Cyclopolymerization of perfluoroisopropenyl vinylacetate

To develop the polymerization exploiting the interconversion of fluorinated carbon radical to hydrocarbon radical, the radical cyclopolymerization of perfluoroisopropenyl vinylacetate [CF₂?C(CF₃)OCOCH₂CH?CH₂] (FIA) was investigated to afford a polymer possessing mainly five‐membered ring structure with bimodal molecular weight distribution having 1 × 10⁵ as the higher molecular weight. This may be the first example wherein the cyclopolymerization between usual allyl group and fluorinated vinyl group is performed. The degree of cyclization was between 70 and 80% determined by ¹⁹F NMR of as‐polymerized products. The polymer preparation from perfluoroisopropenyl group, which shows scarce homopolymerization reactivity was accomplished. The mechanism that the addition of hydrocarbon radical to perfluoroisopropenyl group to produce fluorinated carbon radical followed by the intramolecular addition reaction onto allyl group to form five‐membered ring is proposed. The hydrolysis of the FIA polymer afforded a polymer possessing hydrophobic fluoroalkyl group with hydrophilic hydroxyl and carboxylic acid groups. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3220–3232, 2006     

Polycavernoside C and C2, the new analogs of the human lethal toxin polycavernoside A, from the red alga, Gracilaria edulis

Two new analogs of the human lethal toxin polycavernoside A, polycavernoside C and C2 (0.1-0.2 mg for each), were isolated from the red alga, Gracilaria edulis. The relative stereostructure of polycavernoside C and the absolute structure of polycavernoside C2 were determined by spectroscopic analysis and synthesis of the model of their aglycon.     

Visible fluorescence spectroscopy of single proteins at liquid-helium temperature

Fluorescence spectroscopy of single proteins at liquid-helium temperatures reveals a relation between structural dynamics and biological functions of the proteins. The technical difficulties in detecting visible fluorescence are chromatic aberration and optical background. They were overcome by a new optical design using reflective optics and employing two-photon excitation. The fluorescence spectrum of single green-fluorescent proteins taken at a temperature of 1.5 K makes a distinction between different metastable conformations that last for tens of seconds.     

Temporally controlled modulation of antihydrogen production and the temperature scaling of antiproton-positron recombination

We demonstrate temporally controlled modulation of cold antihydrogen production by periodic RF heating of a positron plasma during antiproton-positron mixing in a Penning trap. Our observations have established a pulsed source of atomic antimatter, with a rise time of about 1 s, and a pulse length ranging from 3 to 100 s. Time-sensitive antihydrogen detection and positron plasma diagnostics, both capabilities of the ATHENA apparatus, allowed detailed studies of the pulsing behavior, which in turn gave information on the dependence of the antihydrogen production process on the positron temperature T. Our data are consistent with power law scaling T (-1.1+/-0.5) for the production rate in the high temperature regime from approximately 100 meV up to 1.5 eV. This is not in accord with the behavior accepted for conventional three-body recombination.     

Preparation of a novel bromine complex and its application in organic synthesis

Although molecular bromine (Br₂) is a useful brominating reagent, it is not easy to handle. Herein, we describe the preparation of a novel air-stable bromine complex prepared from 1,3-dimethyl-2-imidazolidinone (DMI) and Br₂, which was identified to be (DMI)₂HBr₃ by spectral and X-ray techniques. This complex was then used to brominate olefins, carbonyl compounds, and aromatics, as well as in the Hofmann rearrangement. Yields of reaction products using this complex were almost the same or superior to those using other bromine alternatives.     

ANALYSIS ON PSEUDO-STEADY INDENTATION CREEP

Theoretical analysis and finite element （FE） simulation have been carried out for a constant specific load rate （CSLR） indentation creep test. Analytical results indicate that both the representative stress and the indentation strain rate become constant after a transient period. Moreover, the FE simulation reveals that both the contours of equivalent stress and equivalent plastic strain rate underneath the indenter evolve with geometrical self-similarity. This suggests that pseudo-steady indentation creep occurs in the region beneath the indenter. The representative points in the region are defined as the ones with the equivalent stress equal to the representative stress. In addition, it is revealed that the proportionality between indentation strain rate and equivalent plastic strain rate holds at the representative points during the pseudo-steady indentation creep of a power law material. A control volume （CV） beneath the indenter, which governs the indenter velocity, is identified. The size of the CV at the indented surface is approximately 2.5 times the size of the impression. The stress exponent for creep can be obtained from the pseudosteady indentation creep data. These results demonstrate that the CSLR testing technique can be used to evaluate creep parameters with the same accuracy as conventional uniaxial creep tests.