Reactivity of singlet oxygen generated by the photosensitization of tetraphenylporphyrin in liposomes

A hydrophobic porphyrin derivative, tetraphenylporphyrin (TPP), was used as a sensitizer, and an anionic dye, methyl orange (MO), was employed as a substrate of photooxidation. TPP was incorporated into the hydrophobic environment of phosphatidylcholine (PC) bilayer membranes, liposomes. When oxygen was purged out of the liposome suspension by nitrogen bubbling, the degradation of MO was completely inhibited. A specific superoxide scavenger, superoxide dismutase, had no effect on the MO degradation. The replacement of H₂O by D₂O resulted in a 10 times enhancement in the photodegradation of MO. These results suggested that singlet oxygen was generated by the TPP photosensitization and worked as the mediator of the photoreaction from TPP. Trisulphonated TPP,-phenyl-,, -tri(p-sulphonyl)porphyrin (TPPS), is soluble in aqueous solution. The light irradiation to an aqueous solution of TPPS gave rise to the rapid bleaching (decomposition) of the sensitizer itself. On the other hand, TPP in the hydrophobic environment of liposomes was stable during light irradiation and worked as a sensitizer for the continuous photoreaction. Maximum reactivity was observed at the PC/TPP mole ratio of 50. When TPP molecules were incorporated into liposomes at larger concentrations (PC/TPP<50), a part of the excitation energy of the sensitizer molecules was nonradiatively converted into the lattice energy by the resonance between the closely located TPP molecules. This led to lower efficiency for the photoactivation of oxygen. On the other hand, the increase in liposome concentration resulted in the enhancement of the MO binding to lipid membranes and the retardation of MO degradation. Also, the electrostatic attraction and repulsion between the membrane and the substrate influenced the reaction rate greatly. The oxidative degradations of the substrate by singlet oxygen were considered to be much faster in the polar environment than in the less polar environment. The charge transfer or the polarized transition complex of singulet oxygen and MO are presumed to be stabilized in the polar environment. The distribution of substrate between the less polar membrane surface and the polar bulk aqueous solution was another important factor in the photooxidation.     

An in situ study of plasticization of polymers by high-pressure gases

A high-pressure differential scanning calorimetric technique is described for studying polymer plasticization by compressed gases at pressures to 100 atm. The in situ measurements avoid problems due to gas desorption encountered with conventional DSCs, thus providing an accurate way to determine the change in glass transition temperature, T_g, with pressure, p. The entire T_g–p curve can be established in less than 2 days. The glass transition was observed as a sharp step in the case of 100–200-μm thin samples, whereas thicker samples gave a broad transition; highly reproducible results were obtained for the thin samples. For PS–CO₂, the measured T_gs under various pressures were found to be in good agreement with literature values. Results for the systems PS–HFC134a, PVC–CO₂, and PC–CO₂ are also reported. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 977–982, 1998     

High-precision gravimetric technique for determining the solubility and diffusivity of gases in polymers

An in situ gravimetric technique, employing an electrobalance, is described for determining the solubility and diffusivity of gases in polymers over extended ranges of temperature and pressure. Solubilities of CO₂ in polystyrene at 35°C were measured as a test case; the results are in excellent agreement with the literature values determined by the pressure decay method. Solubility and diffusivity results are also reported for PVC-CO₂ at 35°C and for PS-1,1,1,2-tetrafluoroethane at 30, 90, and 120°C. A comparison with other studies shows the in situ method to be more efficient and precise than the ones based on weighing the gas-saturated polymer under ambient conditions. The kinetics of gas sorption were analyzed in terms of two data reduction techniques to derive diffusion coefficients. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2025–2032, 1998     

Preparations and reactions of 2-trifluoromethylketenimines

Preparations and reactions of a series of 2-trifluoromethylketenimines are described. Trifluoromethylketenimines were prepared from trifluoropropanoic acids via corresponding imidoyl chlorides in good yields. 2-Trifluoromethylketenimine was functionalized at its β-position by electrophilic addition of halide, followed by dehydrohalogenation. Addition of nucleophile at α-position gave trifluoroethylated β-amino acid derivative via 1,3-proton shift.     

Biodegradation of bisphenol a by fungi

The biologic degradation of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A [BPA]; 1) was studied with 26 fungi. An initial BPA concentration of 40 ppm in an aqueous solution was degraded in the dark for 14 d. Among the 26 strains tested, 11 degraded BPA at 50% or more. Furthermore, four strains (F. sporotrichioides NFRI-1012, F. moniliforme 2-2, A. terreus MT-13, and E. nidulans MT-98) were more effective for degradation of BPA.     

Observation of B-/+-->rho-/+rho0 decays

We report the first observation of the charmless vector-vector decay process B-/+-->rho(-/+)rho(0). The measurement uses a 78 fb(-1) data sample collected with the Belle detector at the KEKB asymmetric e(+)e(-) collider operating at the Upsilon(4S) resonance. We obtain a branching fraction of B(B-/+-->rho(-/+)rho(0))=[31.7+/-7.1(stat)+3.8-6.7(syst)]x10(-6). An analysis of the rho helicity-angle distributions gives a longitudinal polarization fraction of Gamma(L)/Gamma=0.95+/-0.11(stat)+/-0.02(syst). We also measure the direct-CP-violating asymmetry A(CP)(B-/+-->rho(-/+)rho(0))=0.00+/-0.22(stat)+/-0.03(syst).     

On Aluthge Transforms of p-hyponormal Operators

In this note we give an example of an ∞-hyponormal operator T whose Aluthge transform is not (1+ɛ)-hyponormal for any ɛ > 0 and show that the sequence of interated Aluthge transforms of T need not converge in the weak operator topology, which solve two problems in [6].     

Partial molar volumes of gases dissolved in liquids. Part II. A dilatometer for measuring infinite-dilution partial molar volumes,and results for 40 liquid-gas systems

A dilatometer with an imprecision of less than 0.4% is described for the determination of partial molar volumes of gases dissolved in liquids. Measurements at 298.15 K are reported for 40 liquid-gas systems having n-alkanes and 1-alkanols as the liquid component. The results are interpreted in terms of a number of empirical and semiempirical correlations.     

Myocardial imaging with thallium-201--subtraction imaging with 201TlCl and 99mTcO4- for the visualization of the right ventricle--(author's transl)

The dual radioisotope techniques with 201TlCl and 99mTcO4- were performed in 30 cases inclusive of various heart and lung diseases, using a scintillation camera coupling to a small digital computer. The scintigraphic procedures were started about 5 minutes after intravenous injection of 201TlCl. The myocardial images such as anterior, 60 degrees left anterior oblique, and left lateral view, were obtained. Next, 30 degrees left anterior oblique view was taken and radionuclide angiogram with 99mTcO4- was done in the same position too. This joint use of the myocardial imaging and radionuclide angiography could increase diagnostic reliability. Superimposing the image as iso-count map extracted out of radionuclide angiogram to the brightness image of 201TlCl, the anatomic orientation of the image of 201TlCl was improved. Subtracting the blood pool image with 99mTcO4- or radionuclide angiogram, which showed visualization of the right ventricle, lungs and left ventricle, from the image of 201TlCl, the subtraction image was obtained. The right ventricle was visualized more clearly on this subtraction image than the original image of 201TlCl. Good visualization of the right ventricle was shown in 25 cases on the subtraction image, and in 17 cases on the original image of 201TlCl.