Total synthesis of fumitremorgin B

Total synthesis of fumitremorgin B, one of the potent tremorgic mycotoxins, was achieved in 7 steps.     

Control of energy spread and dark current in proton and ion beams generated in high-contrast laser solid interactions

By using temporal pulse shaping of high-contrast, short pulse laser interactions with solid density targets at intensities of 2 × 10(21) W cm(-2) at a 45° incident angle, we show that it is possible to reproducibly generate quasimonoenergetic proton and ion energy spectra. The presence of a short pulse prepulse 33 ps prior to the main pulse produced proton spectra with an energy spread between 25% and 60% (ΔE/E) with energy of several MeV, with light ions becoming quasimonoenergetic for 50 nm targets. When the prepulse was removed, the energy spectra was broad. Numerical simulations suggest that expansion of the rear-side contaminant layer allowed for density conditions that prevented the protons from being screened from the sheath field, thus providing a low energy cutoff in the observed spectra normal to the target surface.     

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.     

Fundamental diagram in traffic flow of mixed vehicles on multi-lane highway

We study the fundamental diagram for traffic flow of vehicular mixture on a multi-lane highway. We present the car-following model of multi-lane traffic in which slow and fast vehicles flow with changing lanes. We investigate the traffic states of the vehicular mixture under the periodic boundary. Two values of the current appear at a density and two current curves are obtained. Vehicles move with changing lanes in the traffic state of high current, while vehicles move without changing lanes in the traffic state of low current. They depend on the density, the fraction of slow vehicles, and the initial condition. In the high-current curve, the jamming transition between the free flow and the jammed state occurs at a low density. The fundamental diagrams (current-density diagrams) are shown for the single-lane, two-lane, three-lane, and four-lane traffics.     

Protein identification by peptide mass fingerprinting and peptide sequence tagging with alternating scans of nano-liquid chromatography/infrared multiphoton dissociation Fourier transform ion cyclotron resonance mass spectrometry

We have developed a method for protein identification with peptide mass fingerprinting and sequence tagging using nano liquid chromatography (LC)/Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). To achieve greater sensitivity, a nanoelectrospray (nano-ES) needle packed with reversed-phase medium was used and connected to the nano-ES ion source of the FTICR mass spectrometer. To obtain peptide sequence tag information, infrared multiphoton dissociation (IRMPD) was carried out in nano-LC/FTICR-MS analysis. The analysis involves alternating nano-ES/FTICR-MS and nano-ES/IRMPD-FTICR-MS scans during a single LC run, which provides sets of parent and fragment ion masses of the proteolytic digest. The utility of this alternating-scan nano-LC/IRMPD-FTICR-MS approach was evaluated by using bovine serum albumin as a standard protein. We applied this approach to the protein identification of rat liver diacetyl-reducing enzyme. It was demonstrated that this enzyme was correctly identified as 3-alpha-hydroxysteroid dehydrogenase by the alternating-scan nano-LC/IRMPD-FTICR-MS approach with accurate peptide mass fingerprinting and peptide sequence tagging.     

Epoc group: transformable protecting group with gold(iii)-catalyzed fluorene formation

This study presents the novel concept of a transformable protecting group, which changes its properties through structural transformation. Based on this concept, we developed a 2-(2-ethynylphenyl)-2-(5-methylfuran-2-yl)-ethoxycarbonyl (Epoc) group. The Epoc group was transformed into an Fmoc-like structure with gold(iii)-catalyzed fluorene formation and was removable under Fmoc-like mild basic conditions post-transformation even though it was originally stable under strongly basic conditions. As an application for organic synthesis, the Epoc group provides the novel orthogonality of gold(iii)-labile protecting groups in solid-phase peptide synthesis. In addition, the high turnover number of fluorene formation in aqueous media is suggestive of the applicability of the Epoc group to biological systems.

A protecting group removable with gold(iii)-catalyzed fluorene formation and the subsequent addition of piperidine was developed.     

Construction of nitrogen-heterocyclic compounds through zirconium mediated intramolecular alkene-carbonyl coupling reaction of N-(o-alkenylaryl)carbamate derivatives

Intramolecular alkene-carbonyl coupling reaction of N-benzyl-N-(o-alkenylaryl)carbamate derivative derived from o-aminostyrene, o-(aminomethyl)styrene and o-aminoallylbenzene smoothly proceeded by treating with zirconocene-butene complex to give the corresponding lactam derivative.     

HeII(304Å) photoelectron spectrum of N2O4

The 304 Å HeII photoelectron (PE) spectrum of a mixture of NO₂ and N₂O₄ in the gaseous phase has been measured in the region up to 29 eV. By subtracting the HeII spectrum of NO₂ from the mixed spectrum, the HeII spectrum due to N₂O₄ has been deduced, indicating that there are three new PE bands in the region 20—29 eV. Relative band intensities have also been obtained from the HeII of N₂O₄ below 16 eV, corrected for electron collecting efficiency.     

Radiation damage in Si photodiodes by high-temperature irradiation

Results are presented of a detailed study of the effects of high-temperature 4-MeV neutron irradiation on the performance degradation of Si pin photodiodes together with the radiation-induced defects, observed by deep level transient spectroscopy. The degradation of the device performance and the introduction rate of the lattice defects decrease with increasing sample temperature during irradiation. For a 250°C irradiation, the reduction of the reverse current is only 20% of the starting value. This result suggests that the creation and recovery of the radiation damage proceeds simultaneously at high temperatures. Carbon-related complex as hole capture levels is also mainly responsible for the device degradation for high-temperature neutron irradiation.