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.     

Influence of the characteristics of soil and fly ash on the supercritical carbon dioxide extraction of dioxins.

Several investigations on the extraction of dioxins from soil and fly ash with supercritical fluid have been reported; however, few of them describe the influence of components on the extraction. We extracted dioxins from eight samples with different values of organic carbon content and surface area with supercritical CO(2) at a temperature of 463 K, a pressure of 40 MPa, and using 10% toluene as an entrainer. We researched the influence of the characteristics of soil and fly ash on supercritical CO(2) extraction of dioxins. The results revealed that the extraction efficiencies of PCDD/DFs and PCBs were high for all soil samples, while that of fly ash samples decreased with the increase in organic carbon content and surface area. The extraction efficiencies of dioxins from four standard samples, activated carbon, humic acid, alumina, and florisil, were also examined. The results revealed that the extraction efficiencies were strongly influenced by activated carbon like components present in the samples.     

Donaldson–Friedman construction and deformations of a triple of compact complex spaces,II

In a previous paper of the same title the author gave a generalization of the constrution of Donaldson–Friedman, to prove the existence of twistor spaces of n CP ² with a special kind of divisors. In the present paper, we consider its equivariant version. When n = 3, this gives another proof of the existence of degenerate double solid with C *–action, and we show that the branch quartic surface is birational to an elliptic ruled surface. In case n ≥ 4, this yields new Moishezon twistor spaces with C *–action, which is shown to be the most degenerate ones among twistor spaces studied by Campana and Kreußler.     

Design and synthesis of labeling reagents (MS probes) for highly sensitive electrospray ionization mass spectrometry and their application to the detection of carbonyl, alcohol, carboxylic acid and primary amine samples.

Novel labeling reagents, called MS probes, which possess a positively charged quaternary amine moiety and can transform a neutral analyte into a charged compound by simply mixing with the analyte and allowing the mixture to stand from several minutes to 30 min at room temperature or while heating to 50 degrees C, were designed and synthesized for the highly sensitive detection of carbonyl, alcohol, carboxylic acid and primary amine samples by electrospray ionization mass spectrometry (ESI-MS). The positively charged products can be detected with high sensitivity in an ESI-MS system, which is the most popular liquid MS instrument. All of the labeled products showed a remarkably large increase in the molecular-ion peak abundance detection sensitivity of over 500-fold at picomolar concentration levels compared to that of unlabeled analytes in an ESI-MS system. These MS probes, used together with liquid MS detection, are widely applicable as a convenient method for the highly sensitive detection of less than picomolar levels of analytes, and therefore greatly enhance the power of ESI-MS analysis.     

NDMAP: the best material to study the Haldane's prediction

As predicted by Haldane, spin, S=1 one-dimensional (1D) Heisenberg antiferromagnet (HAF) has an energy gap between the singlet ground state and first excited triplet. On application of magnetic field, the triplet state Zeeman splits and the energy of one of the triplet state becomes zero at a critical field, H_c. Above H_c the system recovers magnetism. Then, we expect that a quasi-1D HAF will show a magnetic long-range ordering (LRO) at low temperatures due to the inter-chain coupling. This field-induced LRO has not been observed before due to complication of the crystal structure in the materials studied so far and/or technical difficulty.From a heat capacity measurement on a single crystal of an S=1 quasi-Q1D HAF, Ni(C₅H₁₄N₂)₂N₃(PF₆), we found an anomaly at a temperature in finite fields indicating a field-induced phase transition. A magnetic LRO is confirmed by a neutron diffraction measurement on the same sample. The temperature versus magnetic field phase diagram of this compound is constructed and discussed.     

Measurement of intense microwave field patterns using a neon glow indicator lamp

A novel method using small neon glow lamps with electrodes is developed for measuring intense microwave field patterns. When the lamp axis coincide with the electric field direction, the lamp discharge starts at the feeblest microwave electric field strength. Therefore, the lamp axis shows the field direction and the discharge starting indicates the field strength. The field strength for starting the microwave discharge is less than the strength for AC discharge, because of its low loss discharge mechanism. In the experiments using a microwave oven, it has been demonstrated again comparing with the simulated results that the method is able to use for measuring the intense electric field strength and direction.     

Influence of nuclear reactor accident at Chernobyl' on the environmental radioactivity in Toyama

The environmental radioactivity caused by the reactor accident at Chernobyl' was investigated from May 7 to May 31 of 1986 in Toyama. Measurement of radioactivities in airborne particles, rain water, drinking water, milk, and mugwort are carried out by gamma-ray spectrometry (pure Ge detector; ORTEC GMX-23195). Ten different nuclides (103Ru, 106Ru, 131I, 132Te-I, 134Cs, 136Cs, 137Cs, 140Ba-La) are identified from samples of airborne particles. In the air samples, a maximum radioactivity concentration of each nuclide is observed on 13th May 1986. The time of the reactor shut-down and the flux of thermal neutron at the reactor were calculated from 131I/132I and 137Cs/134Cs ratio. The exposure dose in Toyama by this accident is given as follows: internal exposure; [thyroid] adult-59 microSv, child-140 microSv, baby-130 microSv, [total body] adult-0.2 microSv, child, baby-0.4 microSv, external exposure; 7 microSv, effective dose equivalent; adult-9 microSv, child-12 Sv, baby-11 microSv.     

Analysis of tetracycline antibiotics using HPLC with pulsed amperometric detection.

The analysis of tetracycline, oxytetracyline, chlortetracycline and doxycycline by high-performance liquid chromatography with pulsed amperometric detection using an anodized boron-doped diamond thin film (BDD) electrode is originally reported. The analyses were carried out using the mobile phase, phosphate buffer (0.01 M, pH 2.5)-acetonitrile (80:20; v/v), on a C18 column (250 x 4.6 mm i.d., 5 microm) at a flow rate of 1.0 mL/min. The optimal PAD waveform parameters at the anodized BDD were 1.5 V (versus Ag/AgCl) detection potential (E(det)) for 290 ms (200 ms delay time and 90 ms integration time), 2.0 V (versus Ag/AgCl) oxidation potential (E(oxd)) for 200 ms oxidation time (t(oxd)) and 0.4 V (versus Ag/AgCI) reduction potential (E(red)) for 200 ms reduction time (t(red)). The proposed method showed the simultaneous determination of tetracycline, oxytetracyline, chlortetracycline and doxycycline with a linear range of 0.1 - 100 microg/mL, detection limits of 0.05 - 0.1 microg/mL and recoveries of 70.8 - 96.0%. The application of this method to real samples was demonstrated and validated using a shrimp sample.     

Feasibility study of a strong ultra cold neutron source

The heat that would be produced in a superthermal ultra-cold neutron source proposed by Golub and Pendlebury is evaluated when it is placed in a cold neutron field. The source strength achievable in the present technology is also discussed.Paper based on the KEK Internal Report 83-7 (Dee), p 223, and 84-2 (Dec), p 139, by H.Y. and M.U.