Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

Endoscopic Observation of Tissue by Narrowband Illumination

We propose a new illumination method for a medical endoscope: narrow band imaging (NBI), in which the spectral bandwidth of the filtered light is narrowed. To confirm how the spectral specifications of the filtered light influence a reproduced image, an experiment was conducted observing the endoscopic images of the back mucosa of a human tongue. In addition, the effect of NBI on endoscopic images was investigated through preliminary clinical tests in colonoscopy and upper gastrointestinal endoscopy. It has been shown that NBI can enhance the capillary pattern and the crypt pattern on the mucosa. These patterns are useful features for diagnosing an early cancer.     

A New Method for Rotation and Brightness Invariant Pattern Recognition Based on Modified Multiple Circular Harmonic Expansions

A new method for rotation and brightness invariant pattern recognition was proposed by applying multiple circular harmonic expansions to the joint transform correlator. The amplitudes of the multiple orders of circular harmonic expansions made from a detecting image were synthetically modified to respond to the same auto-correlation peaks. These modified circular harmonic expansions were arranged in the input plane as reference patterns together with an arbitrary target pattern, and the correlation signals between them were calculated in the subtracted joint transform correlator. The fraction of the correlation-peak intensities between the target and the references were extracted as a new discrimination parameter. This new parameter performs pattern recognition under rotation and brightness invariance with good discriminability. Its high discriminability has been proved in computer simulations using the face image patterns of many individuals.     

Magneto-Optical Measurement of Organic Conductor Using Rotational Cavity System

We have developed a new magneto-optical measurement system using a rotational cavity system equipped with a millimeter vector network analyzer and a 14 T solenoid type super conducting magnet. The measurement can be performed in the transmission configuration down to 1.6 K. The results of the precise angular dependence measurement of quasi-one-dimensional organic conductor (DMET)₂I₃ using the new system are shown, and its Fermi surface will be discussed in connection with the previous reports.     

Constructive and Destructive Two-Pulse Excitation Investigated with a White-Light Michelson Interferometer

Linear propagation of two pulses through methanol solution of aluminum phthalocyanine chloride is investigated using a modified white-light Michelson interferometer. The observed coherence time of the white light is 6 fs, and the separation between the two-excitation pulses is set to about 10 fs. The excitation is dependent on the phase-relation between the two pulses. We have observed an enhancement of the excitation when the two pulses are in-phase and strong suppression of the excitation when the two pulses are out of phase by π.     

Tensor analyzing power T 20 of the dd → 3Hen and dd → 3Hp reactions at zero angle for energies 140, 200, and 270 MeV

RIKEN Accelerator Research Facility data on the tensor analyzing power T ₂₀ of the dd → ³Hen and dd → ³Hp reactions at zero angle for deuteron kinetic energies of 140, 200, and 270 MeV are reported. The observed positive sign of T ₂₀ clearly demonstrates the sensitivity to the D/S-wave ratio in the ³He and ³H wave functions in the energy range of the experiment. Data on T ₂₀ for the ³Hen channel are in agreement with those for the ³Hp channel within the experimental errors.     

Structural characterization of Acetobacter diazotropicus levansucrase by matrix-assisted laser desorption/ionization mass spectrometry: identification of an N-terminal blocking group and a free-thiol cysteine residue

High-resolution matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was used to characterize the primary structure of the levansucrase (EC 2.4.1.10) secreted by Acetobacter diazotropicus SRT4. The technique permitted not only the reading frame of this enzyme, the amino acid sequence of which was deduced from DNA, but also the elucidation of an N-terminal blocking group and the position of a disulfide bridge between Cys309 and Cys365 among the three Cys residues. A free cysteine (Cys127) was identified by modifying an intact molecule with a sulfhydryl reagent, 5-(octyldithio)-2-nitrobenzoic acid, under non-reducing conditions. In addition, the enzyme obtained by site-directed mutagenesis at Asp279 to Asn279 was also identified by the above methods. Post-source decay analysis of the tryptic peptide containing the mutation site unequivocally revealed an Asn residue at position 279.