Thermal oxidative degradation of additive-free polypropylene pellets investigated by multichannel Fourier-transform chemiluminescence spectroscopy

Thermal oxidative degradation of additive-free polypropylene pellets heated isothermally in dry air at 150 and 180 °C (below and above the melting point of 163 °C) was investigated by multichannel Fourier-transform chemiluminescence spectroscopy. The initial peak wavelength of chemiluminescence emission at 490 nm remained constant during the early stages of thermal degradation, but new emissions developed with time in the red spectral region over an extended oxidation period. The time-dependent luminescence spectra were deconvoluted into three emission bands by least-squares fitting using Gaussian curves. We concluded that at least three groups of luminescent species (luminophores), having different conjugation lengths, were generated by thermal oxidation over extended periods and show luminescence around 490, 660, and 740 nm.     

Visualizing Hepatic Copper Release in Long–Evans Cinnamon Rats Using Single-Photon Emission Computed Tomography

The potential utility of an imaging agent for the detection of hepatic copper was investigated in a Wilson’s disease animal model. Solid-phase peptide synthesis was used to construct an imaging agent which consisted of a copper-binding moiety, taken from the prion protein, and a gamma ray-emitting indium radiolabel. Long–Evans Cinnamon (LEC) rats were used for the Wilson’s disease animal model. Our evaluation methodology consisted of administering the indium-labeled agent to both LEC and genetically healthy Long–Evans (LE) cohorts via a tail vein injection and following the pharmacokinetics with single-photon emission computed tomography (SPECT) over the course of an hour. The animals were then sacrificed and their livers necropsied. An additional control agent, lacking the copper-binding moiety, was used to gauge whether any change in the hepatic uptake might be caused by other physiological differences between the two animal models. LEC rats injected with the indium-labeled agent had roughly double the amount of hepatic radioactivity as compared to the healthy control animals. The control agent, without the copper-binding moiety, displayed a hepatic signal similar to that of the control LE animals. Additional intraperitoneal spiking with CuSO₄ in C57BL/6 mice also found that the pharmacokinetics of the indium-labeled, prion-based imaging agent is profoundly altered by exposure to in vivo pools of extracellular copper. The described SPECT application with this compound represented a significant improvement over a previous MRI application using the same base peptide sequence.     

Synthesis and Characterization of Aminoporphyrin‐End‐Functionalized Poly(N‐isopropylacrylamide) with Photodynamic and Thermoresponsive Effects

The novel aminoporphyrin‐end‐functionalized poly(N‐isopropylacrylamide) (PNIPAM) polymer H₂N‐TPP‐PNIPAM (TPP=5,10,15,20‐tetraphenyl‐21H,23H‐porphyrin) behaves as a multifunctional platform that displays a photodynamic effect, thermosensitivity, and fluorescence properties. The polymer was designed by using an asymmetrical aminoporphyrin (i.e., H₂N‐TPP‐Cl) as the initiator for the atom‐transfer radical polymerization of N‐isopropylacrylamide (NIPAM). The polydispersity index (PDI) obtained by gel‐permeation chromatography indicated that the molecular‐weight distribution was narrow (1.09<PDI<1.27). The lower critical solution temperatures of H₂N‐TPP‐PNIPAM showed a decreasing trend as the molecular weight was increased as a result of the incorporation of the porphyrin group at the end of the chain. The fluorescence spectra revealed the luminescent properties of the materials. The results of confocal laser scanning microscopy showed that the polymer could enter the cytoplasm through endocytosis. In addition, the multifunctional platform exhibited low toxicity against normal cells (L929) and cancer cells (Hela) and enhanced photodynamic activity towards HeLa cells, without significant necrocytosis towards L929 cells; as a result this material may be useful in the future for practical photodynamic therapy.     

Phase structure of a U(1) lattice gauge theory with dual gauge fields

We introduce a U(1) lattice gauge theory with dual gauge fields and study its phase structure. This system is partly motivated by unconventional superconductors like extended s-wave and d  -wave superconductors in the strongly-correlated electron systems and also studies of the t–J$t\text{–}J$ model in the slave-particle representation. In this theory, the “Cooper-pair” (or RVB spinon-pair) field is put on links of a cubic lattice due to strong on-site repulsion between original electrons in contrast to the ordinary s  -wave pair field on sites. This pair field behaves as a gauge field dual to the U(1) gauge field coupled with the hopping of electrons or quasi-particles of the t–J$t\text{–}J$ model, holons and spinons. By Monte Carlo simulations we study this lattice gauge model and find a first-order phase transition from the normal state to the Higgs (superconducting) phase. Each gauge field works as a Higgs field for the other gauge field. This mechanism requires no scalar fields in contrast to the ordinary Higgs mechanism. An explicit microscopic model is introduced, the low-energy effective theory of which is viewed as a special case of the present model.     

Control of diameter of ZnO nanorods grown by chemical vapor deposition with laser ablation of ZnO

We made a study of controlling diameters of well-aligned ZnO nanorods grown by low-pressure thermal chemical vapor deposition combined with laser ablation of a sintered ZnO target, which was developed by us. Until now, it has been impossible to control diameters of ZnO nanorods, while the growth orientation was maintained well-aligned. In this study we developed a multi-step growth method to fabricate well-aligned nanorods whose diameters could be controlled. Metal Zn vapor and O₂ are used as precursors to grow ZnO nanorods. N₂ is used as a carrier gas for the precursors. A substrate is an n-Si (111) wafer. A sintered ZnO target is placed near the substrate and ablated by a Nd–YAG pulsed laser during ZnO nanorod growth. The growth temperature is 530 C and the pressure is 66.5 Pa. A vertical growth orientation of ZnO nanorods to the substrate is realized in the first-step growth although the diameter cannot be controlled in this step. When an O₂ flow rate is 1.5 sccm, well-aligned nanorods with 100 nm diameter are grown. Next, the second-step nanorods are grown on only the flat tip of the first-step nanorods. The diameters of the second-step nanorods can be controlled by adjusting the O₂ flow rate, and the growth direction is kept the same as that of the first-step nanorods. When the O₂ flow rate in second-step growth is smaller than 0.6 sccm, the diameter of the second-step nanorods is 30–50 nm. When the O₂ flow rate is between 0.75 and 3.0 sccm, the diameter is almost same as that of the first-step nanorods. When the O₂ flow rate is larger than 4.5 sccm, the diameter is increased with increasing O₂ flow rate. Further, the third-step ZnO nanorods with gradually increased diameters can be grown on the second-step nanorods with 1.5 sccm O₂ flow rate and without laser ablation.     

One-dimensional migration of interstitial clusters in SUS316L and its model alloys at elevated temperatures

For self-interstitial atom (SIA) clusters in various concentrated alloys, one-dimensional (1D) migration is induced by electron irradiation around 300 K. But at elevated temperatures, the 1D migration frequency decreases to less than one-tenth of that around 300 K in iron-based bcc alloys. In this study, we examined mechanisms of 1D migration at elevated temperatures using in situ observation of SUS316L and its model alloys with high-voltage electron microscopy. First, for elevated temperatures, we examined the effects of annealing and short-term electron irradiation of SIA clusters on their subsequent 1D migration. In annealed SUS316L, 1D migration was suppressed and then recovered by prolonged irradiation at 300 K. In high-purity model alloy Fe-18Cr-13Ni, annealing or irradiation had no effect. Addition of carbon or oxygen to the model alloy suppressed 1D migration after annealing. Manganese and silicon did not suppress 1D migration after annealing but after short-term electron irradiation. The suppression was attributable to the pinning of SIA clusters by segregated solute elements, and the recovery was to the dissolution of the segregation by interatomic mixing under electron irradiation. Next, we examined 1D migration of SIA clusters in SUS316L under continuous electron irradiation at elevated temperatures. The 1D migration frequency at 673 K was proportional to the irradiation intensity. It was as high as half of that at 300 K. We proposed that 1D migration is controlled by the competition of two effects: induction of 1D migration by interatomic mixing and suppression by solute segregation.