Synthesis,Properties, and π‐Dimer Formation of Oligothiophenes Partially Bearing Orthogonally Fused Fluorene Units

A series of oligothiophenes that incorporate cyclopenta[c]thiophene‐based units bearing spiro‐substituted dialkylfluorene was synthesized. Photophysical measurements indicated that there was no interruption in the conjugation along the oligothiophene backbones, irrespective of the number or position of this unit. Electrochemical measurements showed that the thiophene 7‐mers and 11‐mer exhibit reversible multi‐oxidation waves. The formation of cationic species was clearly observed from UV/Vis/NIR measurements. Furthermore, the UV/Vis/NIR spectra at 223 K under one‐electron oxidation conditions revealed that the unsubstituted thiophene or bithiophene units remained in the absence of intermolecular π–π interactions, whereas the formation of π‐dimeric species was observed for the thiophene 7‐mer containing an unsubstituted terthiophene ( U₃ ) unit. Theoretical calculations indicated that the combination of the U₃ unit and the all‐trans conformation decreased the intermolecular steric repulsion between the fused cyclopentene ring and its facing thiophene, which may contribute to the formation of the dimeric structure.     

Characteristics of high efficiency dye-sensitized solar cells

Impedance spectroscopy was applied to investigate the characteristics of dye-sensitized nanostructured TiO2 solar cells (DSC) with high efficiencies of light to electricity conversion of 11.1% and 10.2%. The different parameters, that is, chemical capacitance, steady-state transport resistance, transient diffusion coefficient, and charge-transfer (recombination) resistance, have been interpreted in a unified and consistent framework, in which an exponential distribution of the localized states in the TiO2 band gap plays a central role. The temperature variation of the chemical diffusion coefficient dependence on the Fermi-level position has been observed consistently with the standard multiple trapping model of electron transport in disordered semiconductors. A Tafel dependence of the recombination resistance dependence on bias potential has been rationalized in terms of the charge transfer from a distribution of surface states using the Marcus model of electron transfer. The current-potential curve of the solar cells has been independently constructed from the impedance parameters, allowing a separate analysis of the contribution of different resistive processes to the overall conversion efficiency.     

Significance of the molecular shape of iron corrphycene in a protein pocket

The iron complex of a new type of corrphycene bearing two ethoxycarbonyl (-CO2C2H5) groups on the bipyrrole moiety was introduced into apomyoglobin. The reconstituted ferric myoglobin has a coordinating water molecule that deprotonates to hydroxide with a pK(a) value of 7.3 and exhibits 3-10-fold higher affinities for anionic ligands when compared with a counterpart myoglobin with the same substituents on the dipyrroethene moiety. In the ferrous state, the oxygen affinity of the new myoglobin was decreased to 1/410 of the native protein. The anomalies in the ligand binding, notably dependent on the side-chain location, were interpreted in terms of a characteristic core shape of corrphycene that produces the longer and shorter Fe-N(pyrrole) bonds. The spin-state equilibrium analysis of the ferric azide myoglobin containing the new iron corrphycene supported the nonequivalence of the Fe-N(pyrrole) bonds. These results demonstrate that the trapezoidal molecular shape of corrphycene exerts functional significance when the iron complex is placed in a protein pocket.     

Infrared multiphoton dissociation spectroscopic analysis of peptides and oligosaccharides by using fourier transform ion cyclotron resonance mass spectrometry with a midinfrared free-electron laser

The fragmentation of peptides and oligosaccharides in the gas phase was investigated by means of electrospray ionization Fourier transform ion cyclotron resonance (FTICR) mass spectrometry coupled with dissociation by a laser-cleavage infrared multiphoton dissociation (IRMPD) technique. In this technique, an IR free-electron laser is used as a tunable source of IR radiation to cause cleavage of the ionized samples introduced into the FTICR cell. The gas-phase IRMPD spectra of protonated peptides (substance P and angiotensin II) and two sodiated oligosaccharides (sialyl Lewis X and lacto-N-fucopentaose III) were obtained over the IR scan range of 5.7-9.5 microm. In the IRMPD spectra for the peptide, fragment ions are observed as y/b-type fragment ions in the range 5.7-7.5 microm, corresponding to cleavage of the backbone of the parent amino acid sequence, whereas the spectra of the oligosaccharides have major peaks in the range 8.4-9.5 microm, corresponding to photoproducts of the B/Y type.     

Thermodynamic study on the interaction of imidazolium salts and POE-type nonionic surfactant in the adsorbed film

The composition of the adsorbed film and the excess Gibbs energy of adsorption $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were evaluated from thermodynamic analysis of surface tensions for the 1-decyl-3-methylimidazoulium bromide (C₁₀mimBr)–tetraethylene glycol monooctyl ether (C₈E₄) and 1-decyl-3-methyl-imidazolium tetrafluorobrorate (C₁₀mimBF₄)–C₈E₄ systems, where the counter anion of imidazolium salts is different from each other. The higher miscibility of two components compared to an ideal mixing and thus negative $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were observed in the former, which comes from the ion–dipole interaction between imidazolium cation and the oxyethylene group of C₈E₄. On the other hand, the lower miscibility and thus positive $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were observed for the latter. Such differences were attributed to that BF₄ ^? forms two hydrogen bonds and has stronger affinity with the cationic head group of C₁₀mim⁺ than Br^?. This results in that the ion–dipole interaction between C₈E₄ and C₁₀mim⁺ cation is diminished in the C₁₀mimBF₄–C₈E₄ system.     

Fabrication of mesoporous ZnO nanosheets from precursor templates grown in aqueous solutions

Mesoporous ZnO nanosheets were successfully prepared by pyrolytic transformation of zinc carbonate hydroxide hydrate, Zn₄CO₃(OH)₆·H₂O. The nanosheets were initially formed as assemblies on glass substrates during chemical bath deposition (CBD) in aqueous solutions of urea and zinc acetate dihydrate, zinc chloride, zinc nitrate hexahydrate, or zinc sulfate heptahydrate at 80°C. It was key to induce heterogeneous nucleation of Zn₄CO₃(OH)₆·H₂O by promoting a gradual hydrolysis reaction of urea and controlling the degree of supersaturation of zinc hydroxide species. Morphology of Zn₄CO₃(OH)₆·H₂O was largely influenced by the anions present in the CBD solutions. The Zn₄CO₃(OH)₆·H₂O nanosheets were transformed into wurtzite ZnO by heating at 300°C in air without losing the microstructural feature.     

Switchable antenna: a star-shaped ruthenium/osmium tetranuclear complex with azobis(bipyridine) bridging ligands

A star-shaped Ru/Os tetranuclear complex, in which a central Os unit is linked to three peripheral Ru units by 4,4'-azobis(2,2'-bipyridine) (azobpy) bridging ligands, was prepared to examine the unique photodynamics regulated by its redox state. The Ru/Os tetranuclear complex exhibits Ru-based luminescence at 77 K, whereas the three-electron reduction (one for each azobpy) of the Ru/Os complex results in luminescence from the Os unit. The photoexcited state of the Ru/Os complex rapidly decays into low energy metal-to-ligand charge-transfer states, in which the excited electron is localized in the azobpy ligand in the form of azobpy(.-). Upon the one-electron reduction of the azobpy ligands, the above-mentioned low-energy states become unavailable to the photoexcited complex. As a result, an energy transfer from the Ru-based excited state to the Os-based excited state becomes possible. Ultrafast transient absorption measurements revealed that the energy transfer process consists of two steps; intramolecular electron transfer from the terminal bipyridine ligand (bpy(.-)) to form azobpy(2-) followed by a metal-to-metal electron transfer. Thus, the Ru/Os tetranuclear complex collects light energy into the central Os unit depending on the redox state of the bridging ligands, qualifying as a switchable antenna.     

Development of hydrophilic fluorogenic derivatization reagents for thiols: 4-(N-acetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole and 4-(N-trichloroacetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole

Sensitive, reactive, and hydrophilic fluorogenic reagents for thiols with the benzofurazan skeleton, 4-(N-acetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (AcABD-F) and 4-(N-trichloroacetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (TCAcABD-F) have been developed. These reagents reacted with thiols within 10 min at 60 degrees C. AcABD-F and TCAcABD-F themselves do not fluoresce but are strongly fluorescent after the reaction with thiol compounds. The generated derivatives were highly water-soluble, since they dissociated a proton and ionized in the neutral pH region. The derivatives with four biologically important thiol compounds were separated on a reversed-phase HPLC column and detected fluorometrically at 504 nm with excitation at 388 nm. The detection limit attained for homocysteine with AcABD-F was 25 fmol on column (11 nM) (signal-to-noise ratio = 3), and that for glutathione with TCAcABD-F was 45 fmol on column (20 nM).     

Dianion of sulfinylacetone as a synthetic equivalent of beta-enolate of propionic acid: a novel synthesis of carboxylic acids from alkyl halides with three-carbon elongation

The reaction of the dianion of phenylsulfinylacetone with alkyl halides afforded beta-keto sulfoxides, which were first chlorinated with hexachloroethane and then treated successively with KH and t-BuLi to give carboxylic acids in three-steps in moderate overall yields from the alkyl halides. This procedure affords a good method for a synthesis of carboxylic acids from alkyl halides with three-carbon elongation.     

Transformation of peptide nanotubes into a vesicle via fusion driven by stereo-complex formation

Two types of peptide nanotubes, one is prepared from an amphiphilic peptide having a right-handed helix segment and the other from that having a left-handed helix segment, are shown to transform the morphology into a vesicle by membrane fusion due to stereo-complex formation between these helical segments.