Synthesis and γ-radiolysis of 2′-deoxy-5-fluorouridine and 5-fluorouridine derivatives

Seventeen compounds having a variety of substituents at the 3- and 5′-positions of 2′-deoxy-5-fluorouridine (5-FUdR) and 5-fluorouridine (5-FUR) were synthesized, and their γ-radiolysis in aqueous solutions were studied. The compounds having thioureido (RNHCSNH, R  H, PhCH₂, acyl) and thiocarbonylamino (XCSNH, X  PhCH₂S, PhO) groups at the 3-position of 5-FUdR were efficiently cleaved to give 5-FUdR with high G values upon γ-irradiation of their aqueous solutions. The active species for these cleavage reactions were hydrated electron (e⁻ _aq), H^• and HO^•. However, the compounds having a dimethylsulfoxyimino group at 3-position of 5-FUdR and 5-FUR afforded 5-FUdR and 5-FUR only under the radiolysis conditions where e⁻ _aq becomes a principal active species. The compound having a 2-benzoylthiazoylthiocarbonylamino group at the 3-position of 5-FUdR showed the highest reactivity toward HO^.. The mechanisms of these γ-radiolysis reactions are discussed. The examination of anticellular activities of γ-irradiated compounds having a thiocarbonylamino group at the 3-position of 5-FUdR toward murine Sarcoma 180 cells revealed that these compounds may be utilized as a candidate for a radiation-induced drug (RID).     

A novel polyaddition of bifunctional acetylenes containing electron-withdrawing groups. III. Synthesis of polymers having β-alkoxyenoate moieties by the reaction of internal diynes with diols

Tri-n-butylphosphine-catalyzed polyadditions of activated internal diynes (bifunctional β-substituted propiolate, 1B and 1C ) with diols are described. Although a terminal bispropiolate ( 1A ) could not produce soluble polymers, with secondary diols, the polyaddition of 1B or 1C with primary as well as secondary diols gave corresponding polymers ( 3 , only composed of E isomeric units) in high yield. The rate of the present polyaddition was estimated by a model reaction of benzyl alcohol with methyl 2-heptynoate ( 4 ), from which the introduction of alkyl groups at the β-position of propiolate moieties was found to decrease the rate of the reaction by 80 times. Furthermore, the rate-determining step on this polymerization system was speculated to be a protonation step of zwitterionic intermediates with protons from diols. © 1996 John Wiley & Sons, Inc.     

Chemical and genetic diversity of Ligularia virgaurea collected in northern Sichuan and adjacent areas of China. Isolation of 13 new compounds

Root chemicals and DNA sequences were analyzed for Ligularia virgaurea collected in the northern Sichuan Province and adjacent areas of China. Thirty-eight samples were found to contain five chemotypes, two known and three new ones. From samples of the new chemotypes, 13 new compounds were isolated, including 3 sesquiterpene dimers and some rearranged eremophilanes. The DNA sequences suggested that the chemotype differentiation had a genetic origin.     

Extremely low vertical-emittance beam in the accelerator test facility at KEK

Electron beams with the lowest, normalized transverse emittance recorded so far were produced and confirmed in single-bunch-mode operation of the Accelerator Test Facility at KEK. We established a tuning method of the damping ring which achieves a small vertical dispersion and small x-y orbit coupling. The vertical emittance was less than 1% of the horizontal emittance. At the zero-intensity limit, the vertical normalized emittance was less than 2.8 x 10(-8) rad m at beam energy 1.3 GeV. At high intensity, strong effects of intrabeam scattering were observed, which had been expected in view of the extremely high particle density due to the small transverse emittance.     

Science and technology: A radiochemist's view

A historical perspective is presented from a radiochemist's point of view.     

Directional dispersion of extraordinary phonons in layer compound InSe

The resonant Raman scattering of polar optical phonons has been measured in trigonal γ-InSe at the E'₁ exciton edge. The two-phonon scattering spectrum widely spreads over the frequency range of 50 cm^-1 with an extremely asymmetric lineshape. This spectrum has been interpreted in terms of the directional dispersion of extraordinary LO and TO phonons.     

Field-ion microscopy of GaAs and GaP

Clean surfaces of GaAs and GaP were studied by field-ion microscope (FIM). Field-ion images with ordered surfaces were first obtained in pure hydrogen, neon-50% hydrogen and pure neon gases at 78 K, by using channeltron electron multiplier arrays (CEMA). The field-ion images of GaAs were quite similar to those of GaP with respect to the surface structure and the image contrast. They showed the anisotropies of the ion emission and the surface structure between the [111] and $\text{[}\text{1}\text{1}\text{1}\text{]}$ orientations. Ring steps expected from a spherical surface were observed on the (111) and {100} planes, but not on the $\text{[}\text{1}\text{1}\text{1}\text{]}$ and {110} planes. The regional brightness of the FIM patterns was discussed in terms of the Knor and Müller model and the atomic and electronic structures of the surface. The image field of these crystals was much lower than that of metals usually used in FIM. For example, the image field strength for the hydrogen and GaAs system was about 1.1 V/Å. The reduction of the field necessary to image was also discussed in terms of the field penetration effect.