In vivo temporal EPR imaging for estimating the kinetics of a nitroxide radical in the renal parenchyma and pelvis in rats

The kinetics of a nitroxide radical in the renal parenchyma and pelvis in rats were investigated by employing an in vivo EPR imaging system equipped with a surface-coil-type resonator (SCR). The exposed kidney of a living rat was inserted into the single-turn coil of the SCR, with the renal major axis aligned with the direction of alternative magnetic field (B(1)). After the injection of nitroxide radical via the tail vein, EPR measurements were repeated. From the temporal EPR images of the kidney on the 2-D projection to the plane which is perpendicular to the direction of B(1,) the decay rate of nitroxide radical in the renal parenchyma and pelvis was estimated. The parenchymal decay rate was found to be significantly shorter than that for the pelvis.     

Asymptotic analysis for the eikonal equation with the dynamical boundary conditions

We study the dynamical boundary value problem for Hamilton‐Jacobi equations of the eikonal type with a small parameter. We establish two results concerning the asymptotic behavior of solutions of the Hamilton‐Jacobi equations: one concerns with the convergence of solutions as the parameter goes to zero and the other with the large‐time asymptotics of solutions of the limit equation.     

Cellulose Peroxides with Structures of Peracid and α-Hydroxyhydroperoxide Types

Cellulose peroxides derived from various cellulose derivatives with hydrogen peroxide were investigated. Fibrous carboxy-methyl cellulose, periodic acid-oxidized cellulose, and methyl vinyl ketone-treated cellulose were employed as cellulose derivatives. Carboxyl and carbonyl groups in the cellulose derivatives were believed to react with hydrogen peroxide to form peroxides with structures of peracid and α-hydroxyhydroperoxide types, respectively. The decomposition of the cellulose peroxides and their abilities to initiate grafting reaction were examined.     

Thermal Degradation Behavior of Vinyl Ketone Polymers and Copolymers with Styrene

Thermal degradation behavior of six alkyl vinyl ketone (RVK) polymers and copolymers with styrene was investigated by means of infrared spectrometry (IR), thermogravimetry (TG), derivative TG (DTG), and differential scanning calorimetry (DSC). The observed TG curves of the RVK polymers changed with both structure of their substituents and initiators used, and the temperature of the beginning of weight loss for the radical polymers increased in the order: poly(methyl isopro-penyl ketone) < poly(methyl vinyl ketone) < poly(ethyl vinyl ketone) < poly(isopropyl vinyl ketone) < poly(tert-butyl vinyl ketone). From the infrared spectral determination of thermally degraded polymers, the formation of a cyclized structure was observed. It was also found from the results of thermal degradation of the RVK copolymers with styrene at 210° C that the formation of such a cyclized unit tended to increase in the order: tert-butyl vinyl ketone < isopropyl vinyl ketone < ethyl vinyl ketone < methyl vinyl ketone.     

Some Factors Affecting the Photosensitized Polymerization of Methyl Methacrylate

The effects of sensitizer, alcohol, and reaction temperature on the photosensitized polymerization of methyl methacrylate in cyclohexane-alcohol mixtures were investigated. A maximum conversion was indicated at a certain concentration of alcohol in the mixture for the systems sensitized with quinones such as anthraquinone, 2-tert-butylanthraquinone, and α-naphthoquinone, while it was not observed for the benzophenone-sensitized system. The concentration of alcohol corresponding to the maximum conversion increased in the order methanol < ethanol < n-propanol < n-butanol, and shifted to the lower side by raising the reaction temperature from 20 to 40°C. Based on the absorption and ESR spectra of irradiated solution of quinones, reasons for maximum conversion at an optimum concentration of alcohol are discussed.     

Temperature-dependent spectral changes of self-aggregates of zinc chlorophylls esterified by different linear alcohols at the 17-propionate

Systematically synthetic zinc 3-hydroxymethyl-13¹-oxo-chlorins esterified by different linear alcohols (methanol, 1-propanol, 1-hexanol, 1-dodecanol and 1-octadecanol) at the 17-propionate were self-assembled in the presence of cetyltrimethylammonium bromide in an aqueous solution. These zinc chlorins exhibited red-shifted Q _y absorption bands and circular dichroism (CD) signals in the corresponding Q _y region after incubation for 17 h, indicating that the zinc chlorins formed self-aggregates like those in natural chlorosomes of green photosynthetic bacteria. Visible absorption and CD spectra of self-aggregates of the zinc chlorins depended on the length of their esterifying alcohols. Zinc chlorins esterified by shorter alcohols gave larger changes in their visible absorption and CD spectra after incubation above 40°C, whereas zinc chlorins esterified by longer alcohols afforded smaller changes. These results indicate that hydrophobic interaction among esterifying chains of chlorin molecules as well as that between the esterifying chains and peripheral surfactants or lipids play an important role in the stability of chlorosomal self-aggregates.     

Self-assembly of zinc chlorophyll derivatives possessing a pyrenyl group at the 17-propionate residue and effects of additional γ-cyclodextrins on their optical properties

Two kinds of zinc 3¹-hydroxy-13¹-oxo-chlorins 1 and 2 possessing a pyrenyl group at the 17-propionate residue, of which the linker length between the chlorin and the pyrene moieties was varied, were synthesised from naturally occurring chlorophyll a, and were self-assembled in an aqueous solution. Both zinc chlorins 1 and 2 exhibited Q_y absorption bands around 720 nm accompanying circular dichroism signals in the Q_y region, indicating that these zinc chlorins could form self-aggregates like chlorosomes of green photosynthetic bacteria. Addition of γ-cyclodextrin into an aqueous solution containing the self-aggregates of zinc chlorin 1 esterified with 1-pyrenylmethanol induced the appearance of excimer emission of the pyrene moieties around 480 nm as well as increased the fluorescence intensities of the pyrene monomers at 378 and 396 nm, while only an increase in fluorescence from the monomeric pyrene moiety was observed in the case of 2 esterified with 4-(1-pyrenyl)butanol. Exogenous γ-cyclodextrin unchanged the spectral features derived from the chlorin moieties of 1 and 2 in the aqueous phase. These suggest that the encapsulation of the pyrenyl groups in the zinc chlorins unchanged their assembling states under the present conditions.