Synthesis of organosilicon polymers containing donor-acceptor type π-conjugated units and their applications to dye-sensitized solar cells

Novel organosilicon polymers having donor-acceptor type π-conjugated units in the backbone were prepared by Stille-coupling reactions of bis(tributylstannylthienyl)silanes with diiodoquinoxialine, benzothiadiazole, and benzothiaselenazole. Dehaloganative copolymerization of di(bromothienyl)silanes and dibromoquinoxaline was also studied, which gave the corresponding random copolymer. Applications of these polymers to dye-sensitized solar cells (DSSCs) were examined and it was found that the polymer containing benzoselenadiazole units as the acceptor exhibited the best performance as the sensitizer among the present polymers.     

Micro-ring cavity mode of dye-doped thin film: Dependence on the excitation energy

We have prepared π-conjugated organic dye specimens embedded in a transparent polymer film and observed a characteristic photoluminescence peak, having very narrow peak width as compared with the fluorescence in solution, when we prepared the film around the perimeter of a multimode silica fiber. The peak position showed no dependence on the excitation wavelength, indicating that it could not be explained by a whispering gallery mode. The peaks can be explained by amplified spontaneous emissions (ASE) because the intensity depended linearly on the excitation intensity with some threshold. When the excitation laser was directly coupled to the fiber core, we observed ASE peaks of the optical fiber itself. These fiber ASE peaks shifted to longer wavelength when we varied the excitation to shorter wavelength, which clearly ruled out the possibility of silicate Raman scattering as the origin.     

Effects of iron on the degradation of triphenyltin by pyoverdins isolated from Pseudomonas chlororaphis

The yellow compound pyoverdin was isolated from the bacteria Pseudomonas chlororaphis, isolated from mud in Japan. A study of the effects of iron, phosphorus, manganese and zinc on degradation of triphenyltin (TPT) by pyoverdin (20 mg) was carried out in distilled water (30 ml) containing 6 µg l^?1 concentration of TPT at 20 °C for 48 or 96 h. The organotins in water were analyzed by gas chromatograph–mass spectrometry in the selected ion mode. The degradation of TPT by pyoverdin decreased with increase of phosphorus at 0–35 mg l^?1 and Fe‐EDTA at 0–2 mg l^?1 concentrations. Also, degradation of diphenyltin by pyoverdin decreased with increase of Mn‐EDTA at 0–1 mg l^?1 and Zn‐EDTA at 0–1 mg l^?1. On the other hand, degradation of TPT by pyoverdin was found to be unaffected by manganese and zinc in water. Copyright © 2002 John Wiley & Sons, Ltd.     

Speciation of protein-binding zinc and copper in human blood serum by chelating resin pre-treatment and inductively coupled plasma mass spectrometry

A method for the speciation of zinc and copper binding with proteins in human serum was explored by chelating resin (Chelex-100) pre-treatment and inductively coupled plasma mass spectrometry (ICP-MS). It was shown by a SEC (size-exclusion chromatography)-ICP-MS system that albumin-zinc and albumin-copper (loosely-bound species) could be selectively removed from serum by adsorption on the Chelex-100 resin after the chelating resin pre-treatment, while alpha 2-macroglobulin-zinc and ceruloplasmin-copper (firmly-bound species) remained in the serum. The zinc and copper bound with alpha 2-macroglobulin and ceruloplasmin, respectively, were then determined by ICP-MS after batch treatment of the serum samples with the Chelex-100 resin. In addition, the total concentrations of zinc and copper were also determined by ICP-MS after a 20-fold dilution with 0.1 M HNO3. The albumin-zinc and -copper were estimated as the differences between the concentrations of total and firmly-bound species. The present batch pre-treatment method was applied to the speciation analysis of zinc and copper binding with proteins in sera donated from 25 healthy volunteers as well as from a pregnant woman and a myelodysplastic syndrome patient. The observed concentrations of alpha 2-macroglobulin-zinc and ceruloplasmin-copper were in the ranges 109-202 ng ml-1 (12.4-31.3% of total zinc) and 513-880 ng ml-1 (90.6-99.7% of total copper), respectively. The present method is simple (only addition of the chelating resin and centrifugation is required) and reproducible (average RSD = 2% for alpha 2-macroglobulin-zinc and 1% for ceruloplasmin-copper in intra-assay measurements, and 5% for alpha 2-macroglobulin-zinc and 4% for ceruloplasmin-copper in inter-assay measurements), and there is less risk of contamination during separation.