Synthesis of indole and biindolyl triflones: trifluoromethanesulfonylation of indoles with Tf2O/TTBP (2,4,6-tri-tert-butylpyridine) system

A convenient synthesis of indole triflones is reported. N-Alkyl, aryl and N-H indole triflones were obtained in 82-96% yields by the Tf(2)O/TTBP System. Biindolyl triflones were accessed in 51-81% yields for the first time by simple treatment of the resulting indole triflones with a base and without any use of organometallic chemistry. An environmentally friendly solvent, Solkane 365/227, can be substituted for this process without any loss of efficiency.     

Selective photoinduced energy transfer from a thiophene rotaxane to acceptor

An energy transfer process was investigated using cyclodextrin-oligothiophene rotaxanes (2T-[2]rotaxane). The excited energy of 2T-[2]rotaxane is transferred to the sexithiophene derivative which is included in the cavity of β-CD stoppers of 2T-[2]rotaxane.     

Highly luminescent SiO(2) beads with multiple QDs: Preparation conditions and size distributions

Multiple CdTe quantum dots (QDs) were incorporated in SiO(2) beads using a reverse micelle route (i.e., a water-in-oil emulsion) and a precursor solution of SiO(2)-coated CdTe QDs as the water phase. The QDs in the beads retained their initial photoluminescence efficiency (56%) because they had a thin SiO(2) shell that prevented removal of the ligands from their surface during incorporation. Because of the SiO(2) sol in the precursor solution, the size of the water pools in water-in-oil emulsion increased to 700±320nm compared to 25±5nm when an aqueous CdTe QD solution was used. The size of the beads prepared in the water pools depended strongly on the preparation parameters (water phase injection speed, tetraethyl orthosilicate concentration, reaction time). The beads were easily separated into three size ranges (60±23, 160±40, and 650±200nm) by filtering for further application.     

Fluorescent trimethyl-substituted naphthyridine as a ligand for C-C mismatch detection in CCG trinucleotide repeats

We report on the selective binding of 2-amino-5,6,7-trimethyl-1,8-naphthyridine (ATMND) to C-C mismatch present in the hairpin structures of (CCG)(n) trinucleotide repeats that are associated with neurological diseases; this binding is accompanied by significant fluorescence quenching of ATMND.     

Localization of the Grover Walks on Spidernets and Free Meixner Laws

In the first part, we have constructed several families of interacting wedge-local nets of von Neumann algebras. In particular, we discovered a family of models based on the endomorphisms of the U(1)-current algebra ${\mathcal{A} ^{(0)}}$ of Longo-Witten. In this second part, we further investigate endomorphisms and interacting models. The key ingredient is the free massless fermionic net, which contains the U(1)-current net as the fixed point subnet with respect to the U(1) gauge action. Through the restriction to the subnet, we construct a new family of Longo-Witten endomorphisms on ${\mathcal{A} ^{(0)}}$ and accordingly interacting wedge-local nets in two-dimensional spacetime. The U(1)-current net admits the structure of particle numbers and the S-matrices of the models constructed here do mix the spaces with different particle numbers of the bosonic Fock space.     

Mechanism of crystallization of enzyme protein thermolysin

The mechanism of crystallization of enzyme protein thermolysin was investigated. The size distribution of thermolysin precipitates was measured by dynamic light scattering during precipitation, and the surface and cross section of the finally obtained precipitate were observed by scanning electron microscopy. The thermolysin precipitates obtained at the initial supersaturation ratio of 8.9 to 164 and pH 7.0 were hexagonal rods having an average size of 9.2×1.5 μm, and were composed of a number of small particles of 15 to 200 nm in diameter. The average size of the small particles was 60 nm in diameter, and the formation of the particles was found to be completed in the early stage of precipitation. Observation of the finally recovered thermolysin precipitate by polarizing microscopy revealed that the precipitate is a crystalline solid. From these data, a possible mechanism of thermolysin crystallization was proposed. The crystallization proceeds through two steps: the first step is the formation of primary particles, and the second step is crystal growth by highly ordered aggregation of the primary particles.     

γ-poly(glutamic acid) as an initiator of cationic polymerization of N-vinylcarbazole and N-vinyl-2-pyrrolidone

The cationic polymerization of vinyl monomers initiated by biosynthesized γ-poly(glutamic acid) (γ-PGA) powder surface was carried out in a heterogeneous system. It was found that the polymerization of N-vinylcarbazole (NVC) and N-vinyl-2-pyrrolidone (NVPD) is initiated by γ-PGA powder. The grafting of polymers onto γ-PGA surface was scarcely observed. The apparent activation energy of the polymerization of NVC and NVPD was estimated to be 20.2 and 24.8 kJ/mol, respectively. The polymerization was totally inhibited by the addition of triethylamine and pyridine, but not hydroquinone. The polymerization rate in nitrobenzene was larger than that in toluene. These results indicated the cationic nature of the polymerization. γ-PGA treated with KOH did not show the initiating activity of the polymerization. Therefore, carboxyl groups on γ-PGA powder surface play an important role in the initiation of the polymerization. It may be suggested that the polymerization is initiated by proton addition to monomer from carboxyl groups on γ-PGA powder surface and the propagation proceeds with carboxylate anion on the surface as counter ion. © 1993 John Wiley & Sons, Inc.     

Permeation flux of organic molecules through silica-surfactant nanochannels in a porous alumina membrane.

The permeation fluxes of phenol, benzene sulfonate (BS) and benzene disulfonate (BDS) through a porous anodic alumina membrane with the perpendicularly oriented silica-surfactant nanochannel assembly membrane (NAM) were measured in water-ethanol mixture media. The permeation flux depended on solute charges and on solvent composition. As the ethanol ratio increased, the fluxes of BS and BDS increased and the flux of phenol decreased. The results of extraction/elution experiments also depended on the solute charges and the solvent composition. Chromatographic experiments in n-hexane showed that dipole and hydrophobic interactions affect the retention of solutes. Permeation of the solute across the NAM in water-ethanol mixture is likely to be determined by various factors such as dipole interaction, hydrophobic interaction, solvation, and anion-exchange efficiencies.     

Deformation and molecular orientation in films of metallocene polypropylene,ethylene–butylene rubber,and their 80/20 (w/w) blend revealed by the simultaneous kinetic measurement of microscopic infrared dichroism,macroscopic stress,and mesoscale strain

Simultaneous kinetic measurement of microscopic infrared dichroism, macroscopic stress, and mesoscale strain was used to study the deformation mechanisms of metallocene polypropylene (MPP), ethylene–butylene rubber (EBR), and their blend (MPP/EBR = 80/20 w/w). As with pure MPP, the molecular orientation in the blend is dominated by the necking of the isotactic polypropylene matrix. During the necking passage through the mesoscale sampling area, the molecular orientation of the polypropylene matrix in the blend is smaller than that in the pure polypropylene film at the same level of mesoscale strain. However, the orientation of the EBR dispersed phase in the blend is larger than that in the pure EBR film. This may result from the partial miscibility of the two ingredients in the amorphous phases and their resultant strong interfacial interaction. The large stress supported by the MPP matrix extends to the island of the EBR domain and leads to its large deformation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1520–1531, 2005