Fluorescence Properties and Exciplex Formation of Emissive Naphthyridine Derivatives: Application as Sensors for Amines

Water-soluble donor–acceptor-type fluorophore 15Nap-Cl having two trifluoromethyl groups and a Cl group on a 1,5-aminonaphthyridine framework was prepared. Fluorophore 15Nap-Cl showed strong solvatochromic fluorescence, and, as the solvent polarity increased, a bathochromic shift was observed accompanied by an increase in the fluorescence quantum yield. In addition, in the presence of amines such as ethylamine, diethylamine, and aniline, further considerable bathochromic shifts in the fluorescence were observed. Density functional calculations identified the source of the fluorescence behavior as exciplex formation between 15-Nap-Cl and the corresponding amine. The fluorescence behavior was exploited to fabricate a sensor that can identify various primary, secondary, and tertiary amines.     

Stereoselective anti-SN2′ Mitsunobu reaction of α-hydroxy-α-alkenylsilanes

A novel silyl group-directed anti-S_N2′ reaction of allylic alcohols under Mitsunobu reaction conditions is described. The Mitsunobu reaction of α-hydroxy-α-alkenylsilanes with a TBS or TIPS group gave the anti-S_N2′ product, in which regio- and stereochemical outcomes of the reaction depended on the steric bulkiness of the silyl group.     

Asymmetric Michael addition of 2-alkoxyphenyl α-substituted nitroacetates to non-prochiral α,β-unsaturated carbonyl compounds catalyzed by podand-type alkali metal 2′-substituted 1,1′-binaphthalen-2-oxides

The asymmetric Michael addition of 2-alkoxyphenyl α-substituted nitroacetates to non-prochiral α,β-unsaturated carbonyl compounds catalyzed by 10 mol % of sodium 2′-[2-(2-methoxyethoxy)ethoxy]-1,1′-binaphthalen-2-oxide gave the desired adducts in high yields with up to 95% ee.     

Effect of poly(ethylene oxide) on the rheological behavior of silica suspensions

The steady-shear viscosity, dynamic viscoelasticity, and sedimentation behavior were measured for silica suspensions dispersed in aqueous solutions of poly(ethylene oxide) (PEO). For suspensions prepared with polymer solutions in which the transient network is developed by entanglements, the viscosity at a given shear rate decreases, shows a minimum, and then increases with increasing particle concentration. Because the suspensions are sterically stabilized under the conditions where the particle surfaces are fully covered with by a thick layer of adsorbed polymer, the viscosity decrease can be attributed to the reduction of network density in solution. But under the low coverage conditions, the particles are flocculated by bridging and this leads to a viscosity increase with shear-thinning profiles. The polymer chains with high molecular weights form flexible bridges between particles. The stress-dependent curve of storage modulus measured by a stress amplitude sweep shows an increase prior to a drastic drop due to structural breakdown. The increase in elastic responses may arise from the restoring forces of extended bridges with high deformability. The effect of PEO on the rheological behavior of silica suspensions can be explained by a combination of concentration reduction of polymer in solution and flocculation by bridging.     

“Molecular Rope Curtain” Type of Liquid Crystals Based on a Sliding Graft Copolymer Having Mobile PEG Side Chains

A sliding graft copolymer having a polyrotaxane main chain and side chains of polyethylene glycol with a molecular weight of 2000 (PEG2000) was found to be a novel “molecular rope curtain” type of liquid crystalline material, which displayed a smectic A mesophase between 51 °C and 250 °C without any rigid mesogenic moieties.     

Three‐component negative‐type photosensitive polyimide precursor based on poly(amic acid), a crosslinker,and a photoacid generator

A new negative‐working and alkaline‐developable photosensitive polyimide precursor based on poly(amic acid) (PAA), 4,4′‐methylenebis[2,6‐bis(hydroxymethyl)]phenol (MBHP) as a crosslinker, and a photoacid generator (5‐propylsulfonyloxyimino‐5H‐thiophen‐2‐ylidene)‐2‐(methylphenyl)acetonitrile (PTMA) has been developed. PAA was prepared by ring‐opening polymerization of pyromellitic dianhydride with 4,4′‐oxydianiline. The photosensitive polyimide precursor containing PAA (65 wt %), MBHP (25 wt %), and PTMA (10 wt %) showed a clear negative image featuring 10 μm line and space patterns when it was exposed to 436 nm light at 100 mJ·cm^?2, post‐exposure baked at 130 °C for 3 min, followed by developing with a 2.38 wt % aqueous tetramethylammonium hydroxide solution at 25 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 593–599, 2005     

Simultaneous determination of cationic surfactants and nonionic surfactants by ion-association titration.

A simultaneous determination of cationic and nonionic surfactants has been developed using ion-association titration. Tetrabromophenolphthalein ethyl ester (TBPE) was used as an indicator. Benzalkonium reacted with TBPE to form a blue ion-associate in the organic phase. When tetrakis(4-fluorophenyl)borate was added dropwise to the solution, the color of the organic phase turned to yellow at the equivalence point. In addition, when a large amount of potassium ion was added to a solution including Triton X-100, Triton X-100 could be determined by the same technique as described above because of formation of the K+-Triton X-100 cation. The proposed method is available for the stepwise determination of cationic and nonionic surfactants in mixtures.     

Arithmetic expressions of Selberg's zeta functions for congruence subgroups

In [P. Sarnak, Class numbers of indefinite binary quadratic forms, J. Number Theory 15 (1982) 229-247], it was proved that the Selberg zeta function for SL₂(Z) is expressed in terms of the fundamental units and the class numbers of the primitive indefinite binary quadratic forms. The aim of this paper is to obtain similar arithmetic expressions of the logarithmic derivatives of the Selberg zeta functions for congruence subgroups of SL₂(Z). As applications, we study the Brun-Titchmarsh type prime geodesic theorem and the asymptotic formula of the sum of the class number.     

Shear-thickening flow of nanoparticle suspensions flocculated by polymer bridging

The steady-shear viscosity, dynamic viscoelasticity, and stress relaxation behavior were measured for suspensions of silica nanoparticles dispersed in aqueous solutions of poly(ethylene oxide) (PEO). The suspensions of silica with diameters of 8-25 nm show striking shear-thickening profiles in steady shear and highly elastic responses under large strains in oscillatory shear. Since the silica particles are much smaller than the polymer coils, one molecule can extend through several particles by intrachain bridging. Each polymer coil may remain isolated as a floc unit and the silica particles hardly connect two flocs. Therefore, the flow of suspensions is Newtonian with low viscosity at low shear rates. When the polymer coils containing several nanoparticles are subjected to high shear fields, three-dimensional network is developed over the system. The shear-thickening flow may arise from the elastic forces of extended bridges. But, the polymer chain is easily detached from particle surface by thermal energy because of large curvature of particles. As a result, the network structures are reversibly broken down in a quiescent state and the suspensions behaves as viscoelastic fluids with the zero-shear viscosity.