Schulzeines A-C, new alpha-glucosidase inhibitors from the marine sponge Penares schulzei

Three new alpha-glucosidase inhibitors, schulzeines A-C (1-3), were isolated from the marine sponge Penares schulzei. Their structures were elucidated by spectral analysis and chemical degradations to be the isoquinoline alkaloids, encompassing two amino acids, and C(28) fatty acid, the last of which was sulfated. Absolute stereochemistry of schulzeines was determined by application of the modified Mosher analysis to fragments obtained by chemical degradation. Schulzeines A-C inhibit alpha-glucosidase with IC(50) values of 48-170 nM.     

Tumor-infiltrating effector cells of alpha-galactosylceramide-induced antitumor immunity in metastatic liver tumor

BACKGROUND: alpha-Galactosylceramide (alpha-GalCer) can be presented by CD1d molecules of antigen-presenting cells, and is known to induce a potent NKT cell-dependent cytotoxic response against tumor cells. However, the main effector cells in alpha-GalCer-induced antitumor immunity are still controversial. METHODS: In order to elucidate the cell phenotype that plays the most important role in alpha-GalCer-induced antitumor immunity, we purified and analyzed tumor-infiltrating leukocytes (TILs) from liver metastatic nodules of a colon cancer cell line (Colon26), comparing alpha-GalCer- and control vehicle-treated mice. Flow cytometry was performed to analyze cell phenotype in TILs and IFN-gamma ELISA was performed to detect antigen-specific immune response. RESULTS: Flow cytometry analysis showed a significantly higher infiltration of NK cells (DX5+, T cell receptor alphabeta (TCR)-) into tumors in alpha-GalCer-treated mice compared to vehicle-treated mice. The DX5+TCR+ cell population was not significantly different between these two groups, indicating that these cells were not the main effector cells. Interestingly, the CD8+ T cell population was increased in TILs of alpha-GalCer-treated mice, and the activation level of these cells based on CD69 expression was higher than that in vehicle-treated mice. Moreover, the number of tumor-infiltrating dendritic cells (DCs) was increased in alpha-GalCer-treated mice. IFN-gamma ELISA showed stronger antigen-specific response in TILs from alpha-GalCer-treated mice compared to those from vehicle-treated mice, although the difference between these two groups was not significant. CONCLUSIONS: In alpha-GalCer-induced antitumor immunity, NK cells seem to be some of the main effector cells and both CD8+ T cells and DCs, which are related to acquired immunity, might also play important roles in this antitumor immune response. These results suggest that alpha-GalCer has a multifunctional role in modulation of the immune response.     

NMR and MO Studies on the Molecular Structure of a Fluoranthene-Benzene Complex

Fluoranthene (FA) forms a 1:1 van der Waals complex with benzene in cyclohexane. The ¹H NMR spectrum of this complex shows that the FA moiety in the complex state has five kinds of hydrogen atoms and that the ¹H NMR peaks assigned to the protons attached to the naphthalene skeleton are largely shifted to higher magnetic field on complex formation with benzene. These observations indicate that the complex takes the structure of C_S symmetry, in which the benzene molecule mainly interacts with the electronic system localized on the naphthalene moiety of FA. The present ab initio calculations reproduce well the ¹H NMR spectral shifts mentioned above and the experimentally predicted C_S structure of the complex. According to the PPP calculations for the electronic absorption spectral changes on the complex formation, the FA-benzene complex is considered to take a sandwich type structure.     

Ligand-ligand redox interaction through some metal-cluster units

The ligand-ligand redox interaction separated by di-, tri-, and hexanuclear cluster units is discussed in terms of the splitting of the redox waves (DeltaE(L)) and the comproportionation constants (Kcom(L)) of the ligand-based mixed valence state. Although two redox-active monodentate ligands in the mononuclear ruthenium(II) complexes (either cis or trans configurations) do not show appreciable splitting in their reduction waves, interestingly those separated by giant triruthenium and hexarhenium cluster units clearly show splitting. The molecular orbital considerations in the literature suggest that these units possess some pi-type molecular orbitals composed of metal dpi and possibly ligand ppi orbitals. Absence of the redox interactions in oxo-bridged diruthenium(II) and oxo-centered trirhodium(III) complexes where such pi molecular orbitals (including an antibonding one) are fully occupied, indicates the importance of empty pi* orbitals for the ligand redox communication.     

Observation of radiative B-->phi K gamma decays

The radiative decay B-->phi K gamma is observed for the first time. The branching fraction for the charged B--->phi K- gamma decay mode is measured to be B(B--->phi K- gamma)=(3.4+/-0.9+/-0.4)x10(-6). The photon energy distribution for the B--->phi K- gamma decay is presented. The signal for the neutral B(0)-->phi K(0)gamma decay mode is not statistically significant and an upper limit, B(B(0)-->phi K(0)gamma)<8.3x10(-6) at 90% C.L., is set. The analysis is based on a data set of 90 fb(-1) collected by the Belle experiment at the e(+)e(-) asymmetric collider KEKB.     

Highly enantioselective catalytic carbon dioxide incorporation reaction: nickel-catalyzed asymmetric carboxylative cyclization of bis-1,3-dienes

A method for nickel-catalyzed asymmetric carbon dioxide (CO2) incorporation via carbon-carbon bond formation was developed. In the presence of a catalytic amount of Ni(acac)2 and MeO-MOP, various bis-1,3-dienes reacted with CO2 (1 atm) and a diorganozinc reagent (Me2Zn or Ph2Zn) to afford cyclic carboxylic acids in good yields (71-100%) and with high enantioselectivities (90-96% ee).     

Measurement of branching fractions for B-->eta(c)K(*) decays

We report measurements of branching fractions for charged and neutral B-->eta(c)K decays where the eta(c) meson is reconstructed in the K(0)(S)K+/-pi(-/+), K+K-pi(0), K(*0)K-pi(+), and pp; decay channels. The neutral B0 channel is a CP eigenstate and can be used to measure the CP violation parameter sin(2phi(1). We also report the first observation of the B0-->eta(c)K(*0) mode. The results are based on an analysis of 29.1 fb(-1) of data collected by the Belle detector at KEKB.     

Magnetic-field-induced localization of quasiparticles in underdoped La(2-x)SrxCuO4 single crystals

Magnetic-field-induced ordering of electrons around vortices is a striking phenomenon recently found in high-T(c) cuprates. To identify its consequence in the quasiparticle dynamics, the magnetic-field (H) dependence of the low-temperature thermal conductivity kappa of La(2-x)SrxCuO4 crystals is studied for a wide doping range. It is found that the behavior of kappa(H) in the subkelvin region changes drastically across optimum doping, and the data for underdoped samples are indicative of unusual magnetic-field-induced localization of quasiparticles; this localization phenomenon is probably responsible for the unusual "insulating normal state" under high magnetic fields.