Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Isolation of mitogenic substance from sclerotia of Sclerotinia sclerotiorum IFO 9395 extracted with phosphate buffer.

The buffer extracts (3S) of sclerotia of Sclerotinia sclerotiorum IFO 9395 contained mitogenic substance(s) to murine splenocytes (Shinohara et al. Chem. Pharm. Bull., 38, 2219 (1990)). Although the native 3S was slightly mitogenic, heating of 3S induced significant mitogenic activity. To isolate the mitogen, we separated 3S by ion-exchange and gel filtration chromatographies. The isolated mitogen, named sclerogen, has a molecular mass of 32 kilodaltons (kDa) on sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and the isoelectric point (pI) of 5.9 by chromatofocusing. Sclerogen was significantly mitogenic in vitro against murine splenocytes after heat denaturation, and also showed the augmentation of the primary mixed lymphocyte reaction (MLR) in vitro. However, sclerogen did not show the activation of an alternative pathway of complement and hemagglutination activity. These results suggest that sclerogen is a unique mitogen which differs from lectins and shows mitogenicity after heat denaturation.     

Oxygen isotope effect of superconducting (Nd1−xCex)2CuO4−δ system

The effect of oxygen isotope substitution on the transition temperature T_c of a superconducting (Nd_1−xCe_x)₂CuO_4−δ system was studied, where the special synthetic method was taken to minimize ambiguous factors on the oxygen concentration and to guarantee the complete substitution of ¹⁶O by ¹⁸O. The isotope exponent in the relationship of T_c∝1/M was estimated to be less than 0.15 by magnetic susceptibility measurements.     

Structural developments in synthetic rubbers during uniaxial deformation by in situ synchrotron X‐ray diffraction

The molecular orientation and strain‐induced crystallization of synthetic rubbers—polyisoprene rubber, polybutadiene rubber, and butyl rubber [poly(isobutylene isoprene)]—during uniaxial deformation were studied with in situ synchrotron wide‐angle X‐ray diffraction. The high intensity of the synchrotron X‐rays and the new data analysis method made it possible to estimate the mass fractions of the strain‐induced crystals and amorphous chain segments in both the oriented and unoriented states. Contrary to the conventional concept, the majority of the molecules (50–75%) remained in an unoriented amorphous state at high strains. Each synthetic rubber showed a different behavior of strain‐induced crystallization and molecular orientation during extension and retraction. Our results confirmed the occurence of strain‐induced networks in the synthetic rubbers due to the inhomogeneity of the crosslink distribution. The strain‐induced networks containing microfibrillar crystals and oriented amorphous tie chains were responsible for the ultimate mechanical properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 956–964, 2004     

Simultaneous determination of serotonin and 5-hydroxyindole-3-acetic acid in human urine by automated precolumn derivatization and semi-microbore column liquid chromatography with fluorescence detection.

An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification.     

Improved detectability with a polymer-based trapping device in rapid HPLC analysis for ultra-low levels of bisphenol A (BPA) in environmental samples.

A new high-performance liquid chromatography (HPLC) method has been developed to detect ultra-low concentrations of bisphenol-A (BPA) (below 1 ng/L (ppt)) using column switching electrochemical detection (ECD). The results were superior to those obtained from manual pretreatment procedure with membrane stationary phase. BPA is inherently ubiquitous in the environment, including tools and solvents used for its analysis; to obtain meaningful results, therefore, the concentration of the overall BPA contamination must be below the detection limit for BPA using the analytical system. Therefore, purified water for preparing the standard BPA solution must be filtered with a hydrophobic membrane to suppress BPA background levels of contamination. In addition, we investigated methods for effectively preserving environmental water containing BPA. The addition of a small amount of ethylenediaminetetraacetic acid (EDTA) provided good recovery even after overnight storage. By employing these precautionary measures and procedures to reduce BPA contamination from the analytical procedure, we could accurately determine l(-10) ppt of BPA in environmental water samples using a column switching HPLC system.     

Determination of midodrine in human plasma by high-performance liquid chromatography with fluorescence detection.

A simple and sensitive fluorometric high-performance liquid chromatographic method was developed for the determination of midodrine in human plasma. After liquid-liquid extraction from plasma, the drug and 2-phenylglycinol (internal standard) were convened into the corresponding fluorescent derivatives by reaction with 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxoquinoxaline-2-carbonyl chloride, a fluorescence derivatization reagent for amines. The derivatives were separated within 30 min on a reversed-phase column using isocratic elution with acetonitrile-methanol-water (10:30:60, v/v) and were detected spectrofluorometrically at 485 nm with excitation at 400 nm. The detection limit for midodrine was 0.3 pmol (76 pg) per mL plasma at a signal-to-noise ratio of 3.     

Stability analysis of abnormal multiplication of plankton using parameter identification technique

This paper presents the mathematical approach for the abnormal multiplication of plankton. An abnormal multiplication can be expressed as an unstable problem and the stability of the system is investigated by introducing eigenvalues of a mathematical equation. The stability of the system can be judged by an eigenvalue based on the Lyapunov's stability theory. In this paper, the Arnoldi‐QR method is used to obtain eigenvalues and eigenvectors of the system. The mode superposition method is employed to create spatial distribution needed to analyse the stability. To obtain the objective eigenvalue, the parameter identification technique is employed. The finite element method is used for the discretization in space. Lake Kasumigaura, which is located in Ibaraki Prefecture in Japan, is selected and actual data in 1975, 1976, 1991 and 2000 are used in order to investigate the stability of the specified lake in Japan. Copyright © 2004 John Wiley & Sons, Ltd.     

Collisional frequency shift with a primary frequency standard

When a hydrogen atom trapped in finite space formed by two parallel perfectly conducting plates, the transition rates can be modified. Life-time of the hydrogen 2P _1/2-state is estimated to be shorter as much as 56.3ps with a separation distance of b = 1.2μm between two plates. Although the modification is dependent on position of the atom, the life-time can be shorten or lengthen by adjusting the separation distance even for the case that the atom is placed at the center between two plates.