Stimuli‐responsive reversible physical networks. I. Synthesis and physical network properties of amphiphilic block and random copolymers with long alkyl chains by living cationic polymerization

The living cationic polymerization of octadecyl vinyl ether (ODVE) was achieved with an 1‐(isobutoxy)ethyl acetate [CH₃CH(OiBu)OCOCH₃]/EtAlCl₂ initiating system in hexane in the presence of an added weak Lewis base at 30 °C. In contrast to conventional polymers, poly(octadecyl vinyl ether) underwent upper‐critical‐solution‐temperature‐type phase separation in various solvents, such as hexane, toluene, CH₂Cl₂, and tetrahydrofuran, because of the crystallization of octadecyl chains. Amphiphilic block and random copolymers with crystallizable substituents of ODVE and 2‐methoxyethyl vinyl ether (MOVE) were synthesized via living cationic polymerization under similar conditions. Aqueous solutions of the copolymers yielded physical gels upon cooling because of strong interactions between ODVE units, regardless of the copolymer structure. The product gels, however, exhibited different viscoelastic properties: A 20 wt % solution of a block copolymer (400/20 MOVE/ODVE) became a soft physical gel that behaved like a typical gel, whereas the corresponding random copolymer gave a transparent but stiff gel with a certain relaxation time. Differential scanning calorimetry analysis confirmed that the crystalline–amorphous transition of the octadecyl chains was a key step for inducing such physical gelation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1155–1165, 2005     

Molecular structure of (-)-3-acetyl-6 beta-(acetylthio)-N-(cyclopropyl-methyl) normorphine and its 14-hydroxy congeners

The stereochemistry of the title compound 3 was confirmed by X-ray analysis. The 6-acetylthio derivatives with an OH group at C-14 were also designed and synthesized.     

Nutritional improvement of soybean oil via lipase-catalyzed interesterification

In order to decrease the content of linoleoyl moiety in soybean oil, soybean oil that contains 22.8% oleoyl, 54.8% linoleoyl, and 7.1% α-linolenoyl moieties as molar acyl moiety composition was interesterified in hexane with oleic acid or α-linolenic acid, using an immobilized sn-l,3-specific lipase (Lipozyme® IM) fromMucor miehei. The reactions were carried out in a batch reactor at 37°C in the following system: molar ratio of fatty acid to soybean oil = 1.0 ～ 6.0, 5.0 mL of hexane/500 μmol soybean oil, and 10.0 or 15.0 batch interesterification units of enzyme/500 μmol soybean oil. Under these reaction conditions, the rates of interesterification of acyl moieties in soybean oil were of the order: stearoyl > palmitoyl > linoleoyl > oleoyl > α-linolenoyl, and the reaction with oleic acid occurred without a significant loss of α-linolenoyl moiety. At the molar ratio of 3.0 and the reaction time of 6 h, triacylglycerols (TGs), which contain 50.8% oleoyl, 38.8% linoleoyl, and 5.4% α-linolenoyl moieties, were produced in the reaction with oleic acid; TGs that contain 13.5% oleoyl, 40.8% linoleoyl, and 40.4% α-linolenoyl moieties were obtained with α-linolenic acid. Approximately 86-88% of the interesterification of linoleoyl moiety, which occurred in 10 h, took place within 1 h.     

Stability of human insulin in solutions containing sodium bisulfite.

The stabilities of human insulin (HI) in aqueous solutions were investigated in the pH range of 4.0-7.0 in the presence (1.0-3.0 x 10(-3) M) and absence of sodium bisulfite (SBS) both in the dark and under scattered light (1000 lux) using high performance liquid chromatography. Increasing concentrations of SBS tended to degrade HI. In the presence of SBS, with an increase in the pH value, the stability of HI decreased in the pH range of 4.0-7.0. There was a partial difference in the stability of HI in the presence of SBS in the dark and that under scattered light. HI was stabilized by glucose in the presence of SBS in the dark, and the stability of HI was revealed to depend on the concentration of free SBS. The reason for this phenomenon was postulated to be the formation of bisulfite-glucose adduct.     

Doubly-dendronized linear polymers

Doubly-dendronized polymers were synthesized by grafting polybenzyl ether dendrons onto a poly(hydroxy) styrene polymer with polyaliphatic esters.     

The novel and efficient direct synthesis of N,O-acetal compounds using a hypervalent iodine(III) reagent: an improved synthetic method for a key intermediate of discorhabdins

The use of hypervalent iodine(III) reagents allowed us to develop the novel and efficient direct synthesis of N,O-acetal compounds via the oxidative fragmentation reaction of alpha-amino acids or alpha-amino alcohols; furthermore, we succeeded in developing an improved synthesis of the key intermediate of discorhabdins.     

Electron acceleration in an ultraintense-laser-illuminated capillary

An ultraintense laser injected a 10 J of power at 1.053 microm in 0.5 ps into a glass capillary of 1 cm long and 60 microm in diameter and accelerated plasma electrons to 100 MeV. One- and two-dimensional particle codes describe wakefields with 10 GV/m gradient excited behind the laser pulse, which are guided by a plasma density channel far beyond the Rayleigh range. The blueshift of the laser spectrum supports that a plasma of 10(16) cm(-3) is inside the capillary. A bump at the high energy tail suggests the electron trapping in the wakefield.     

Application of PSP to low density gas flows

Recently optical pressure measurement systems using pressure sensitive paints (PSP) have actively developed to measure continuous pressure distributions on solid surfaces. However, the pressure range has been almost limited above 130 Pa (about 1 Torr) and there is no application to lower pressure range because the pressure sensitivity seems to be not so high in that range. In this study, we have applied three types of PSP [two types are composed by organic dye and polymer (luminophore/binder); PtOEP/GP197 and PtTFPP/poly(TMSP), and another one is Bath-Ru adsorbed on anodized aluminum] to the rarefied gas flow mainly lower than 130 Pa and examine those fundamental properties such as pressure sensitivity, leading to selection of the most suitable PSP among them for the low-pressure range. Since PtTFPP/poly(TMSP) has the highest sensitivity, it is applied successfully to the measurement of the two-dimensional pressure distribution on the surface interacting with a low density supersonic free jet.     

Metallic behavior of lightly doped La2-xSrxCuO4 with a Fermi surface forming an arc

Lightly doped La2-xSrxCuO4 in the so-called "insulating" spin-glass phase has been studied by angle-resolved photoemission spectroscopy. We have observed that a "quasiparticle" (QP) peak crosses the Fermi level in the node direction of the d-wave superconducting gap, forming an "arc" of Fermi surface, which explains the metallic behavior at high temperatures of the lightly doped materials. The QP spectral weight of the arc smoothly increases with hole doping, which we attribute to the n approximately x behavior of the carrier number in the underdoped and lightly doped regions.     

Search for supernova relic neutrinos at Super-Kamiokande

A search for the relic neutrinos from all past core-collapse supernovae was conducted using 1496 days of data from the Super-Kamiokande detector. This analysis looked for electron-type antineutrinos that had produced a positron with an energy greater than 18 MeV. In the absence of a signal, 90% C.L. upper limits on the total flux were set for several theoretical models; these limits ranged from 20 to 130 macro nu(e) cm(-2) s(-1). Additionally, an upper bound of 1.2 macro nu(e) cm(-2) s(-1) was set for the supernova relic neutrino flux in the energy region E(nu)>19.3 MeV.