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.     

Large-volume injection electrothermal AAS combined with tungsten-treated pyrolytic graphite furnace: determination of cadmium in tap, snow and river water samples with phosphate modifier.

A large-volume (100 microl) injection-ETAAS with W-treated PG furnace combined with a phosphate modifier was applied to the determination of unpolluted levels of Cd in tap, snow and river-water samples. The limit of detection of 1.1 ng l(-1) was observed for a 4 w/v% NH4H2PO4 modifer. Matrix interference studies were tested for major ion species well found in fresh water. The direct determination of Cd in certified river water (12 +/- 2 ng l(-1)) was carried out and the observed value was in agreement with the certified one. The good recoveries of Cd added to real environmental water samples were also observed. This method was applied to the determination of Cd in unpolluted environmental water samples.     

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.     

Preparation and certification of the new reference materials; plastics (disk form, JSAC 0621-0625) for determination of mercury using x-ray fluorescent analysis.

The Japan Society for Analytical Chemistry has developed some new plastic certified reference materials (CRMs) for the analysis of mercury in polyester disks using XRF analysis. These CRMs (named as JSAC 0621-0625) were prepared by casting polyesters including a toluene solution of organometallic compounds as a standard. Concentrations of the five levels of mercury ranged from 0 to 250 mg/kg. Homogeneity tests of prepared disks had shown excellent results. Interlaboratory comparison study for the certification was performed by 15 laboratory participants. The z-scores in robust statistical method was applied for the evaluation of outliers. The certified values were assigned after discarding outliers. The uncertainties of certified values were determined as the confidence levels of 95%.     

Sensitive determination of anandamide in rat brain utilizing a coupled-column HPLC with fluorimetric detection

A fluorimetric determination method for N-arachidonoylethanolamine (anandamide) was developed using a precolumn fluorescence derivatization followed by coupled-column high-performance liquid chromatography (HPLC). Anandamide extracted from the rat brain tissue was derivatized with 4-N-chloroformylmethyl-N-methylamino-7-N, N-dimethylaminosulfonyl-2,1,3-benzoxadiazole (DBD-COCl), purified by a solid-phase extraction (Emporetrade mark), and assayed by the coupled-column HPLC. The HPLC consisted of phenyl (100 x 4.6 mm i.d. ) and octadecylsilica columns (250 x 4.6 mm i.d.), both connected by a six-port valve. The concentration of anandamide in rat brain was 3. 37 +/- 0.73 pmol/g with 6.47 and 3.57% of intra- and inter-day precisions, respectively. Using this method, we investigated the alteration of anandamide concentration in rat brain 30 min after administration of anandamide (2 mg/kg, i.p.) to rats pretreated with or without phenylmethylsulfonyl fluoride (PMSF; 30 mg/kg, i.p.), an inhibitor of amidohydrolase. In rats pretreated with PMSF, the brain concentration of anandamide was approx. 16-fold higher than that of rats without PMSF (p < 0.01).