Thickness decrease of a grafted polyelectrolyte membrane exposed to shear flow

The effect of the shear flow on the thickness change of a polyelectrolyte membrane grafted onto a glass substrate was directly investigated with a flow cell combined with a confocal laser scanning microscope. The membrane thickness decreased proportionally to an increase in the shear stress of the flow when the shear rate exceeded a critical value of 1 s^?1. The higher the ionic strength was of the fluid, the greater the thinning effect was. The correlation between the critical shear rate and the relaxation of the polymer in the gel membrane was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2808–2815, 2003     

Simple and rapid determination of hydrogen peroxide using phosphine-based fluorescent reagents with sodium tungstate dihydrate.

A simple batch method for the fluorometric determination of hydrogen peroxide using phosphine-based fluorescent reagents has been developed. A rapid, mild and selective derivatization reaction was achieved by adding sodium tungstate dihydrate to the reaction mixture of hydrogen peroxide and a phosphine-based fluorescent reagent. When 4-diphenylphosphino-7-methylthio-2,1,3-benzoxadiazole was used as a reagent, the derivatization reaction was completed after 2 min at room temperature. The calibration curve was linear between 12.5 and 500 ng hydrogen peroxide in a 10 microL sample solution. This method is accurate and has potential for on-line applications.     

Two synthetic approaches to rebeccamycin

Two synthetic approaches to a new indolocarbazole antitumor antibiotic, rebeccamycin, were developed. The absolute configuration of rebeccamycin was determined by a total synthesis.     

Fluorometric Determination of Trace Amounts of Fluoride Ion Using an Expanded Porphyrin

A highly selective and sensitive method of fluorometry is described for determination of the fluoride ion at the parts per billion level via the ion-pair complex formation of the fluoride ion with an expanded prophyrin [2,23-diethyl-8,17-bis(2-ethoxycarbonylethyl)-3,7,12,13,18,22-hexamethylsapphyrin (H₃sap)]. The ion-pair complex gives out an enhanced fluorescence intensity at 680 nm on excitation at 450 nm. Since the present method is based on a direct reaction of the fluoride ion with the sappyrin, a 200-fold amount of the aluminum (III) ion [10⁻⁴M (M = mol dm⁻³)] and a 2000-fold amount of the iron(III) ion (10⁻³M) over the fluoride ion did not interfere with determination of the fluoride ion at concentrations as low as 5 × 10⁻⁷M in the presence of 1,2-diaminocyclohexane-N,N,N′,N′-teraacetic acid. The proposed method was applied to determination of the fluoride ion in various water samples (tap water, river water, rain water, underground water, and hot spring water) and satisfactory results were obtained.     

Evaluation of Photocatalytic Activity of Transparent Anatase Nanocrystals-Dispersed Silica Films Prepared by the Sol-Gel Process with Hot Water Treatment

Anatase nanocrystals were precipitated mainly at the surface of the silica-titania gel films with hot water treatment, whereas the addition of poly(ethylene glycol) (PEG) in the films led to the dispersion of anatase nanocrystals in the whole of the films after the treatment. Both films with and without PEG showed high photocatalytic activities for acetaldehyde, NO _x and stearic acid in the gas-solid system, and for methylene blue and potassium iodide in the liquid-solid system. The addition of PEG improved the photocatalytic activities of the resultant films due to the smaller anatase crystallites and the porous film structure. The residual silica under-layer of the superficially anatase-precipitated films is expected to act as a protective one for an organic polymer substrate against the photocatalytic degradation.     

Stereoselective synthesis of (25R)-25,26-dihydroxy-23-oxovitamin D3 and its enzymatic conversion to (25R)-1α,25,26-trihydroxy-23-oxovitamin D3, a putative metabolite of vitamin D3

(25$\text{R}$)-25,26-Dihydroxy-23-oxovitamin D₃ was synthesized efficiently and stereoselectively, and it was converted enzymatically to (25$\text{R}$)-1α,25,26-trihydroxy-23-oxovitamin D₃, a putative metabolite of 1α,25-dihydroxyvitamin D₃. The spectral and chemical properties of (25$\text{R}$)-25,26-dihydroxy-23-oxovitamin D₃ and its 1α,hydroxylated derivative disagree with those reported for the isolated metabolite.     

Preparation of Titania Nanosheet-Precipitated Coatings on Glass Substrates by Treating SiO2-TiO2 Gel Films with Hot Water Under Vibrations

Titania nanosheet-precipitated coatings have been prepared by treating SiO₂-TiO₂ gel films on glass substrates with hot water at 90°C under vibration. Longitudinal vibrations at about 6 Hz during the treatment enhanced the formation of titania nanosheet. The titania nanosheet consisted of several layers with a spacing of about 0.6 nm and was identified as hydrated titania with a lepidocrocite-type structure. The morphology of the titania nanosheet-precipitated coatings is probably achieved by lowering of the concentration of hydrolyzed titania species at the surface due to rapid water flow driven by the vibrations. The coatings were transparent in the visible range and showed high photocatalytic activity and antifogging property.     

Water-soluble stilbene dendrimers

The third generation of novel photo-responsive water-soluble stilbene dendrimer (trans- and cis-G3 WSD) undergoes unusual one-way trans-to-cis isomerization to give 100% of cis isomer at the photostationary state on UV irradiation in water.     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.