Measurement of circular dichroism spectra of liquid/liquid interface by centrifugal liquid membrane method.

The direct measurement of the circular dichroism (CD) spectra of liquid/liquid interface has been achieved for the first time by the centrifugal liquid membrane (CLM) method combined with a conventional CD spectropolarimetry. In the sample chamber of the CD spectropolarimeter, a cylindrical glass cell containing small amounts of organic and aqueous phases was rotated at ca. 7000 rpm to generate a two-phase liquid membrane with a high specific interfacial area. The CD spectra of the J-aggregate of protonated 5,10,15,20-tetraphenylporphyrin formed at the toluene/sulfuric acid interface in the rotating cell have been measured. The results demonstrated the novelty and advantages of this method.     

A multiple character sum and a multipleL-function

In this paper we introduce a certain sum by using Dirichlet characters. We investigate the Riesz mean of the sum using the analytic properties of the MultipleL-function systematically. Eine überarbeitete Fassung ging am 6. 8. 2001 ein     

Breakage of λ-DNA by inorganic tin and organotin compounds as environmental pollutants

In proportion to the environmental pollution problems caused by organotin compounds, the genotoxicities of tin compounds in the environments have become of interest so as to estimate their safety in recent years. In this work, isolated λ-DNA (double-strand DNA) was incubated with inorganic tin(II) and tin(IV) and five organotin compounds [n-butyltin trichloride, di(n-butyltin) dichloride, methyltin trichloride, dimethyltin dichloride and trimethyltin chloride] in reaction systems both with and without hydrogen peroxide (H₂O₂) content. The tin compounds tested in this study did not induce DNA breakage in the absence of hydrogen peroxide. Divalent inorganic tin (SnCl₂) and tetravalent inorganic tin (SnCl₄) caused DNA breakage in the presence of hydrogen peroxide (10 mM), and the DNA damage activity of inorganic tin was much more potent in divalent inorganic tin (SnCl₂) than in tetravalent inorganic tin (SnCl₄). Divalent inorganic tin (SnCl₂) induced DNA breakage in a concentration-dependent fashion at concentrations greater than 0.1 mM of SnCl₂ in the presence of hydrogen peroxide (10 mM). DNA breakage was not caused by n-butyltin compounds and methyltin compounds either in the presence or in the absence of hydrogen peroxide.     

Total synthesis of tylosin

Tylosin has been synthesized byregio- and stereoselective introduction of the amino disaccharide moiety and D-mycinose onto the previously synthesized 16-membered-ring aglycone.     

First isolation of 1,3,2-dithiaphosphetane 2-sulfide

The treatment of tert-alkyl phenyl thioketones with Lawesson’s reagent (LR) gave two diastereomeric 1,3,2-dithiaphosphetane 2-sulfides in high yields. The structure of one of the major diastereomers was determined by X-ray crystallography. The reaction of 2-adamantanethione with LR yielded the corresponding spiro-1,3,2-dithiaphosphetane 2-sulfide derivative in 87% yield.     

Hydrogen analysis in solid samples by utilizing He metastable atoms induced by TEA CO2 laser plasma in He gas at 1 atm

A TEA CO₂ laser (350 mJ–1.5 J, 10.6 μm, 200 ns, 10 Hz) was focused onto a metal sub-target under He as host gas at 1 atmospheric pressure with a small amount of impurity gas, such as water and ethanol vapors. It was found that the TEA CO₂ laser with the help of the metal sub-target is favorable for generating a strong, large volume helium gas breakdown plasma at 1 atmospheric pressure, in which the helium metastable-excited state was then produced overwhelmingly. While the metal sub-target itself was never ablated. The helium metastable-excited state produced after the strong helium gas breakdown plasma was considered to play an important role in exciting the atoms. This was confirmed by the specific characteristics of the detected H emission, namely the strong intensity with low background, narrow spectral width, and the long lifetime. This technique can be used for gas and solid samples analysis. For nonmetal solid analysis, a metal mesh was introduced in front of the nonmetal sample surface to help initiation of the helium gas breakdown plasma. For metal sample, analysis can be carried out by combining the TEA CO₂ laser and an Nd–YAG laser where the Nd–YAG laser is used to ablate the metal sample. The ablated atoms from the metal sample are then sent into the region of helium gas breakdown plasma induced by the TEA CO₂ laser to be excited through the helium metastable-excited state. This technique can be extended to the analysis of other elements, not limited only to hydrogen, such as halogens.     

Preparation and characterization of silica—polyimide composite membranes coated on porous tubes for CO2 separation

Silica-polyimide microcomposite membranes were prepared on γ-alumina-coated α-alumina support tubes, and their gas permeation properties were evaluated with He, N₂ and CO₂. Smoothing of the substrate surface and hybridization of silica and polyamic acid were both effective to form defect-free thin composite membranes. The CO₂ permeance of a membrane with a silica content of 68 wt% was one order of magnitude higher than that of a polyimide membrane having the same thickness. The permselectivity of CO₂ to N₂ was 30 at 30°C and 13 at 100°C. Contributions of the silica and polyimide phases to permeance of the composite membrane were analyzed with a two-phase permeation model. The effective thickness of the rate-controlling polyimide phase was less than one-tenth of the total thickness of the silica-polyimide membrane.     

Staphylionosides A-K: megastigmane glucosides from the leaves of Staphylea bumalda DC

Chemical investigation of leaves of Staphylea bumalda DC., collected in the suburbs of Hiroshima City, afforded 11 new megastigmane glucosides, named staphylionosides A-K (3-13), along with two known megastigmane glucosides (1, 2). The relative structures were elucidated from spectroscopic evidence, and the absolute structures of the aglycones were determined by means of the combination of beta-D-glucosylation-induced shift-trends and the modified Mosher's method.