Visco-elastic properties of reentrant nematic liquid crystalline mixtures

The visco-elastic properties for binary mixtures of 4-n -hexyloxy-4′-cyanobiphenyl (6OCB) and 4-n-octyloxy-4′-cyanobiphenyl (8OCB) are investigated in detail by a light scattering technique. The mixtures exhibit a reentrant nematic (RN) phase between the smectic A (SmA) and crystal phases in the range 22.0–29.5 wt % of 6OCB. The viscosity and the elastic constant increase with cooling in both the nematic and reentrant nematic phases. It is also found that the mixtures exhibit anomalously large values of viscosity and elastic constant near the phase transition, i.e. a pretransitional phenomenon can be observed. The activation energy for viscosity is smaller in the RN phase than in the ordinary nematic phase appearing at higher temperatures, while the normalized elastic constant (defined as the ratio of the elastic constant to the square of the dielectric anisotropy) is larger. Moreover, the visco-elastic behaviour depends on the specific time during which the sample has been kept in the SmA phase. These results confirm that the SmA phase has a strong influence on the formation of molecular aggregates, which plays an important role in the reentrant phenomenon of these systems.     

Highly oriented growth of titanate nanotubes (TNTs) in micro and confinement spaces on sol–gel derived amorphous TiO2 thin films under moderate hydrothermal condition

Synthesis of titanate nanotubes (TNTs) from sol–gel derived amorphous TiO₂ thin films under moderate hydrothermal condition has been reported. TNTs from film possess a tubular morphology that is the same crystalline phase as one synthesized from TiO₂ powder so far. TNTs obtained in this study are not entangled one another but oriented and isolated on the substrate. Growth of highly oriented TNTs is observed in micro grooves of amorphous TiO₂ thin film. Their orientation is also maintained with the growth of TNTs.     

Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes

A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation.     

Synthesis of cis-3-arylated cycloalkylamines through palladium-catalyzed methylene sp carbon–hydrogen bond activation

Methylene sp³ carbon–hydrogen bond activation of N-picolinoylcycloalkylamines provides a useful method for synthesizing cis-3-arylated cycloalkylamine derivatives. Pd(II) species catalyzed the γ-arylation of N-picolinoylcycloalkylamines with aryl iodides in the presence of silver carbonate to afford cis-3-arylated N-picolinoylalkylamines in up to 87% yield. Hydrolysis of the amide linkage to give the corresponding cis-3-arylated cycloalkylamines was also demonstrated.     

Synthesis of N-labeled 4-oxo-2,2,6,6-tetraethylpiperidine nitroxide for EPR brain imaging

A scalable synthetic route for ¹⁵N-labeled 4-oxo-2,2,6,6-tetraethylpiperidine nitroxide (¹⁵N-TEEPONE) is described. This ¹⁵N-labeled nitroxide is suitable for electron paramagnetic resonance imaging of brain, and its higher sensitivity compared with that of its ¹⁴N-counterpart is an important advantage of the labeled derivative.     

Dibenzo[a,f]perylene Bisimide: Effects of Introducing Two Fused Rings

Perylene bisimides (PBIs) are fascinating dyes with various potential applications. To study the effects of introducing a dibenzo‐fused structure to the perylene moiety, π‐extended PBI derivatives with a dibenzo‐fused structure at both of the a and f bonds were synthesized. The twisted structure was characterized by X‐ray crystal structure analysis. In the cyclic voltammograms, the dibenzo[a,f]‐fused PBI showed a reversible oxidation wave at much less positive potential, relative to a dibenzo[a,o]‐fused PBI derivative. These data indicated that two ring fusions at both sides of a naphthalene moiety, which construct a tetracene core, effectively raise the HOMO level compared to fusion of one ring at each naphthalene moiety (two anthracene cores). The dibenzo[a,f]‐fused PBI derivative showed an absorption band at 735 nm with a shoulder band reaching 900 nm.     

Morphological Investigation of Midblock‐Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity

Recent developments regarding charged multiblock copolymers that can form physical networks and exhibit robust mechanical properties herald new and exciting opportunities for contemporary technologies requiring amphiphilic attributes. Due to the presence of strong interactions, however, control over the phase behavior of such materials remains challenging, especially since their morphologies can be solvent‐templated. In this study, transmission electron microscopy and microtomography are employed to examine the morphological characteristics of midblock‐sulfonated pentablock ionomers prepared from solvents differing in polarity. Resultant images confirm that discrete, spherical ion‐rich microdomains form in films cast from a relatively nonpolar solvent, whereas an apparently mixed morphology with a continuous ion‐rich pathway is generated when the casting solvent is more highly polar. Detailed 3D analysis of the morphological characteristics confirms the coexistence of hexagonally‐packed nonpolar cylinders and lamellae, which facilitates the diffusion of ions and/or other polar species through the nanostructured medium.

     

α-Trifluoromethyl Chalcones as Potent Anticancer Agents for Androgen Receptor-Independent Prostate Cancer

α-Trifluoromethyl chalcones were prepared and evaluated for their antiproliferative activities against androgen-independent prostate cancer cell lines as well as five additional types of human tumor cell lines. The most potent chalcone 5 showed superior antitumor activity in vivo with both oral and intraperitoneal administration at 3 mg/kg. Cell-based mechanism of action studies demonstrated that 5 induced cell accumulation at sub-G1 and G2/M phases without interfering with microtubule polymerization. Furthermore, several cancer cell growth-related proteins were identified by using chalcone 5 as a bait for the affinity purification of binding proteins.