Extra coupling with sodium of an amino radical adsorbed on the zeolite

ESR spectra were observed from amino radicals adsorbed on the pre-heat-treated zeolite sorbing ammonia molecules. The extra coupling with the sodium ²³Na in the zeolite was observed in the spectrum from the amino-radicals.     

The radical cation of hexafluoro-1,3-butadiene: An ESR study

Two distinct radical cations have been observed by ESR in a γ-irradiated solid solution of hexafluoro-1,3-butadiene in freon. INDO calculations of ES     

Observation of electrostatically released DNA from gold electrodes with controlled threshold voltages

DNA oligo-nucleotides, localized at Au metal electrodes in aqueous solution, are found to be released when applying a negative bias voltage to the electrode. The release was confirmed by monitoring the intensity of the fluorescence of cyanine dyes (Cy3) linked to the 5' end of the DNA. The threshold voltage of the release changes depending on the kind of linker added to the DNA 3'-terminal. The amount of released DNA depends on the duration of the voltage pulse. Using this technique, we can retain DNA at Au electrodes or Au needles, and release the desired amount of DNA at a precise location in a target. The results suggest that DNA injection into living cells is possible with this method.     

Novel hydrogen peroxide sensors based on peroxidase-carrying poly[pyrrole-co-[4-(3-pyrrolyl)butanesulfonate]] copolymer films.

Amperometric hydrogen peroxide biosensors were fabricated by incorporating horseradish peroxidase (HRP) into poly[pyrrole-co-[4-(3-pyrrolyl)butanesulfonate]] (Py-PS) copolymer films deposited on an SnO2 electrode surface by electropolymerization. The HRP/Py-PS electrodes exhibited an extended dynamic range and a markedly improved operational and storage stability, compared with HRP-incorporated polypyrrole (PPy) electrodes prepared under similar conditions. The linear range was expanded from 10(-7)-10(-4) M to 10(-7)-10(-3) M H2O2. In about 80 measurements over three weeks, the HRP/Py-PS electrode retained 60% of its initial response, while the HRP/PPy electrode almost completely lost activity. The influence of the electrodeposition solution pH on the sensor response was also investigated. Our results suggest that an expansion of the linear range and an enhancement of lifetime are due to electrostatic interactions of HRP with a negatively-charged Py-PS copolymer.     

Furopyridines. XXXI. Birch reduction of furopyridines

Birch reduction of four furopyridines 1a‐d effected the characteristic cleavage of the furan ring, giving ethnylpyridinols 2a‐d , vinylpyridinols 3b,d , and ethylpyridinols 4a‐d , and the reduction of the furan ring, giving dihydrofuropyridine 5c,d.     

Transformation of peptide nanotubes into a vesicle via fusion driven by stereo-complex formation

Two types of peptide nanotubes, one is prepared from an amphiphilic peptide having a right-handed helix segment and the other from that having a left-handed helix segment, are shown to transform the morphology into a vesicle by membrane fusion due to stereo-complex formation between these helical segments.     

A study of the dynamic equilibrium between symmetrical and distorted 1,2,3-trimethylcyclohexane radical cations

Radical cations of the 1,2,3-trimethylcyclohexane isomers stabilized in various γ-irradiated solute/halocarbon matrices have been investigated by means of ESR in the temperature range 4–77K. At 4 K the ESR spectra are dominated by contributions from an asymmetrically distorted structure with the unpaired electron localized to the C1-C2 bond. On increasing the temperature a reversible change occurs in the ESR line-shape of the cations of the two symmetrical isomers. Using a two-site jump model to reproduce the temperature dependent line-shape, the phenomenon is explained in terms of an interconversion between two such distorted structures, each being the mirror image of the other. The Arrhenius plot associated with the process is markedly nonlinear towards the low temperature region. The experimental data are also modelled by postulating that another (different) electronic ground state, having higher symmetry, becomes populated with the increase of temperature. In this way, the spectral changes can be simulated using a three-site jump model which couple the thermally activated two-site jump process (E _a ca. 0.137 kcal/mol) with a dynamical equilibrium between the asymmetrical ground state and a symmetrical structure 0.058 kcal/mol higher in energy. The energy barrier to pass from the distorted to the symmetrical structure was evaluated to be 0.085 kcal/mol.     

Synthesis of glycosaminoglycans via enzymatic polymerization

Hyaluronic acid and chondroitin were successfully synthesized as representative molecules of glucosaminoglycans and galactosaminoglycans found in a glycosaminoglycan family via enzymatic polymerization catalyzed by testicular hyaluronidases. A newly designed N-acetylhyalobiuronate oxazoline derivative with a β-D -glucuronyl-(1→3)-N-acetyl-D -glucosamine disaccharide structure served as a transition-state analogue substrate monomer for the enzyme, giving rise to artificial hyaluronic acid in 52% yields with a number-average molecular weight of 1.35 × 10⁴ through ring-opening polyaddition in a perfect regioselective and stereoselective manner. A novel N-acetylchondrosine oxazoline derivative with a β-D -glucuronyl-(1→3)-N-acetyl-D -galactosamine disaccharide structure also acted as a transition-state analogue substrate monomer for the enzyme, yielding artificial chondroitin in 35% yields with a number-average molecular weight of 2.5 × 10³. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3541–3548, 2003     

The crystal structure of Mg51Zn20

The crystal structure of Mg₅₁Zn₂₀, a phase designated conventionally as “Mg₇Zn₃,” has been determined by the single-crystal X-ray diffraction method. It was solved by the examination of a Patterson synthesis, and refined by the ordinary Fourier and least-squares method; the R value obtained was 4.8% for 1167 observed reflections. The crystal is orthorhombic, space group Immm, with a = 14.083(3), b = 14.486(3), c = 14.025(3) Å, and Z = 2. There are 18 independent atomic sites, Zn1Zn6, Mg1Mg10, A, and B, and the last two sites are statistically occupied by Zn and Mg atoms with the occupancies; 0.46(2)Zn7 + 0.52(2)Mg11 and 0.24(2)Zn8 + 0.74(2)Mg12, for A and B, respectively. The structure of the crystal is described as an arrangement of icosahedral coordination polyhedra, to which all the atomic sites but Zn3 site belong. In this arrangement the Zn atoms other than the Zn3 and Zn8(B) center the icosahedral coordination polyhedra with coordination number 12. The Zn3, Zn8 atoms, and all the Mg atoms except Mg11(A) are located at the centers of various coordination polyhedra with the coordination numbers from 11 to 15. The distances between neighboring atoms are 2.71–3.07, 2.82–3.65, and 2.60–3.20 Å for ZnZn, MgMg, and ZnMg, respectively.