Synthesis and properties of poly(phenylacetylene)s having dialkylamino groups

Summary Poly(phenylacetylene)s bearing dialkylamino groups were prepared by the polymerization of p-(N,N-dialkylamino)phenylacetylenes with [Rh(nbd)Cl]₂, and their electrochemical behavior was examined. Rh-catalyzed polymerization of p-(N,N-diethylamino)phenylacetylene (DEAPA) and p-(N,N-di-n-butylamino)phenylacetylene (DBAPA) in toluene in the presence of triethylamine gave good yields of the polymers (86 and 90%, respectively). Poly(DEAPA) was soluble in chloroform and dichloromethane, and poly(DBAPA) dissolved in various solvents such as toluene, THF, dichloromethane and chloroform. Poly(DEAPA) and poly(DBAPA) showed onset temperatures at 248 and 190°C, respectively, and absorptions around 300–400 nm. Electrochemical doping of the polymer films resulted in the shift of the absorptions to a region around 680 nm, which accompanied a color change of the polymer films from green ocher to deep blue. Received: 26 October 1998/Revised version: 6 November 1998/Accepted: 12 November 1998     

Photo atomic layer deposition of transparent conductive ZnO films

Low-resistivity ZnO films were grown by photo atomic layer deposition (photo-ALD) technique using diethylzinc (DEZ) and H₂O as reactant gases. Self-limiting growth was achieved for the temperature range from 105°C to 235°C. It was found that UV light irradiation was very effective to increase the electron concentration of the films and the electron concentration of 5 × 10²⁰ cm⁻³ was achieved even in undoped ZnO. Thus, the resistivity of the films grown with UV irradiation was one order of magnitude less than that grown without UV irradiation. The minimum resistivity of 6.9 × 10⁻⁴Ω cm was obtained by photo- ALD method without any intentional doping.     

Occurrence and sources of perfluorinated surfactants in rivers in Japan

We analyzed perfluorinated surfactants (PFSs) in 20 river samples and 5 wastewater secondary effluent samples in Japan to reveal their occurrence and sources. Nine PFS species were determined: perfluorooctanesulfonate (PFOS), perfluorooctane sulfonamide (FOSA), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), perfluorododecanoate (PFDDA), and perfluorotridecanoate (PFTDA). PFSs were detected in all rivers, revealing nationwide contamination of rivers. In particular, 11 out of 20 river samples exceeded New Jersey guidance for PFOA in drinking water (40 ng/L). PFOS, PFHpA, PFOA, and PFNA were major species in Japan. Concentrations of PFOS, PFHpA, and PFNA in rivers were strongly correlated with population density, suggesting that the chemicals were derived from urban activities. PFOA showed a significant but weak correlation. We used crotamiton, a marker of sewage effluent, for further source analysis. Concentrations of PFOS, PFHpA, and PFNAwere strongly correlated with those of crotamiton, and plots of secondary effluents fell near the regression lines of rivers, indicating that the PFOS, PFHpA, and PFNA in rivers were derived from sewage effluent. On the other hand, PFOA was found at remarkably high levels (54-192 ng/L) in seven river samples containing low levels of crotamiton, suggesting that it was derived from nonsewage point sources, as well as sewage effluent. The total fluxes of sewage-derived PFOS, PFHpA, PFOA, and PFNA from Japan were estimated to be 3.6, 2.6, 5.6, and 2.6 t/year, respectively. This is the first report to identify PFOA in several rivers, derived from nonsewage point sources, by using a marker of sewage effluent.     

A concentrator module of spherical Si solar cell

Spherical Si solar cell, which is made up of Si spheres with a diameter of approximately 1.0 mm, is expected to be a promising candidate for low consumption of Si feedstock and simple process technology. This paper describes the formation process and the structure of a concentrator module in detail. The concentrator lens was formed by casting with ultraviolet light hardening resin. The concentration ratio was 4.4 times and the pitch between the spheres was 2.0 mm. By this module design, it was possible to realize a consumption of the Si feedstock of about 3.0 g/W. Conversion efficiencies of 11.3% from single-sphere cell, 8.5% from a 23-spheres module and 5.2% from a 105-spheres module under AM1.5, 100 mW/cm² illumination were achieved.     

Functional analyses of neutrophil-like differentiated cell lines under a hyperglycemic condition

Diabetic patients are prone to severe bacterial infections. The functional alterations of neutrophils by hyperglycemia are thought to be partially responsible for such infections. In this study, we investigated the functional changes of neutrophil-like differentiated cell lines (dHL-60, dTHP-1, and dNB-4) by treatment with 5.5 mM, 11 mM, or 35 mM of glucose. In dHL-60 cells, the incubation with high glucose (35 mM) resulted in the enhancement of cell aggregation, the suppression of cellular fragility, the induction of reactive-oxygen species (ROS) production by phorbol myristate acetate (PMA) stimulation, and the impairment of phagocytosis. In dTHP-1 cells, the treatment with higher glucose generated the suppression of cellular fragility and extremely impaired phagocytosis (by 35 mM), and induced ROS production due to PMA stimulation (by 11 mM). Furthermore, the higher glucose exposure to dNB-4 cells enlarged intracellular vacuoles (by 35 mM) and induced ROS production due to PMA stimulation (by 11 mM). Since the ROS generation of those cells was enhanced only after PMA stimulation under the higher glucose conditions, glucose may have a priming effect rather than a triggering effect. These extraordinary sensitivities caused by the higher glucose treatments may reflect the dysfunction or overactivation of neutrophils.     

Thickness estimation of interface films formed on Li1−xCoO2 electrodes by hard X-ray photoelectron spectroscopy

Solid electrolyte interface (SEI) films formed on Li_1−xCoO₂ electrodes were observed with hard X-ray photoelectron spectroscopy (HX-PES). This paper particularly focuses on film thickness estimation using HX-PES with theoretical calculation. The validity of the calculation was proven by experiments using model SEI films. The native film formed on a LiCoO₂ composite electrode was estimated to be LiF with its thickness of 5 nm. Formation of Co (II) species on top of LiCoO₂ was also indicated. Storage of the electrode at 60 °C brought about considerable film growth (30-40 nm) with carbonate compounds formation. SEI film changes during charging of the LiCoO₂ electrode were also examined. The main component in the film was deduced to be LiF or a kind of fluorite, with its thickness decreased during charging. The SEI formation mechanisms are also elucidated.     

Moisture migration in idealized bilayer systems: relationships among water-associated properties, structure, and texture

The effects of composition and thermal treatment on the water sorption and diffusional properties of idealized protein gels arranged in bilayer configurations were determined; these water binding/migration properties were related to the mechanical characteristics of the gels. Samples were prepared from whey protein concentrate (WPC), they consisted of water:WPC ratios of 1.5 to 5.67, and were thermally set for 20–60 min. Moisture migration rates from samples interfaced with filters were determined, as were moisture sorption capacities of samples immersed in water. The physical properties of the gels were assessed by uniaxial compression and microscopy. Results showed that gel strength and consequent extent of protein interaction—as affected by thermal treatment—controlled the ability of the gel structure to absorb water. Sorption was exponentially correlated with gel modulus and linearly correlated with a function of protein content, heating time, and immersion time. Rates of diffusion from interfaced gels were dependent solely on water content. It was concluded that the degree of protein interaction, whether influenced by concentration or thermal treatment, affected network extensibility and thus the capacity of the gels to act as receptors of moisture. Results have implications for the functionality of shelf-stable sandwiches and other multicomponent foods.     

Staged combustion properties for pulverized coals at high temperature

Staged combustion properties for pulverized coals have been investigated by using a new-concept drop-tube furnace. Two high-temperature electric furnaces were connected in series. Coal was burnt under fuel-rich conditions in the first furnace, then, staged air was supplied at the connection between the two furnaces. Reaction temperature (1800–2100 K) and time (1–2 s) were similar to those used in actual boilers. When coal was burnt at the same stoichiometric ratio as in actual boilers, similar combustion performance values as for actual boilers were obtained regarding NO_x emission and carbon in ash. The most important factor for low NO_x combustion was to raise the combustion temperature above the present range (1800–2100 K) in the fuel-rich zone. The NO_x emission was significantly increased with decrease of burning temperature in the fuel-rich zone when the temperature was lower than 1800 K. But, NO_x emission was cut to around 100–150 ppm, for sub-bituminous coal and hv-bituminous coal, in the latest commercial plants by forming this high-temperature fuel-rich region in the boilers. If the temperature and stoichiometric ratio could be set to the most suitable conditions, and, burning gas and air were mixed well, it would be possible to lower NO_x emission to 30–60 ppm (6% O₂). The most important NO_x reduction reaction in the fuel-rich zone was the NO_x reduction by hydrocarbons. The hydrocarbon formation rate in the flame was varied with coal properties and combustion conditions. The NO_x was easily reduced when coals which easily formed hydrocarbons were used, or, when burning conditions which easily formed hydrocarbons were chosen. Effects of burning temperature and stoichiometric ratio on NO_x emission were reproduced by the previously proposed reaction model. When solid fuel was used, plant performance values varied with fuel properties. The proposed drop-tube furnace system was also found to be a useful analysis technique to evaluate the difference in combustion performance due to the fuel properties.     

Bulk heterojunction organic solar cells utilizing 1,4,8,11,15,18,22,25-octahexylphthalocyanine

Bulk heterojunction solar cells utilizing soluble phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH₂) have been investigated. The active layer was fabricated by spin-coating the mixed solution of C6PcH₂ and 1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM). The photovoltaic properties of the solar cell with bulk heterojunction of C6PcH₂ and PCBM demonstrated the strong dependence of active layer thickness, and the optimized active layer thickness was clarified to be 120 nm. By inserting MoO₃ hole transport buffer layer between the positive electrode and active layer, the FF and energy conversion efficiency were improved to be 0.50 and 3.2%, respectively. The tandem organic thin-film solar cell has also been studied by utilizing active layer materials of C6PcH₂ and poly(3-hexylthiophene) and the interlayer of LiF/Al/MoO₃ structure, and a high V_oc of 1.27 V has been achieved.     

Enhancement of solar radiation absorption using nanoparticle suspension

The radiation absorption characteristics of a Ni nanoparticle suspension were investigated by spectroscopic transmission measurement. It was demonstrated that the absorption coefficient of the nanoparticle suspension is much higher than that of the base liquid for visible to near-infrared wavelengths. Radiation characteristics predicted by the Mie theory showed good agreement with the increase of absorption coefficient in wavelengths where the base liquid is transparent. It was also confirmed that a new transmittance measurement technique for a liquid sample using a liquid cell with no spacer was quite useful for evaluating a material possessing an extremely strong absorption band. The proposed measurement method and successive Kramers-Kronig analysis were validated by measuring the optical properties of water. The measurement and prediction process of the thermal radiation properties of nanoparticle suspensions developed here could be used in developing direct absorption solar collectors.