Concise Synthesis of 3D π‐Extended Polyphenylene Cylinders

The synthesis of structurally well‐defined, monodisperse carbon nanotube (CNT) sidewall segments poses a challenge in materials science. The synthesis of polyphenylene cylinders that comprise typical benzene connectivity to resemble precursors of [9,9] and [15,15] CNTs is now reported, and the products were characterized by X‐ray crystallography. To investigate the oxidative cyclodehydrogenation of ring‐strained molecules as a final step towards a bottom‐up synthesis of CNT sidewall segments, phenylene‐extended cyclic p‐hexaphenylbenzene trimers ([3]CHPB) were prepared, and NMR studies revealed a strain‐induced 1,2‐phenyl shift. It was further shown that an increase in ring size leads to selectively dehydrogenated macrocycles. Larger homologues are envisioned to give smooth condensation reactions toward graphenic sidewalls and should be used in the future as seeds for CNT formation.     

Effect of swirling flow on unburned ratio and nitrogen oxide concentration in a spray combustion system

The effect of swirling flow on the unburned ratio and NO concentration in exhausted gas was studied for slurry [coal-water mixture (CWM)] spray combustion with variations of swirl numbers. A numerical analysis for CWM combustion was performed for axisymmetric flow in a cylindrical geometry. First, to check the performance of three previous k-ε turbulence models modified with swirling flow, velocity components of isothermal swirling jets were measured by laser-Doppler anemometry (LDA) and compared with predicted results. The two modified models gave more reliable results than the conventional one. Next, as the swirl number could not be estimated by the angular momentum derived from the vane angle of the circular swirler, the reduction rate of the tangential momentum flux through the tube of the circular swirler was measured and calculated. Both measured and predicted results showed that when the swirl number S′ given by the vane angle was 2.0, the effective swirl number S_eff decreased by about 60% to S′. To take the results mentioned above into consideration, effects of swirl number on both the exhausted NO concentration and unburned ratio were investigated. The predicted unburned ratio showed good agreement with the experimental results. Both experimental and calculated results showed that the optimum operating conditions controlling the exhausted NO concentration and unburned ratio in this spray combustion system were obtained when the swirl number S_eff was about 0.5.     

Kinetics of the esterification of palmitic acid with isobutyl alcohol

Kinetics of the sulfuric acid catalyzed esterification of palmitic acid with isobutyl alcohol has been studied and reviewed critically. A theoretical rate equation is derived by the following reaction mechanism: (1) The reaction of sulfuric acid and isobutyl alcohol produces isobutyl sulfuric acid which acts as a catalyst; (2) Palmitic acid is protonated by the catalyst to form the reaction intermediate; and (3) The esterification proceeds reversibly. The experimental results are consistent with this rate equation.     

Enantiomer-selective membrane electrode for amino acid methyl esters

Polymeric membrane electrodes based on the chiral crown ether, 2,3:4,5-bis-[1,2-(3-phenylnaphtho)]-1,6,9,12,15,18-hexaoxacycloeicosa-2,4-diene, were prepared, and their characteristics were examined. The electrodes showed good enantiomer-selectivity for many amino acid methylesters, the enantiomer-selective factor reaching the high value of 13 for phenylglycine methyl ester. The electrodes responded preferably to the enantiomer forming the more stable complex with the crown ether. The electrodes proved useful for determining the concentrations of each enantiomer. The calculated concentrations from the potential changes of the electrodes were in good agreement with the predicted ones.     

Release and transfer of polystyrene dewetting pattern by hydration force

We studied the release and transfer of polystyrene (PS) microdots on mica. The PS dots were released from the mica in water. The release was affected by the density of K(+) ions on the mica surface, which was controlled by pretreatment with K(2)CO(3) solutions. The release of PS dots became dominant at the concentrations above [K(+)]crit = 1 x 10(-4) M in the K(2)CO(3) solution. In this concentration region, repulsive forces appeared as a result of the hydration of K(+) ions on the mica (J. Colloid Interface Sci. 1981, 83, 531). This result suggests that the repulsive hydration force causes the release of the PS dots. Followed by the release process, we successfully demonstrated the transfer of the array of PS dots from the mica to another substrate.     

Electrokinetic effect of the bottom surface of a vessel on pearl-chain formation of silica particles

We have tackled in situ electric conductance measurements under microscopic observations for alignments of silica particles that are induced by ionic polarization of the electrical double layer (EDL) around the particles. Using the in situ conductance measurements, we have presented evidence that electro-osmotic flow at a vessel bottom/water interface would be coupled with the ionic polarization in the EDL of spherical silica particles settling at the bottom (Langmuir 2007, 23, 8797). In this study, we followed this phenomenon further. We altered the zeta potential of a platform of a glass plate on which a pearl chain of silica particles was formed under an ac electric field to control the mobility of electro-osmotic flow at the macroscopic interface of the platform/water. As the magnitude of the zeta potential of the platform increased, the surface distance between neighboring particles in the pearl chains decreased and the in situ conductance totally increased due to the enhancement of the dipole moments induced by the ionic polarizations of the particles. These results could be explained by considering that the electro-osmotic contribution to the surface conduction around the particles would be coupled with that occurring at the platform/water interface.     

Structural characterization and self-association of (Arylimido)vanadium(V) triisopropoxides

(Arylimido)vanadium(V) triisopropoxides, [( p-RC 6H 4N)V(O (i) Pr) 3] (R = NMe 2, OMe, H, CN, NO 2, Br), were prepared by the reaction of VO(O (i) Pr) 3 with the aryl isocyanates without solvent. The structures of the (arylimido)vanadium(V) triisopropoxides were characterized by single-crystal X-ray structure determination to elucidate the substituent effect on the self-association properties. Controlled association of the (arylimido)vanadium(V) triisopropoxides to the mu-oxo-bridged dimer complexes or the mu-imido-bridged dinuclear complex was achieved by changing the p-substituent on the benzene rings, which regulates the nature of the imido bonds. Furthermore, the one-dimensional linear polymer complex or the one-dimensional zigzag one through mu-oxo-bridging was formed in a solid state with the bimetallic (arylimido)vanadium(V) complex, [( (i) PrO) 3V(N- p-C 6H 4N)V(O (i) Pr) 3] or [( (i) PrO) 3V(N- m-C 6H 4N)V(O (i) Pr) 3], respectively.     

Variation in the chromatographic,material, and chemical characteristics of methacrylate‐based polymer monoliths during photoinitiated low‐temperature polymerization

Both the separation behavior and the structure of a polymer monolith column depends on both the reaction solution composition and the polymerization conditions. In photoinitiated low‐temperature polymerization, polymerization temperature, irradiation intensity, and polymerization time were key factors to control the monolith characteristics. In this study, the effect of polymerization time on the chromatographic, material, and chemical characteristics of poly(butyl methacrylate‐co‐ethylene dimethacrylate) monoliths was studied using pyrolysis‐gas chromatography, Raman spectroscopy, inverse size exclusion chromatography, scanning electron microscopy, and chromatographic methods. Both butyl methacrylate and ethylene dimethacrylate monomers were incorporated into the monolith as the polymerization time increased, and it resulted in increases in both the flow resistance (decrease in both permeability and total/through pore porosities) and retention factors. The longer polymerization time led to lower relative amounts of free methacrylate functional groups in the monolith, i.e. cross‐linking was enhanced. The increase of the polymerization time from 8 to 12 min significantly reduced the separation efficiency for the retained analyte, whereas an increase in the fraction of the mesoporosity was observed.