Novel soft chemical method for optically transparent Ru(bpy)3-K4Nb6O17 thin film

A unique guest-guest ion exchange method was developed for preparing a thin film of a nano-layered K(4)Nb(6)O(17).3H(2)O that possesses both (1) optical transparency and (2) ion-exchangeability under ambient conditions without calcination at high temperature. An optically transparent Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin film, a photoresponsive electrode, was successfully prepared by the guest-guest exchange method by use of the intercalation compound MV(2+)-K(4)Nb(6)O(17) as a precursor. The optically transparent Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin films have been characterized by X-ray diffraction, SEM, AFM, IR, and UV spectroscopies, as well as elemental analysis. The electrochemical behavior of the ITO/Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin film electrode was studied; it also exhibits swift photoresponse in the visible region.     

Reversible light-driven structural changes between the mono- and bilayer stacking alignments in 4-octadecyloxystilbazolium arylcarboxylate films

The present investigation deals with the light-driven morphological changes in multilamella films of N-methyl-4-octadecyloxystilbazolium arylcarboxylates (C18OStz+X-) cast on glass slides. The results of XRD analysis show a photostimulated layer expansion and shrinkage of the stacked thin films along the c-axis under alternative illumination at >350 and 254 nm, respectively. It was revealed that such lamellar changes could be switched either way by a reversible transformation between the mono- and bilayer units in these stacked multilamella films. Moreover, such controlled structural adjustments in the alignment could be initiated by the photocyclodimerization of the stilbazolium moieties of the arylcarboxylate salts; i.e., a monolayer-to-bilayer transformation could be induced at a stage of only 10% cyclodimer formation. The photoinduced patterning on the surface of the films was also analyzed by SEM and fluorescence microscopic investigations.     

Reversible color changes in lamella hybrids of poly(diacetylenecarboxylates) incorporated in layered double hydroxide nanosheets

The present study is an investigation of a reversible thermal color change induced in lamella hybrids of poly(diacetylenecarboxylates) incorporated in layered double hydroxide (LDH) nanosheets. These poly-[m,n]/LDH hybrids prepared by the photo- or gamma-ray-induced polymerization of diacetylenecarboxylates, i.e., CH(3)(CH(2))(m)()(-)(1)CC-CC(CH(2))(n)()(-)(1)CO(2)(-) (mono-[m,n]), and intercalated in LDH lamella sheets, were observed to develop colors ranging from yellow to blue. The change in color was found to depend greatly on the alkyl carbon numbers of the mono-[m,n] (m,n = 10,11; 5,11; 10,5; 16,1) values. Moreover, the conformational alignment of the mono-[m,n] within the LDH was observed to be a crucial factor in color development, which was greatly affected by the intercalation degrees and extent of poly(ene-yne) linkage elongation of the polymers. For the poly-[m,n]/LDH hybrids investigated, a reversible color change was found to occur repeatedly and remarkably for the poly-[10,11]/LDH hybrid. This color change occurred at temperatures between ca. 20 and 80 degrees C back and forth from purple red to bright orange, in stark contrast to the irreversible color change for poly-[10,11] without LDH. Moreover, DSC and Raman spectroscopic studies of the LDH hybrids showed that the thermochromic temperature corresponded to the phase transition temperature of 80 degrees C. XRD analysis also indicated that the poly-[m,n]/LDH hybrid could retain its lamella structure during such thermochromic color changes, enabling conformational recovery in the polymer chains by a cooling down of the hybrids to temperatures lower than the transition temperature, while the nonhybrid poly-[10,11] powders exhibited an irreversible color change at 60 degrees C, above which the polymer powder turned amorphous.     

Characteristic curved structure derived from collagen-containing tubular giant vesicles under static magnetic field

Collagen-containing tubular giant vesicles (Col–tGVs) under a high static magnetic field were found to constitute characteristic curved structures (e.g. circular, 8-figure, and hairpin-loop), which were sustained by polymerization of collagen units inside the tGV. We ascribed the formation of these structures to the elasticity of the tGV and to the competing diamagnetic anisotropies between collagen and the tGV. These curved structures can be well expressed by the equation of elastica.     

S0 ring-puckering potential energy function for coumaran

With the aid of a reported inversion splitting value, the far-infrared spectrum resulting from the ring-puckering vibration of coumaran has been reassigned and the one-dimensional potential energy function has been determined. The barrier to planarity is 155 +/- 4 cm(-1) and the dihedral angle is 25 degrees . These results agree well with the millimeter wave spectra values of 152 cm(-1) and 23 degrees , which utilized different data and a different type of potential function for the calculations. The MP2/cc-pvtz ab initio values of 238 cm(-1) and 26.5 degrees agree more poorly. If the benzene ring is assumed to remain rigid, the calculated barrier drops to 204 cm(-1). The puckering potential functions for the ring-flapping and ring-twisting vibrationally excited states were also determined and the barriers were found to be 149 and 156 cm(-1), respectively.     

Asymmetric benzoin condensation promoted by chiral triazolium precatalyst bearing a pyridine moiety

Chiral triazolium salts bearing a pyridine ring were developed as N-heterocyclic carbene precursors. In the presence of the chiral triazolium salt and a base, the catalytic asymmetric benzoin condensation proceeded to afford the product in high level of chemical yield and enantioselectivity. A wide range of aromatic aldehydes were applicable to this reaction.     

A function space model approach to the rational evaluation subgroups

Let f : U → X be a map from a connected nilpotent space U to a connected rational space X. The evaluation subgroup G _*(U, X; f), which is a generalization of the Gottlieb group of X, is investigated. The key device for the study is an explicit Sullivan model for the connected component containing f of the function space of maps from U to X, which is derived from the general theory of such a model due to Brown and Szczarba (Trans Am Math Soc 349, 4931–4951, 1997). In particular, we show that non Gottlieb elements are detected by analyzing a Sullivan model for the map f and by looking at non-triviality of higher order Whitehead products in the homotopy group of X. The Gottlieb triviality of a fibration in the sense of Lupton and Smith (The evaluation subgroup of a fibre inclusion, 2006) is also discussed from the function space model point of view. Moreover, we proceed to consideration of the evaluation subgroup of the fundamental group of a nilpotent space. In consequence, the first Gottlieb group of the total space of each S ¹-bundle over the n-dimensional torus is determined explicitly in the non-rational case.