Preparation and Acid‐Responsive Photophysical Properties of T‐Shaped π‐Conjugated Molecules Containing a Benzimidazole Junction

T‐shaped π‐conjugated molecules with an N‐methyl‐benzimidazole junction have been synthesized and their acid‐responsive photophysical properties owing to the change in the π‐conjugation system are discussed. T‐shaped π‐conjugated molecules consist of two orthogonal π‐conjugated systems including a phenyl thiophene extended from the 2‐position and alkyl phenylenes connected through various π‐spacers from the 4,7‐positions of the N‐methyl‐benzimidazole junction. The π‐spacers, such as thiophene, ethyne, and ethane, have an effect on the acid response of photophysical properties in terms of changes in conformation, excited‐state energy and charge‐transfer (CT) characteristics. In particular, the π‐conjugated molecule with ethynyl spacers exhibited a marked redshift in the fluorescence spectrum with a large Stokes shift upon the addition of acid, whereas the other molecules showed substantial quenching. The redshift in emission was studied in detail by temperature‐dependent fluorescence measurements, which indicated the transition to a CT state over the finite activation energy at the excited state. The change in the frontier molecular orbitals upon acid addition was further discussed by means of DFT calculations.     

Structures and fluorescence of secondary products produced from the cope-knoevenagel reaction of 2-phenylpropionaldehyde with methyl cyanoacetate

The Cope-Knoevenagel reaction of 2-phenylpropionaldehyde ( 7 ) with methyl cyanoacetate ( 8 ) produced methyl (E)-2-cyano-4-phenylpent-2-enoate ( 9 ) and the two highly fluorescent secondary products, 2-amino-3-carbomethoxy-6-phenyl-4-(1-phenylethyl)pyridine ( 10 ) and 3-cyano-6-phenyl-4-(1-phenylethyl)-2-pyridone ( 11 ). The structure of 10 was determined by X-ray crystallography while the structure of 11 was confirmed by the conversion of 9 into 11 . The mechanism of their formation is discussed. Fluorescence of 10 and 11 and the related compounds are also described.     

Electrochemical and thermal properties of hyperbranched polymer electrolytes for batteries

Terminal-acetylated hyperbranched poly(ethylene glycol) derivatives containing diethylene, triethylene, and hexaethylene and 3,5-dioxybenzoate branching units (poly-Ac1a, poly-Ac1b, and poly-Ac1c) were synthesized. Electrochemical and thermal properties of the hyperbranched polymer electrolytes with lithium salts such as LiCF₃SO₃ and LiN(CF₃SO₂)₂, the composite hyperbranched polymer electrolytes with LiN(CF₃SO₂)₂ containing α-LiAlO₂ and γ-LiAlO₂ fillers, and the hyperbranched polymer blended poly(ethylene oxide) electrolytes with LiN(CF₃SO₂)₂ were investigated and discussed. Paper presented at the 8th EuroConference on Ionics, Carvoeire, Algarve, Portugal, Sept. 16–22, 2001.     

Application of resonant X-ray emissions for molecular/electronic structure analysis of boron nitrides

* –B1s^-1 transitions were observed in w-BN composed of four-fold boron atoms and in h-BN composed of three-fold boron atoms, when the photon energy of the incident undulator beams coincided with the B1s–B2pπ^* absorption energy. However, no resonance was observed in c-BN composed of four-fold boron atoms. The resonant X-ray emission reflects the electronic structure of unoccupied molecular orbitals which strongly depend on the conformnations of the boron atoms. These findings confirm that resonant X-ray emissions can be useful indices for molecular and electronic structure analysis of boron nitrides. Accepted: 6 March 1997     

A new dual-type DMA for measuring nanoparticles emitted from combustion engines

A new dual-type differential mobility analyzer (dual-type DMA) was developed in order to detect transient number concentrations of airborne nanoparticles with diameters centralized at around 10 nm (for nuclei mode particles) and 100 nm (for accumulation mode particles) in automobile exhaust gas. The apparatus divides the gas sample into two parts, and each part is sent through one of two coaxially nested sections for analysis. For the scanning mode measurement, the nanoparticles are charged by ²⁴¹Am and their size distributions are determined by varying the applied voltage over 2 min. The transient mode measurement, on the other hand, fixes the voltages for the two sections at peaks near 10 and 100 nm in order to monitor the transient behavior of the exhaust nanoparticles. The measurement principles and design of the dual-type DMA are detailed and the results for time response experiments are presented using model nanoparticles charged by a corona charger. The transient concentrations of the nuclei mode and the accumulation mode particles from a diesel engine were shown to be detected by this method, when ²⁴¹Am was used for charging the particles.     

Miscibility evaluation of SPS/APS blend investigated from crystallization dynamics

The miscibility of crystalline syndiotactic polystyrene (SPS)/non-crystalline atactic polystyrene (APS) blend was estimated by the crystallization dynamics method, which evaluated the nucleation rate, the crystal growth rate and the surface free energy parameter. The melting temperature depression suggested that SPS/APS blends were the miscible system but not in molecular level. The relationship between the blend content and the chemical potential difference evaluated at a constant crystal growth rate showed a good linear relationship. These facts suggested that SPS/APS blends contained the concentration fluctuation with the size between few nm to less than 80 nm. This revised version was published online in July 2006 with corrections to the Cover Date.