Peptidehelicenes in solution and gel: chiral discrimination through interactions between two types of helixes

Helical [5]thiaheterohelicene 5HM, which rapidly interconverts between P and M enantiomers in solution, was connected to helical l-phenylalanine oligomers with an ester linkage to give peptidehelicenes (5Fn, where n: number of bonded phenylalanines). The characteristics of 5F4 and 5F5 with two types of helixes in a molecule were investigated, particularly in comparison with those of 5F1–5F3 with an incomplete coil of a peptide moiety. l-Phenylalanine peptide chains induced a shift in the equilibrium between the P and M helixes of 5HM toward the P side for all the 5Fns examined. The enantiomeric excess (ee) of the P form increased with a decrease in temperature, together with an elongation of the peptide chains. 5F4 and 5F5 in hot solutions of some solvents formed a gel at room temperature, whereas 5F1–5F3 showed no such behavior. In this gel, the stable helical form of the 5HM moiety in 5F4 and 5F5 was observed to be the M form in contrast to that in their solutions.     

Heavy-Ion-Induced Sucrose and L-α-Alanine Radicals Investigated by EPR

We investigated the details of sucrose and L-α-alanine radicals produced by heavy-ion irradiation with various linear energy transfer (LET) values. The impact of the heavy ions on samples produced stable free radicals, which were analyzed by electron paramagnetic resonance (EPR). The spectral patterns obtained were similar among those for the irradiation of carbon (C), neon (Ne), silicon (Si), and argon (Ar) ions. The radical production of irradiated sucrose and alanine samples showed a linear relation with the absorbed dose. The total spin concentration obtained by heavy-ion irradiation decreases as logarithmic function of the LET. Quantitative EPR analysis showed that the production of sucrose and alanine radicals depended on both the ion species and the LET values under the same dose. Moreover, the radical-production cross sections for sucrose and alanine irradiated with C ions (290 MeV/u) were about 1.3 · 10⁻⁸ and about 3.0 · 10⁻⁹ μm², respectively. The results of the cross section suggest that each molecule becomes a stable radical with the interaction of several particles. Authors' address: Kouichi Nakagawa, Radioisotope Research Center, Fukushima Medical University, 1 Hikari-gaoka, Fukushima 960-1295, Japan     

Radical and void formation in ultradrawn polyoxymethylene

In the production of ultrahigh-modulus (45–60 GPa) polyoxymethylene (POM) by microwave heating drawing, ultradrawing to draw ratios over 20 causes formation of numerous voids and radicals. The volume fraction of the internal voids is proportional to the drawing-induced radical concentration. On the basis of the idea that the rupture of taut tie-molecules (TTM) is responsible for void and radical formation, the relationship between the fraction of tiemolecules that are taut and the fraction that are ruptured is discussed by assuming both a Takayanagi structure model and the normal distribution of the tie-molecule lengths. The results indicate that longer tie-molecules are successively converted to TTM's followed by ruptures of shorter TTM's in the ultradrawing process; a small variance in the tie-molecule length distribution is effective for increasing TTM's without void formation. The maximum value of the volume fraction of taut tie-molecules for highly oriented POM tubes is estimated to be about 0.5.     

Degradation of hydroxymaleimide in 2-propanol by irradiation of energetic heavy ions (II)—N2-saturated system

Hydroxymaleimide was irradiated in N₂-saturated 2-propanol solutions by high-energy heavy ions over a wide range of LET values. The differential G-values of the degradation of hydroxymaleimide by irradiation with the heavier ions were lower than those of the lighter ions for the same LET value. An opposite result obtained in the air-saturated system. The degradation efficiency was 1.5 times higher, when the dose rate was 1/10 times lower. When irradiated at an LET value lower than 8 eV/nm, the G-values converged to a value less than that obtained by γ-irradiation.     

Robust and precise length stabilization of a 25-km long optical fiber using an optical interferometric method with a digital phase-frequency discriminator

We have developed an optical fiber length stabilization system for the distribution of reference millimeter wave signals in a long-baseline phased-array radio telescope. The fiber length was compared with an absolute wavelength reference laser using a Michelson interferometer. We used a digital servo system including a digital phase-frequency discriminator with a wide phase dynamic range and a digital signal processor (DSP) for the digital servo system. All-digital servo system made it possible to realize a robust and precise length stabilization of a 25-km long optical fiber. PACS 42.62.Eh; 42.81.Uv; 95.55.Jz     

Retardation of discoloration of poly(vinyl chloride) and decolorization of discolored poly(vinyl chloride) with diimide

Retardation of discoloration of poly(vinyl chloride) with diimide was studied in dimethylformamide at 130°C. with the use of p-toluenesulfonylhydrazide (PSH) as a source of diimide. A process was proposed that involved prolonging the induction periods of discoloration by inhibiting the development of conjugated polyene structure. The optimum proportion of PSH was one fourth of the poly(vinyl chloride), the best results. Furthermore, poly(vinyl chloride) discolored by thermal degradation in o-dichlorobenzene or gamma-ray irradiation under vacuum was decolorized in solution at 130°C. by addition of PSH. The decolorized poly(vinyl chloride) thus obtained was thermally stable compared with that obtained by oxidative methods.