Electrochemical properties of protoporphyrin IX zinc(II) films

The electrochemical properties of protoporphyrin IX zinc(II) (ZnPP) films on indium-tin oxide (ITO) substrate have been studied for three types of films with different arrangements, which were an adsorbed film of ZnPP and LB films of ZnPP and its hybrid with hexadecyltrimethylammonium bromide. Cyclic voltammetry (CV) measurement showed that, as the adsorbed amount of ZnPP increases, an irreversible oxidation peak of ZnPP film is intensified. This reveals that electrochemical properties depend on the adsorbed amount rather than the orientation of porphyrin molecules. It was also supported from CV measurement and ultraviolet-visible absorption spectroscopy that porphyrins adsorbed on ITO substrate were desorbed after the single scan of potential. Additionally, photoresponse of these ZnPP films was investigated by photocurrent measurement. The photocurrent generation is due to carboxylic acid moieties but not ZnPP macrocycles.     

P NMR investigation of a ringing gel phase and adjacent phases

The temperature-surfactant concentration phase diagram was examined for the dodecyltrimethylammonium dimethylphosphate/3-methyl-3-methoxybutanol/water ternary system. The phase diagram contained a highly elastic gel phase which is known as a “ringing gel phase”. The ringing gel phase and adjacent phases in the ternary system were investigated by polarized optical microscopy, freeze-fracture transmission electron microscopy, and ³¹P NMR. Globular textures were observed in an optically isotropic gel phase. Since the globules were larger than those found in an isotropic solution, the texture consists of domains of aggregated units in the cubic (I₁) phase. Structure units of domains are equivalent to microemulsions which are constructed by surfactant molecules and swollen by alcohol in the isotropic (L₁) phase. Characteristic polarized microscopic textures were visualized in two phases with higher surfactant concentrations. These phases were identified as being hexagonal (H₁) and lamellar (L) liquid crystals which was confirmed by transmission electron microscopy. The ³¹P NMR signal of the ringing gel showed a sharp singlet the same as that of the L₁ phase, indicating the fully averaged anisotropic interaction of the aggregates. The characteristic NMR signals of the anisotropic hexagonal and lamellar liquid crystal phases displayed chemical shielding with an asymmetric lineshape.     

Synthesis of new-type donor–acceptor π-conjugated benzofuro[2,3-c]oxazolo[4,5-a]carbazole fluorescent dyes and their photovoltaic performances of dye-sensitized solar cells

New-type donor–acceptor π-conjugated benzofuro[2,3-c]oxazolo[4,5-a]carbazole fluorescent dyes with various lengths of non-conjugated alkyl chains containing a carboxyl group at the end position have been developed and their photovoltaic performances of dye-sensitized solar cells are investigated. It is found that in spite of the lengths of the alkyl chains, due to flexibility of alkyl chain, the cyano group of the dyes is located in close proximity to TiO₂ surface and thus a good electron communication between the dyes and TiO₂ surface is established.     

Solubilization properties of aqueous solutions of alkyltrimethylammonium halides toward a water-insoluble dye

The solubility of a water-insoluble dye, Sudan Red B, in aqueous sodium halide solutions of tetradecyl-, cetyl-, and stearyltrimethylammonium halides has been measured at different surfactant and salt concentrations, and the dependence of solubilization properties on alkyl chain length has been discussed with reference to the micelle size and shape. At low ionic strengths where only spherical micelles exist, the solubilization power of micellar surfactant slightly increases with increasing the ionic strength, but it sharply increases at high ionic strengths above the threshold value of sphere-rod transition. However, the solubilization power becomes independent of the ionic strength, if their rodlike micelles are sufficiently long. The solubilization capacity increases linearly with increasing the molecular weight, almost independent of counterion species, but the rod-like micelle has a higher solubilization capacity than the spherical micelle. The solubilization capacity is larger for a surfactant with longer alkyl chain, indicating that the dye is solubilized more readily in a larger hydrophobic core. The solubilized dye is situated in a rodlike micelle of alkyltrimethylammonium halides, on average, 4.5–7.5 nm apart from each other.     

Synthesis and characterization of poly(ethyleneimine) dendrimers

Poly(ethyleneimine) (PEI) dendrimers up to the third generation (G3) were prepared by a divergent synthesis method from an ethylenediamine (EDA) core. The amine terminals were bonded with vinylbromide by a Michael addition reaction. Then, the bromide terminals were converted to amine groups using a Gabriel amine synthesis method. PEI dendrimers displayed pH-dependent luminescence, and their emission intensities at pH 6 increased over time. Fluorescence intensities also increased with increasing dendrimer generation from G1 to G3. Air-bubbling in aqueous solutions of dendrimers made to incorporate detectable amount of oxygen in dendrimers. EDA also behaved similarly in luminescence and oxygen incorporation.

Novel amphiphilic linear polymer/dendrimer block copolymer: Synthesis of poly(2-methyl-2-oxazoline)-block-poly(amido amine) dendrimer

Novel linear polymer/dendrimer block copolymers, poly(2-methyl-2-oxazoline)-block-poly(amido amine) dendrimers (water-soluble full-generation type 4 (G = 4.0 and 5.0) and amphiphilic half-generation type 5 (G = 3.5, 4.5, and 5.5)), were synthesized by divergent-growth dendrimer construction with ω-ethylenediamine-terminated poly(2-methyl-2-oxazoline), which was prepared by living ring-opening polymerization of 2-methyl-2-oxazoline. Assembly of the amphiphilic dendrimer-based block copolymer (G = 5.5) was investigated by surface tension measurements (critical micelle concentration, 0.49 wt.-%) and by small-angle neutron scattering analysis (spherical particles; assembled number, ca. 10³).     

Investigation of organic thermoelectric materials using potential-step chronocoulometry: Effect of polymerization methods on thermoelectric properties of poly(3-hexylthiophene)

To establish the correlation between the thermoelectric properties of conducting polymers and their doping levels, we have utilized the potential-step chronocoulometry for the quantitative estimation of the doping levels. In this paper, three types of poly(3-hexylthiophene)s synthesized by different polymerization methods were investigated. The electrical conductivities and the Seebeck coefficients of poly(3-hexylthiophene)s with various doping levels were measured and plotted against the doping level. It was found that the electrical conductivity linearly increased with increasing the doping level in the range of 1–10%, and then saturated. On the other hand, the relationship between the Seebeck coefficient and the doping level showed a good linearity in all the polymers.     

Thermoelectric properties of PEDOT films prepared by electrochemical polymerization

Thermoelectric (TE) properties of flexible and free‐standing poly(3,4‐ethylenedioxythiophene) (PEDOT) films synthesized via galvanostatic polymerization of 3,4‐ethylenedioxythiophene in propylene carbonate containing sulfated poly(β‐hydroxyethers) (S‐PHE) as polymer electrolyte were elaborately studied. Both electrical conductivities (σ ) and Seebeck coefficients (S ) of the PEDOT:S‐PHE films were increased by decreasing the temperature (T ) or by increasing the current density (J ) during electrosynthesis. Possible reasons for the lack of a trade‐off relation commonly observed between σ and S are discussed on the basis of SEM and oxidation‐level measurements. Preparation of the PEDOT:S‐PHE films was optimized with respect to T and J . In addition, the oxidation level of the PEDOT:S‐PHE films was controlled by potential and the change of their TE performances was discussed in conjunction with the change of chemical species involved. The power factor (PF = σS ²) of the PEDOT:S‐PHE films reached 7.9 μW m^?1 K^?2, leading to a dimensionless TE figure‐of‐merit (ZT ) of 0.013. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 524–531     

Flexible thermoelectric materials based on conducting polymers doped with silicone polymer electrolyte

Abstract

Novel conducting polymers doped with siloxane-based polyanion have been synthesized and their mechanical and thermoelectric properties were investigated. Free-standing properties and flexibility of these polymer films were compared with conducting polymers doped with conventional polyanion composed of carbon-carbon backbone. Thermoelectric properties were found to not be affected by the chemical structures of dopant polyanions.