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.     

Alkylation‐, Heating‐, and Doping‐Induced Emission Enhancement of a Polyaromatic Tube in the Solid State

A polyaromatic tube with a subnanometer‐sized cavity was efficiently prepared on a gram‐scale through the stereo‐controlled cyclotrimerization of a diphenylanthracene derivative as a key step. The facile exterior alkylation of the polyaromatic framework leads to a moderately fluorescent tube (R=‐OC₁₀H₂₁; Φ_F=20 %) in the solid state. The emission intensity of the solid‐state alkyl‐substituted tube is remarkably enhanced upon heating (up to 1.6 times, Φ_F=31 %) as well as doping with fluorescent dyes (up to 4.2 times, Φ_F=83 %) through efficient energy transfer.     

Electrostatic Assembly of Dendrimer Electrolytes: Negatively and Positively Charged Dendrimer Porphyrins

Carboxylate and ammonium functionalities—32 of each— facilitate electrostatic interaction between oppositely charged dendrimer electrolytes and porphyrin cores, which leads in protic media to a supramolecular, fluorescence-active aggregate of two chromophores that communicate and have a predictable topology (see drawing on the right; A=acceptor, D=donor). In contrast to the complexation of linear polyelectrolytes, the contact area for the two dendrimer molecules is very limited, just as one would expect for an assembly of spherical molecules.     

Complexation and chiral recognition thermodynamics of 6-amino-6-deoxy-beta-cyclodextrin with anionic, cationic, and neutral chiral guests: counterbalance between van der Waals and coulombic interactions

The stability constant (K), standard free energy (Delta G degrees), enthalpy (Delta H degrees), and entropy changes (T Delta S degrees) for the complexation of 6-amino-6-deoxy-beta-cyclodextrin with more than 50 negatively or positively charged as well as neutral guests, including 22 enantiomer pairs, have been determined in aqueous phosphate buffer (pH 6.9) at 298.15 K by titration microcalorimetry. The thermodynamic parameters obtained in this study and the relevant data for native beta-cyclodextrin indicate that the complexation and chiral discrimination behavior of the cationic host with charged guests are governed by the critical counterbalance between the electrostatic interactions of the charged groups in host and guest and the conventional intracavity interactions of the hydrophobic moiety of guest, such as hydrophobic, van der Waals, solvation/desolvation, and hydrogen-bonding interactions.     

Optimum packing density and crystal structure of tin-doped indium oxide thin films for high-temperature annealing processes

The influence of high-temperature annealing on the electrical properties and microstructure of tin-doped indium oxide (ITO) thin films was investigated as a function of oxygen gas flow ratio to argon gas during the sputtering deposition. The ITO thin films were annealed at 500 °C in air after the deposition. It was found that the ITO thin films, which were deposited in relatively low oxygen gas flow ratio, exhibited high Hall mobility and low-resistivity after the annealing. Furthermore, the X-ray reflectivity and diffraction measurement revealed that the ITO thin film with low-resistivity after annealing exhibited high packing density, smooth surface and low crystallization degree. It can be considered that the carrier electron scattering was suppressed with increasing in the packing density of the ITO thin film; as a result, the Hall mobility and resistivity were improved.     

A new method for the synthesis of novel 1,2,4-triazolo[3,4-f][1,2,4]triazines

Novel compounds 8-(quinoxalin-2-yl)-1,2,4-triazolo[3,4-f][1,2,4]triazines 3a,b were obtained by a new annulation method in the 1,2,4-triazine synthesis.     

Synthesis and tautomeric behavior of 3-(pyrazolylhydrazonomethyl)-2-oxo-1, 2-dihydroquinoxalines. Specification of hydrazone imine and diazenyl enamine forms

3-(Pyrazolylhydrazonomethyl)-2-oxo-1, 2-dihydroquinoxalines were synthesized, and their tautomer ratios between hydrazone imine and diazenyl enamine forms were specified by pmr spectral data.     

Structure and properties of ethyl (2-benzimidazolyl)cyanoacetimidate

The revision of the structure of hydrolytic product from 4-cyano-1-ethoxypyrirnido[1,6-a]benzimidazole (1) and the properties of ethyl (2-benzimidazolyl)cyanoacetimidate (3a) are described.     

Enhancement in sensitivity of a blood perfusion parameter for frame-rate analysis of bio-speckle image

We have previously presented a blood perfusion parameter by means of the spatial contrast of speckle patterns observed for blood perfusion in skin tissue and a blood vessel. This parameter permits us to visualize a relative blood perfusion distribution from a single speckle pattern. Therefore, it can estimate the blood perfusion with a frame rate of an imaging device employed. This parameter is, however, dependent on the speckle size and the condition of image processing of speckle patterns. In the present study, we estimated this condition with relation to the speckle size for obtaining high sensitivity and good linearity of the parameter to the blood perfusion. Experiments were conducted for ground-glass model, flow model and human wrist to investigate perfusion sensing characteristics of the present parameter.