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.     

Analysis method of the angiotensin-I converting enzyme inhibitory activity based on micellar electrokinetic chromatography.

A micellar electrokinetic chromatography (MEKC) method was developed for estimating the angiotensin-I converting enzyme (ACE) inhibitory activity by separating the hippuric acid liberated in the ACE reaction mixture in the presence of an inhibitor, captopril. The hippuric acid was successfully separated and detected by MEKC with a 25 mM sodium dodecyl sulfate solution in a 25 mM phosphate-50 mM borate buffer at pH 7.0; the total analysis took about 5 min. A good linear relationship was observed between the inhibitor and the peak area of hippuric acid release. No significant difference in the ACE inhibitory activity (IC50) of captopril (an antihypertensive medicine) or autolyzed-mushrooms (functional foods) was observed between the conventional method and the MEKC method. The MEKC method was found to be a useful technique for a rapid assay of the ACE inhibitory activity.     

Status of heavy element research using a gas-filled recoil separator at RIKEN

A gas-filled type of recoil separator for heavy element research was installed at an experimental hall of RIKEN Linear Accelerator facility to realize getting higher intensity of primary beam and long beam time. Performance of the separator was studied using target recoils and various nuclear reactions. The results show the high performance of the separator for heave element research. As an application of the GARIS, production and identification of an isotope of the 110th element ²⁷¹[110] have been performed using the ²⁰⁸Pb(⁶⁴Ni,1n)²⁷¹[110] reaction. Three decay chains coincide well both in decay times and energies with the ones reported by the group of SHIP experiment at GSI, Germany. Our results provide a confirmation of the synthesis of an isotope ²⁷¹[110] of element 110.     

Classification for dimethylarsenate-decomposing bacteria using a restrict fragment length polymorphism analysis of 16S rRNA genes.

A new monitoring system for bacterial communities involving dimethylarsinic acid (DMAA) decomposition was provided by combining the MPN (Most Probable Number) method and RFLP (restriction-fragment-length polymorphism analysis). The abundance of DMAA decomposing bacteria was estimated by the MPN method using a bacterial culture medium, which included DMAA as the sole carbon source, indicating bacterial cell densities of 1700 cells/ml in Lake Kahokugata and 330 cells/ml in Lake Kibagata. After isolating the dominant bacteria using agar plates, the isolates were classified into some genotype groups by RFLP analysis using 16S rDNA sequences. Classification of the RFLP analysis indicated that 14 isolates of Lake Kahokugata were classified into 6 types, which included 2 dominant types related to genus Pseudomonas, while 8 isolates of Lake Kibagata displayed 6 types including one or two isolates. Moreover, the RFLP types were unique for each lake, suggesting that DMAA decomposing bacteria were specific for the aquatic environment related to the arsenic cycle. The activities of DMAA decomposition mostly matched with the RFLP type category of the isolates. Accordingly, combining the MPN method with the RFLP analysis will play an important role in elucidating the distributions and dynamics of the DMAA-decomposing bacterial community.     

High-resolution infrared spectra of NCCN and NCCN

High-resolution spectra of ¹⁵N¹²C¹²C¹⁵N and ¹⁴N¹³C¹³C¹⁴N have been measured and analyzed from 200 to 3600 cm⁻¹. All the vibrational levels below 900 cm⁻¹ have been observed and characterized. The Fermi resonance between ν₂ and 2ν₄ has been studied and the resonance constant has been determined for several cases. Several Σ⁻ states have been directly observed for the first time for each isotopomer, the (0001111)0f, (0011111)0f, and (0002222)0f states. The pattern of the energy levels for clusters of l-type resonance coupled levels, such as 0001131,3, has been determined for cyanogen for the first time. Among other things this involved the determination of the vibrational l-type resonance constant, r₄₅. Many of the power series constants, α_i and x_ij, and higher order constants have been determined.     

Application of ODMR to the study of DNA complexes of bisintercalating antibiotics and their biosynthesized derivatives

The DNA complexes of triostin A, echinomycin, and the monoquinoline (1QN) and bisquinoline (2QN) biosynthesized derivatives of echinomycin were investigated by optical detection of triplet-state magnetic resonance (ODMR) spectroscopy, with the quinoxaline and quinoline moieties of the DNA-binding peptides used as intrinsic probes. Plots of zero-field splitting (zfs)D parameter versus monitored wavelength revealed heterogeneity in the phosphorescence emission of echinomycin, triostin A, and 2QN ascribed to the occurrence of major and minor forms of the peptides in aqueous solution. ODMR results, in conjunction with findings from phosphorescence studies, indicate that the quinoxaline and quinoline chromophores of the major forms of the peptides are involved in aromatic stacking interactions in complexes with the natural DNAs fromMicrococcus lysodeikticus, Escherichia coli, and calf thymus as evidenced by red shifts in the phosphorescence 0,0 bands of the drugs, reductions in the phosphorescence lifetimes and zfsD andE parameters, and polarity reversal of the ODMR slow passage signals upon drug complexation. The reversal in ODMR signal polarity of echinomycin and 2QN is a consequence of changes in the triplet-state sublevel decay constants upon peptide binding to the natural DNAs. The extent of reduction of theD parameter for the major form of echinomycin, 2QN, and the quinoline moiety of 1QN upon complexation with polymeric DNAs was found to correlate with the binding affinities measured for these targets [1], but no correlation was found for the quinoxaline moiety of 1QN. Preliminary studies of triostin A-DNA complexes also revealed no correlation between the reduction in zfsD-value upon complexation and binding affinity, although the largest reductions inD-value among the peptides investigated in this report were exhibited by the poly(dG-dC)·poly(dG-dC) and natural DNA complexes of triostin A.