Synthesis of (--)-Muricatacin via alpha- and alpha'-C-H bond functionalization of tetrahydrofuran

(--)-Muricatacin, a potent cytotoxic (4R,5R)-5-hydroxyheptadecan-4-olide, has been synthesized through alpha-C--H hydroxyalkylation and alpha'-C--H oxidation of tetrahydrofuran. This study presents a novel method for C--H bond functionalization as a means for preparing gamma-(hydroxyalkyl)-gamma-butyrolactones.     

Measurements of LET-distribution, dose equivalent and quality factor with the RRMD-III on the Space Shuttle Missions STS-84, -89 and -91

Dosimetric measurements on the Space Shuttle Missions STS-84, -89 and -91 have been made by the real-time radiation monitoring device III (RRMD-III). Simultaneously, another dosimetry measurement was made by the Dosimetry Telescope (DOSTEL) on STS-84 and by the tissue-equivalent proportional counter (TEPC) on STS-91. First, the RRMD-III instrument is described in detail and its results summarized. Then, the results of DOSTEL and TEPC are compared with those of the RRMD-III. Also, the absorbed doses obtained by TLD (Mg2SiO4) and by RRMD-III on board STS-84 and -91 are compared.     

Ion-exchange resin decomposition in supercritical water

Abstract

Using supercritical water oxidation, the cation exchange resin was decomposed fast and completely to water, carbon dioxide and sulfuric acid. While the resin decomposition yield increased with the reaction time and the amount of hydrogen peroxide added as oxidizing agent, it was constant in the resin concentration from 0.14 to 1.9 dry resin weight percent to water. More than 99% of the cation exchange resin was decomposed with hydrogen peroxide added in the amount of 7 times the stoichiometric value at 673 K and 30MPa for 30 minutes of the reaction time. The cation exchange resin is decomposed through two main reaction pathways. One has a rate controlling intermediate such as acetic acid whose decomposition rate was very slow, and the other does not have stable intermediates. The decomposition of the acetic acid is a significant factor for the complete decomposition of the resin, although it does not dominate the whole resin decomposition. A simple kinetic model that estimates the resin decomposition yield was developed.     

The TEPSICO-II apparatus at UVSOR and threshold electron spectra of some molecules over the wavelength range 35–120 nm

An apparatus designed for studies of state selected unimolecular and ion-molecule reactions using synchrotron radiation is described. It is installed in the UVSOR storage ring in Okazaki. Threshold electron spectra of some rare gas atoms and diatomic and polyatomic molecules taken with this apparatus are presented and discussed.     

The anomalous behaviour of Gd atoms (Fe1−xMnx)2 compounds

The educed Gd atoms in the X-structure (Th₆Mn₂₃-type) of Gd(Fe_1−xMn_x)₂ were magnetically investigated by comparing with Gd₆(Fe_1−yMn_y)₂₃ whose structure is Th₆Mn₂₃-type. The magnetic properties of Gd(Fe_1−xMn_x)₂ (0.4≤x≤0.7) were observed to be quite similar to those of Gd₆(Fe_1−yMn_y)₂₃ (0.4≤y≤0.7).     

Characterization of certified reference material for quantification of polychlorinated biphenyls and organochlorine pesticides in fish

Fish certified reference material (CRM), NMIJ CRM 7404-a, for the analysis of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) was developed by the National Metrology Institute of Japan, part of the National Institute of Advanced Industrial Science and Technology. Fish samples (Japanese seabass) used for the preparation of the CRM were collected from Tokyo Bay, and the edible part was freeze-dried, pulverized, sieved, homogenized, and sterilized by γ-irradiation. This sample is in the form of a powder comprising approximately 10 g stored in a brown glass bottle. The certification was carried out using multiple analytical methods such as pressurized liquid extraction, Soxhlet extraction, saponification, and homogenization to ensure the reliability of analytical results; the certified values of target PCBs (PCB 28, PCB 70, PCB 105, PCB 153, and PCB 170) and OCPs (trans-nonachlor, dieldrin, p,p′-DDE, p,p′-DDT, and p,p′-DDD) were 1.05–14.0 μg kg⁻¹ and 1.57–18.0 μg kg⁻¹ for PCBs and OCPs, respectively. This is the first fish powder CRM in which PCBs and OCPs were determined by isotope dilution mass spectrometry.     

Freeze-thawing single human embryonic stem cells induce e-cadherin and actin filament network disruption via g13 signaling

Poor adhesion of single human embryonic stem (hES) cells after freeze-thawing causes death. To investigate mechanisms responsible for this, Rho-dependent protein kinase (ROCK) inhibitor Y-27632-treated and untreated single hES cells were analyzed for E-cadherin and F-actin distribution by immunostaining and phalloidin staining respectively and for G13 signaling pathway components by DNA microarray and quantitative polymerase chain reaction (PCR). Y-27632-treated cells clustered rapidly and maintained E-cadherin and F-actin distribution without losing Oct-3/4. Immediately after thawing, E-cadherin in untreated hES cells dotted along the membrane and then displayed eccentric cytoplasmic localization. Bleb formation and early Oct-3/4 loss occurred after F-actin network condensation in the cytoplasm. Microarray analyses and quantitative PCR indicated upregulation of two actin reorganization-associated components of the G13 signaling pathway, Arhgdib and Cdc42, in untreated cells. Considering these findings and that cell death was partly interrupted by Y-27632, E-cadherin and actin cytoskeleton network disruption through the G13 signaling pathway may cause hES cell death after freeze-thawing.     

Proton response of high sensitivity CR-39 copolymer

We studied the track response for the copolymer of CR-39 monomer with N-isopropylacrylamide (NIPAAm) as well as etching properties. It was found that copoly (CR-39/NIPAAm/Naugard 445) composed in wieght ratio of 99/1/0.01 is highly sensitive to low LET particles in the region below 10 keV/μm of LET and able to record normally incident particles of LET down to 1.5 keV/μm, recording protons up to the energy of 27 MeV. These results were compared with the responses for two types of CR-39 detectors containing a small quantity of antioxidant. The threshold energy proton registration is discussed.