Stereoselective synthesis of the beta-anomer of 4'-thionucleosides based on electrophilic glycosidation to 4-thiofuranoid glycals

Three types of 4-thiofuranoid glycal with different 3,5-O-silyl protecting groups were prepared and their electrophilic glycosidation was investigated. The 3,5-bis-O-(tert-butyldimethylsilyl)-4-thiofuranoid glycal (5) was obtained through mesylation of 2-deoxy-4-thio-D-erythro-pentofuranose (4) and subsequent base-promoted elimination, while thermal elimination of sulfoxide derivatives was suitable for the preparation of 3,5-O-(tetraisopropyldisiloxane-1,3-diyl) (9) and 3,5-O-(di-tert-butylsilylene) (11) 4-thioglycals. The glycosidation reactions of these 4-thioglycals were carried out, in the presence of either PhSeCl or NIS, by using silylated derivatives of uracil, thymine, cytosine, and N(6)-benzoyladenine. Among the three 4-thioglycals, 11 was found to be an excellent glycosyl donor, forming the desired beta-anomer exclusively irrespective of the nucleobase employed.     

Synthesis,crystal structures,and redox potentials of 2,3,12,13-tetrasubstituted 5,10,15,20-tetraphenylporphyrin zinc(II) complexes

Zinc(II) complexes of antipodal beta-tetrasubstituted meso-tetraphenylporphyrin with trifluoromethyl (Zn(TPP(CF(3))(4)) (1a)), bromine (Zn(TPPBr(4)) (2a)), and methyl groups (Zn(TPP(CH(3))(4)) (3a)) were synthesized in order to examine the steric and the electronic effects of trifluoromethyl groups on the macrocycle. The analysis of X-ray crystal structures of the five-coordinate complexes Zn(TPP(CF(3))(4))(EtOH)(3) (1b), Zn(TPPBr(4))(MeOH)(DMF) (2b), and Zn(TPP(CH(3))(4))(THF)(1.6)(CHCl(3))(0.4) (3b) revealed distorted macrocyclic cores where significant differences in the Zn-N distance between the beta-substituted and the non-beta-substituted side were observed. The difference was significant in 1b due to the strong steric interactions among the peripheral substituents and the electronic effects of trifluoromethyl groups. The macrocycles of 1b-3b are saddle-distorted and slightly ruffled due to the five-coordination of zinc(II) and the peripheral substitution. Distortion of the macrocycles of 2b and 3b were modest. On the other hand, distortion in 1b was severe due to the peripheral strain. Cyclic voltammetric measurements of the four-coordinate complexes Zn(TPP) and 1a-3a were performed and their redox potentials were analyzed together with previously reported potentials of Zn(TPP(CN)(4)). The oxidation potential of 1a did not gain as much as expected from the electron-withdrawing effect of the four trifluoromethyl groups. The HOMO-LUMO gap of 1a was very small (1.5 V) and cannot just be explained by macrocyclic distortion. The magnitude of this gap is very similar to that of Zn(TPP(CN)(4)). Compound 2a also exhibited a modest gap contraction. Compound 3a was easier to oxidize and harder to reduce than Zn(TPP), even though the HOMO-LUMO gap of 3a was similar to that of Zn(TPP).     

On simple families of cyclic polynomials

We study polynomials giving cyclic extensions over rational function fields with one variable satisfying some conditions. By using them, we construct families of cyclic polynomials over some algebraic number fields. And these families give non-Kummer (or non-Artin-Schreier) cyclic extensions. In this paper, we see that our polynomials have two nice arithmetic properties. One is simplicity: our polynomials and their discriminants have more simple expressions than previous results, e.g. Dentzer (1995), Malle and Mazat (1999) and Smith (1991), etc. The other is a ``systematic' property: if one of our polynomials gives an extension , then for every intermediate field we can easily find polynomials giving from systematically.

     

An agar-microchamber cell-cultivation system: flexible change of microchamber shapes during cultivation by photo-thermal etching

A new type of cell-cultivation system based on photo-thermal etching has been developed for the on-chip cultivation of living cells using an agarose microchamber array. The method can be used to flexibly change the chamber structure by photo-thermal etching, even during the cultivation of cells, depending upon the progress in cell growth. We used an infrared (1064 nm) focused laser beam as a heat source to melt and remove agar gel at the heated spot on a thin chromium layer. The melting of the agar occurred just near the chromium thin layer, and the size of the photo-thermally etched area depended almost linearly on the power of the irradiated laser beam from 2 microm to 50 microm. Thus by using photo-thermal etching with adequate laser power we could easily fabricate narrow tunnel-shaped channels between the microchambers at the bottom of the agar-layer even during cell cultivation. After 48 h of cultivation of nerve cells, the nerve cells in two adjacent chambers made fiber connections through the fabricated narrow tunnel-shaped channels. These results suggest that photo-thermal etching occurred only in the area where an absorbing material was used, which means that it is possible to photo-thermally etch lines without damaging the cells in the microchambers. The results also suggest that the agar-microchamber cell cultivation system in combination with photo-thermal etching can potentially be used for the next stage of single cell cultivation including the real-time control of the interaction of cells during cell cultivation.     

Phylogenetic studies of dogs with emphasis on Japanese and Asian breeds

The first domestication of the dog occurred in East Asia, and major ancestor of the dog was a wolf subspecies, Canis lupus chanco. This finding derives from data on the nucleotide sequences of mtDNA and the frequency of genes controlling blood protein polymorphisms in various subspecies of wolves and dog breeds around the world. The results of the allele frequency distribution of genes controlling 16 blood protein polymorphisms, and the incidence of dogs possessing erythrocytes with high potassium (HK) in Japan, East Asia and Europe allowed us to posturate the following hypothesis about the origins of Japanese dogs and the history of their development. In the Jomon period the first dogs entered the Japanese archipelago from southern or northern continental Asia. These dogs eventually spread throughout Japan. Then, during the Yayoi and Kofun periods, other dogs were brought over via the Korean Peninsula, and crossbreeding occurred with the original dogs. The resulted offspring can be assumed to be the ancestors of most of the Japanese breeds that exist today. Ethological studies have revealed a significant breed difference in behavioral traits among canine breeds with Japanese dogs, showing more aggressive dispositions than most of European dogs.     

Spectral sets of certain unbounded functions

Summary A. Beurling introduced the concept of spectral sets of unbounded functions to study the possibility of the approximation of those by trigonometric polynomials. We consider spectral sets of unbounded functions in a certain class which contains the square of the Riemann zeta-function as a typical example.     

A15Nb3Si produced by high-pressure annealing of amorphous sputter deposits

A high-pressure annealing technique has been used to convert an amorphous Nb-23.7 at.% Si alloy, prepared by sputtering, into the A15 phase alloy. X-ray diffraction examination of the alloy samples quenched to ambient conditions has shown that they are in an almost single-phased state with a lattice parameter of 0.5120 nm and a high degree of atomic ordering. An onset of superconductivity has been detected at 8.9 K and a temperature derivative of upper critical field is 14 kOe/K (MA/4π mK).     

The first utilization of acidic ionic liquid for preparation of tetraarylporphyrins

A phase-separated acidic ionic liquid affords to catalyze a reaction of pyrrole with benzaldehyde in dichloromethane, forming porphyrins in a comparable yield to the Lindsey method and is reusable at least ten times without loss of catalytic activity.     

Generation of 5-W deep-UV continuous-wave radiation at 266 nm by an external cavity with a CsLiB6O10 crystal

A Brewster-cut CsLiB6O10 crystal is employed as an external resonant frequency doubler to generate cw deep-UV radiation at 266 nm. We have generated 5.0 W of usable cw output power, which is 6.1 W in the crystal, for an incident green power of 9.6 W, corresponding to an internal conversion efficiency of 61.8%. The power obtained is, to our knowledge, three times higher than previously reported for cw 266-nm generation.