A novel fucan sulfate (Hor-1) was isolated from the hot water extract of an edible brown alga, Sargassum horneri (Turner) C. Agardh. The fucan sulfate was revealed to have sugar linkage types, sulfate content and uronic acid content different from those of sodium hornan (Na-HOR), another fucan sulfate isolated from this alga. However, it exhibited inhibitory activity against replication of herpes simplex virus type 1 with similar potency to Na-HOR.     

Inversion of Optical Activity in the Synthesis of Mercury Sulfide Nanoparticles: Role of Ligand Coordination

Optical activity in inorganic colloidal materials was controlled through interactions of chiral molecules with the nanoparticle (NP) surface. An inversion of optical activity in the synthesis of mercury sulfide (HgS) NPs was demonstrated with an intrinsically chiral crystalline system in the presence of an identical chiral capping ligand. A continuous decrease in the positive first Cotton effect and an eventual reversal of CD profile were observed upon heating the aqueous solution of HgS NPs capped with N‐acetyl‐l ‐cysteine (Ac‐l ‐Cys) at 80 °C. Ac‐l ‐Cys afforded two bidentate coordination configurations with an almost mirror image of each other using the thiolate and either of carboxylate or acetyl–carbonyl groups on the HgS core. Experiment and calculation suggest that a shift in the distribution of the NP formation with energy in response to the combinations of ligand coordination structure and chiral crystalline surface is responsible for the inversion of optical activity.     

Carbon Monoxide Oxidation by Polyoxometalate‐Supported Gold Nanoparticulate Catalysts: Activity,Stability, and Temperature‐ Dependent Activation Properties

Nanoparticulate gold supported on a Keggin‐type polyoxometalate (POM), Cs₄[α‐SiW₁₂O₄₀]?n H₂O, was prepared by the sol immobilization method. The size of the gold nanoparticles (NPs) was approximately 2 nm, which was almost the same as the size of the gold colloid precursor. Deposition of gold NPs smaller than 2 nm onto POM (Au/POM) was essential for a high catalytic activity for CO oxidation. The temperature for 50 % CO conversion was ?67 °C. The catalyst showed extremely high stability for at least one month at 0 °C with full conversion. The catalytic activity and the reaction mechanism drastically changed at temperatures higher than 40 °C, showing a unique behavior called a U‐shaped curve. It was revealed by IR measurement that Au^δ+ was a CO adsorption site and that adsorbed water promoted CO oxidation for the Au/POM catalyst. This is the first report on CO oxidation utilizing Au/POMs catalysts, and there is a potential for expansion to various gas‐phase reactions.     

An Efficient Method for the Conjugation of Hydrophilic and Hydrophobic Components by Solid‐Phase‐Assisted Disulfide Ligation

Chemical conjugation between hydrophilic and hydrophobic components is difficult because of their extremely different solubility. Herein, we report a new versatile method with a solid‐phase‐assisted disulfide ligation to overcome the difficulty of conjugation attributed to solubility. The method involves two steps in a one‐pot process: 1) loading of a hydrophobic molecule onto a resin in an organic solvent, and 2) release of the solid‐supported hydrophobic molecule as a conjugate with a hydrophilic molecule into an aqueous solvent. This strategy allows the use of a suitable solvent system for the substrates in each step. Conjugates of a water‐insoluble drug, plinabulin, with hydrophilic carriers that could not be prepared by solution‐phase reactions were obtained in moderate yields (29–45 %). This strategy is widely applicable to the conjugation of compounds with solubility problems.     

In Situ Immobilization of Ultrafine Particles Synthesized in a Water/Oil Microemulsion

We investigated the in situ immobilization of ultrafine particles synthesized in a water/oil (w/o) microemulsion to silica for its possible application to supported metal catalysts. ZnS particles immobilized to silica by the ME method were consistent with those synthesized in a w/o microemulsion. Therefore, ZnS particles in a w/o microemulsion could be immobilized to silica without aggregation by this method. The relationship between the method of synthesizing Rh ultrafine particles in a w/o microemulsion and the diameter and diameter distribution of Rh particles immobilized to silica was studied. Rh-SiO(2) catalysts with a sharp diameter distribution could be prepared by immobilizing Rh-hydrazine complex particles because these complex particles would be very stable in a w/o microemulsion. The Rh particle diameters of Rh-SiO(2) catalysts prepared by changing the amount of silica produced were almost identical. Accordingly, the Rh particle diameter of Rh-SiO(2) catalysts could be controlled independently of Rh content by the ME method. Copyright 2001 Academic Press.     

Cover Picture

The cover picture shows a section of the electron charge density of the first metal carbide endohedral metallofullerene (Sc(2)C(2))@C(84) obtained from a synchrotron X-ray powder diffraction study by the maximum entropy method (MEM). The several density maxima, which correspond to scandium and carbon atoms, are clearly seen inside the C(84) carbon cage. The MEM charge density distribution also reveals that the C(84) cage has D(2d) symmetry (no. 23) and that the C(2) axis is parallel to the <100> face-centered cubic (fcc) direction of the unit cell. As a consequence of the site symmetry being 4mm, the C(2) axis of (Sc(2)C(2))@C(84) is oriented to six equivalent <100> directions and shows a merohedral disorder. The resultant Sc small middle dot small middle dot small middle dotSc distances and C-C bond lengths of the Sc(2)C(2) cluster are 0.429(2) and 0.142(6) nm, respectively. The observed C-C bond length is between that of a typical single and a double bond, and is very close to that of the C-C bond (0.143 nm) combining two pentagons in a C(60) molecule. More about this fascinating structure can be found in the contribution by Shinohara and co-workers on p. 397 ff.     

Chloroprene as a source of fine chemicals: palladium-catalyzed synthesis of terminal allenes

[reaction: see text] Several functionalized terminal allenes were prepared in moderate to excellent yield by a palladium-catalyzed reaction of chloroprene (2-chloro-1,3-butadiene) with soft nucleophiles.     

Preparation of highly concentrated super-hot [gamma-32P]ATP using small-scale ion-exchange chromatography

In order to obtain a highly concentrated, pure and super-hot [gamma-32P]ATP, we improved the purification method of super-hot [gamma-32P]ATP which was synthesized by the method of Johnson and Walseth (1979). The super-hot [gamma-32P]ATP was synthesized in a relatively large volume (2 ml) of reaction mixture and purified using semi-micro scale anion exchange chromatography (Dowex 1 X 2, 60-70 microliters column volume). In combination with washing the reaction product with certain organic solvents, this chromatography technique makes it possible to obtain a highly concentrated and pure super-hot [gamma-32P]ATP (approx. 7,000 Ci/mmol; 20-30 mCi/ml) from [32P]Pi of any commercial source in a good yield.     

Spectrophotometric determination of copper(II) with carbon disulfide,a secondary amine and triton X-100

Copper(II) is determined by non-extractive spectrophotometry as a complex of butylene dithiocarbamate formed in situ by reaction between carbon disulfide and pyrrolidine in aqueous Triton X-100 medium. This method is similar to that with butylene dithiocarbamate as starting material in the sense of simplicity, sensitivity, precision and accuracy. Pyrrolidine is the best of seven secondary amines tested in this way for copper determinations.     

TUMOR IMAGING WITH [111niIn]MONO-DTPA-ETHYLENEGLYCOL-Ga-DEUTEROPORPHYRIN

Abstract Mono-DPTA-ethyleneglycol-Ga-deuteroporphyrin (MDEGD) was synthesized, by coordinating non-radioactive Ga in the porphyrin ring and connecting DTPA (diethylene-triamine-N,N,N,N,N,-pentaacetic acid) to its side chain. By labeling with 111_In, chemicals for scintigraphy were developed. They were applied to Syrian golden hamsters with implanted pancreatic gland cancers and C57-black mice with Lewis lung cancer to enable tumor imaging and biodistribution examination. A comparative study was also conducted with [⁶⁷Ga]citrate. In the resultant data, [¹¹¹In]MDEGD showed larger tumor/lung, tumor/kidney and tumor/blood ratio with [⁶⁷Ga]citrate. The affinity of [ⁿIn]MDEGD in inflammatory tissue was much lower than that of ⁶⁷Ga citrate. [¹¹¹In]MDEGD lost its photosensitivity.