Dynamics of a supercooled ionic liquid studied by optical and dielectric spectroscopy

We have measured the dynamics of solvation of a triplet state probe, quinoxaline, in the glass-forming ionic liquid dibutylammonium formate near its glass transition temperature Tg=153 K. The Stokes-shift correlation function displays a relaxation time dispersion of considerable magnitude and the optical line width changes systematically along the solvation coordinate. The solvent dynamics in the viscous regime is compared with the rotational behavior of the solute and with the dielectric relaxation of the ionic liquid. Among the different quantities derived from the dielectric experiments, the relaxation of the macroscopic electric field, i.e., the modulus Mt, matches best the solvent response Ct regarding time scale and stretching exponent. Many other properties are reminiscent of the behavior of polar molecular liquids which lack the ionic character.     

A photoelectrochemical device with a nanostructured SnO2 electrode modified with composite clusters of porphyrin-modified silica nanoparticle and fullerene

A silica nanoparticle has been successfully employed as a nanoscaffold to self-organize porphyrin and C60 molecules on a nanostructured SnO2 electrode. The quenching of the porphyrin excited singlet state on the silica nanoparticle is suppressed significantly, showing that silica nanoparticles are promising scaffolds for organizing photoactive molecules three-dimensionally in nanometer scale. Marked enhancement of the photocurrent generation was achieved in the present system compared with the reference system, where a gold core was employed as a scaffold of porphyrins instead of a silica nanoparticle. The rather small incident photon-to-current efficiency relative to a similar photoelectrochemical device using a silica microparticle may result from poor electron and hole mobility in the composite film due to poor connection between the composite clusters of a porphyrin-modified silica nanoparticle and C60 in micrometer scale.     

Porogen approach for the fabrication of plasma-polymerized nanoporous polysiloxane films

Nanoporous polysiloxane films were fabricated by plasma polymerization of hexamethyldisiloxane mixed with cyclohexane under different conditions. The pores were generated through the elimination of carbonaceous aggregates (porogen) by annealing at 600 degrees C. Results of spectroscopic ellipsometry, Fourier transform infrared spectroscopy, and positron annihilation lifetime spectroscopy suggest that not only film porosity but also average pore size depends on the amount of the decomposable porogen. The pore size was controllable in a range between 0.6 and 1.0 nm in radius by proper selection of the substrate temperature and precursor composition.     

High-resolution analysis of (Sc3C2)@ C80 metallofullerene by third generation synchrotron radiation X-ray powder diffraction

The X-ray structure of Sc(3)C(82) is redetermined by the MEM/Rietveld method by using synchrotron radiation powder data at SPring-8, where the C(2) encapsulated structure available to discuss the Sc-Sc interatomic distances has been determined. The encapsulated three scandium atoms form a triangle shape. A spherical charge distribution originating from the C(2) molecule is located at the center of the triangle. Interatomic distances between Sc and Sc are 3.61(3) A in the triangle. The distance between Sc and the center of the C(2) molecule is 2.07(1) A.     

Application of a pulsed slow-positron beam to polymers

Pulsed slow positrons were produced using a time-varying moderator bias with an interval of 82 ns; 97% of the positrons were compressed within 2 ns width at the target position. Both the positron annihilation lifetime and Doppler broadening of the positron annihilation radiation (DBPR) of polytetrafluoroethylene (PTFE) were measured as a function of the incident energy of slow positrons. It was shown that the lifetime and intensity of the long-lived component of positron annihilation are independent of the positron incident energy above 1.2 keV. However, the width of the Doppler-broadened annihilation γ-ray increased in the energy region below 1.2 keV.     

Imaging,Chemical and Spectroscopic Studies of the Methylation-induced Decomposition of Melanosomes†

The morphological and chemical changes associated with the exposure of melanosomes to methyl iodide are assessed by a variety of analytical, imaging and spectroscopic methods. Scanning electron microscopy, light scattering and N₂ adsorption measurements all indicate significant changes in the morphology of the pigment following methylation. Solid-state nuclear magnetic resonance (SS-NMR) spectroscopy and chemical degradation analysis reveals the methylation results in the introduction of ester groups into the pigment structures. Amino acid analysis further reveals that Arg, Cys, His, Ser and Tyr undergo methylation; the SS-NMR data provide additional evidence for the methylation of the sulfur of Cys. Methylation results in increased solubility of the melanosome; the absorption properties of the dissolved material are characterized by an absorption maximum at 225 nm, with a long tail throughout the UV-A and UV-B, indicating that the solubilized material is a combination of protein and pigment. The methylation-induced decomposition of the melanosomes provides new insights into both the observed increase in O-methyl derivatives of the indolic precursor to eumelanin in the urine of melanoma patients and how increased levels of biologic methylating agents in the brain induce symptoms that resemble Parkinson’s disease.     

Eicosapentaenoic acid release from the red alga Pachymeniopsis lanceolata by enzymatic degradation

Forty-eight species of seaweeds from Japanese waters were screened for the valuable polyunsaturated fatty acids eicosapentaenoic acid (EPA). The eight species that contained the highest levels of these compounds were analyzed in detail. Of all species tested the red alga Pachymeniopsis lanceolata contained the highest EPA concentration, and it was present as both the free and bound forms. EPA constituted 38.7% of total fatty acids, and polar lipids were the main constituent of the total lipids in P. lanceolata. EPA was obtained from the marine algae P. lanceolata by enzymatic hydrolysis of the total lipids extract using phospholipase A₂(PLA₂). The release of EPA reached a plateau after 10 min of enzymatic treatment. These results suggest that P. lanceolata is a useful natural source of EPA and that PLA₂ treatment is a convenient method for obtaining EPA from the red alga.