Reversed phase liquid chromatographic separation of some mono-substituted phenols with calix[6]arene-ρ-sulfonate-modified eluents

Summary The utility of water-soluble calix[6]arene--sulfonate as a mobile phase additive has been investigated for the reversed phase liquid chromatographic separation of some monosubstituted phenol isomers. Retention factors and separation factors for regioisomers of methoxyphenol, aminophenol, and nitrophenol were measured using methanol — water and acetonitrile —water mobile phases of varying composition containing calix[6]arene--sulfonate, and the values were compared with those obtained using mobile phases containing no additive. It was observed that addition of calix[6]arene--sulfonate to both acetonitrile — water and methanol —water caused a reduction in the retention of the phenol isomers but generally increased the separation between them, thereby improving the overall separation efficiency.     

An investigation into the effect of electric field on the performance of Dielectric Barrier Discharge plasma actuators

The influence of the inter-electrode electric field of a single Dielectric Barrier Discharge (DBD) actuator on the performance of the device was investigated. The electric field of the actuator was manipulated through the variation of the angle between the electrodes of the actuators. Response forces generated by the plasma actuators were used as performance indicators for these devices. These forces were measured directly utilizing a highly sensitive balance scale. It was verified that depending on the orientation of the variation of the angle between the electrodes, the performance of the actuator may be decreased or increased when compared to a DBD on a flat dielectric plate more commonly investigated in literature. The manner in which the ionic wind flows over the actuators was also explored in the effort to elucidate the influence of the variation of the angle between the electrodes on the response force generated by the device. Results demonstrated that the response forces generated by the actuators may be improved by up to 50% compared to the actuator configuration on a flat dielectric plate commonly investigated. These results indicate the potential available to advance plasma technology by physically manipulating these devices to increase the performances of the actuators.     

Ancillary Ligand Effects on Heteroleptic IrIII Dye in Dye-Sensitized Photocatalytic CO2 Reduction: Photoaccumulation of Charges on Arylated Bipyridine Ligand and Its Control on Catalytic Performance

Herein, we report the synthesis, and photochemical and -physical properties, as well as the catalytic performance, of a series of heteroleptic Ir^III photosensitizers (IrPSs), [Ir(C^N)₂(N^N^Aryl)]⁺, possessing ancillary ligands that are varied with aryl-substituents on bipyridyl unit [C^N=(2-pyridyl)benzo[b]thiophen-3-yl (btp); N^N^Aryl=4,4′-Y₂-bpy (Y=−Ph or −PhSi(Ph)₃]. We found that the π-extension of bipyridyl ligand by aryl-substitution put bipyridyl ligand in use as an electron relay unit that performed charge accumulation before delivering to the catalytic center, greatly improving the overall CO₂-to-CO conversion activities. In a typical run, the aryl-substituted IrPS ( ^{t Bu} IrP-Ph^Si )-sensitized homogeneous systems (IrPS+Re^I catalyst) gave a turnover number of 1340 (Φ_CO=24.2 %) at the early stage of photolysis (<5 h). This study demonstrates that the π-character modulation on the ancillary bipyridyl ligand is critical for forthcoming catalytic performance.     

Constitutive equation with fractional derivatives for the generalized UCM model

A fundamental problem on the constitutive equation with fractional derivatives for the generalized upper convected Maxwell model (UCM) is studied. The existing investigations on the constitutive equation are reviewed and their limitations or deficiencies are highlighted. By utilizing the convected coordinates approach, a mathematically rigorous constitutive equation with fractional derivatives for the generalized UCM model is proposed, which has an explicit expression for the stress tensor. This model can be reduced to the linear generalized Maxwell model with fractional derivatives, the UCM model and some other existing models. In addition, the rheological properties of this proposed model in the start-up of simple shear and elongation flows are investigated. It is shown that this generalized UCM model can describe the various stress evolution processes and the strain hardening effect of the viscoelastic fluids.     

Probing enantioselectivity on chirally modified Cu(110), Cu(100), and Cu(111) surfaces

Temperature programmed desorption methods have been used to probe the enantioselectivity of achiral Cu(100), Cu(110), and Cu(111) single crystal surfaces modified by chiral organic molecules including amino acids, alcohols, alkoxides, and amino-alcohols. The following combinations of chiral probes and chiral modifiers on Cu surfaces were included in this study: propylene oxide (PO) on L-alanine modified Cu(110), PO on L-alaninol modified Cu(111), PO on 2-butanol modified Cu(111), PO on 2-butoxide modified Cu(100), PO on 2-butoxide modified Cu(111), R-3-methylcyclohexanone (R-3-MCHO) on 2-butoxide modified Cu(100), and R-3-MCHO on 2-butoxide modified Cu(111). In contrast with the fact that these and other chiral probe/modifier systems have exhibited enantioselectivity on Pd(111) and Pt(111) surfaces, none of these probe/modifier/Cu systems exhibit enantioselectivity at either low or high modifier coverages. The nature of the underlying substrate plays a significant role in the mechanism of hydrogen-bonding interactions and could be critical to observing enantioselectivity. While hydrogen-bonding interactions between modifier and probe molecule are believed to induce enantioselectivity on Pd surfaces (Gao, F.; Wang, Y.; Burkholder, L.; Tysoe, W. T. J. Am. Chem. Soc. 2007, 129, 15240-15249), such critical interactions may be missing on Cu surfaces where hydrogen-bonding interactions are believed to occur between adjacent modifier molecules, enabling them to form clusters or islands.