Efficient and beta-Stereoselective Synthesis of 4(5)-(beta-D-Ribofuranosyl)- and 4(5)-(2-Deoxyribofuranosyl)imidazoles(1)

A synthetic route to 4(5)-(beta-D-ribofuranosyl)imidazole (1), starting from 2,3,5-tri-O-benzyl-D-ribose (5), was developed via a Mitsunobu cyclization. Reaction of 5 with the lithium salt of bis-protected imidazole afforded the corresponding 5-ribosylimidazole 7RS. Hydrolysis of 7RS gave a 1:1 mixture of diol isomers 8R and 8S having an unsubstituted imidazole. Mitsunobu cyclization of the mixture 8RS using N,N,N',N'-tetramethylazodicarboxamide and Bu(3)P exclusively afforded benzylated beta-ribofuranosyl imidazole 9beta in 92% yield, accompanied by alpha-anomer 9alpha, in a ratio of 26.3:1. The configuration of 9beta was established by X-ray crystallography of ethoxycarbonyl derivative 10beta. Reductive debenzylation of 9beta over Pd/C was carried out, and the synthesis of 1 was attained from starting 5 in four steps and 87% overall yield. This synthetic methodology was extended to the synthesis of 4(5)-(2-deoxy-beta-D-ribofuranosyl)imidazole (2). Mitsunobu cyclization of a 1:1 mixture of the corresponding diol isomers 14RS produced 15beta and 15alpha in a ratio of 5.4:1. The synthesis of 2 was attained in a 59% overall yield from the starting 3,5-di-O-benzyl-2-deoxy-D-ribose (12). beta-Stereoselective glycosylation in the key step is discussed and explained by intramolecular hydrogen bonding between an NH in the imidazole and the oxygen functional group in the sugar moiety.     

Estimation of secondary electron effect in the J-PARC rapid cycling synchrotron after first study

The J-PARC 3 GeV rapid-cycling synchrotron (RCS) is required to provide 1 MW pulsed protons to the spallation neutron target and the 50 GeV main ring. Since the RCS finally accelerates very high intensity beam such as 8.3 × 10¹³ ppp, the secondary electron cloud may affect the accelerator performance. We measured the secondary electron emission from the TiN coating surface and the ferrite sample. By using these measurement results, we estimated the effect of the electron cloud made by the emitted secondary electron at present beam parameters.     

Development and validation of a liquid chromatographic method for the analysis of positron emission tomography radiopharmaceuticals with Ru(bpy)(3)(2+)-KMnO(4) chemiluminescence detection.

A sensitive, selective and rapid high-performance liquid chromatographic (HPLC) method with chemiluminescence (CL) detection was developed and validated for the analysis of positron emission tomography (PET) radiopharmaceuticals. This method is based on the CL reaction of PET compounds with tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)] and acidic potassium permanganate [KMnO(4)]. After optimization of the reaction conditions, 12 of the 14 PET compounds investigated could be successfully detected and showed good performance in terms of sensitivity, linearity and reproducibility. In particular, for compounds with a tertiary amine functional group, the limits of detection were ppb levels for a 20 microL injection volume. Finally, this method was used to determine PET compounds for calculating of specific radioactivity in pharmaceutical samples.     

Nuclear spin dynamics of nuclear-ordered solid<Superscript>3</Superscript>He in the low field phase

Pulsed NMR was used to investigate nuclear spin dynamics of nuclear-ordered solid³He in the low field phase. The nuclear spin motion became unstable under certain conditions. Under stable conditions the spin motion can be described by the OCF equations. The tipping-angle-dependent frequency shift and multiple spin echoes were observed, which are similar to the case of superfluid³He. The onset of the instability of spin motion is attributed to the stimulated emission mechanism through the three-magnon relaxation process, which is similar to the Suhl instability in electronic magnetism. We derived the magnon life time from the analysis of the instability. During the instability, a largenegative frequency shift was observed. This negative shift is explained by the extension of Fomin-Ohmi's theory to include the state of decayed magnon and this explanation is consistent with the instability model.     

Writing of crystal line patterns in glass by laser irradiation

We examined the laser-induced crystallization to form the fresnoite type Ba₂TiGe₂O₈ crystal line patterns in transition metal ion doped BaO–TiO₂–GeO₂ glass. Ba₂TiGe₂O₈ crystal line was written in 0.6FeO–33.3BaO–16.7TiO₂–50GeO₂ glass by continuous wave yttrium–aluminum–garnet (YAG) laser irradiation. We obtained polarization dependence of Raman spectra in crystal line pattern. Second harmonic generation (SHG) indicated unique fringe patterns from Ba₂TiGe₂O₈ crystal lines.     

Time-series analysis of sleep-wake stage of rat EEG using time-dependent pattern entropy

We performed electroencephalography (EEG) for six male Wistar rats to clarify temporal behaviors at different levels of consciousness. Levels were identified both by conventional sleep analysis methods and by our novel entropy method. In our method, time-dependent pattern entropy is introduced, by which EEG is reduced to binary symbolic dynamics and the pattern of symbols in a sliding temporal window is considered. A high correlation was obtained between level of consciousness as measured by the conventional method and mean entropy in our entropy method. Mean entropy was maximal while awake (stage W) and decreased as sleep deepened. These results suggest that time-dependent pattern entropy may offer a promising method for future sleep research.