Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Application of pressure sensitive paint measurement to a low-solidity cascade diffuser of a transonic centrifugal compressor

A pressure sensitive paint (PSP) measurement has been known as a pressure field measurement technique based on the oxygen quenching phenomenon of luminescence of specific luminophores. A PSP measurement was applied for pressure field measurement in a low-solidity circular cascade diffuser of a single-stage transonic centrifugal compressor with 5 in pressure ratio for HFC134a gas. The oxygen concentration was about 500 ppm. Ru (bath-phen) was adsorbed on a silica-gel thinlayer chromatography sheet, and the sheet was pasted onto the side-wall between the cascade vanes. A drastic change in luminescent intensity was recognized during a surge condition. Also the pressure variations based on luminescent intensity agreed well with the pressure fluctuations measured using a semiconductor pressure sensor with high-frequency-response. It was shown that a PSP measurement worked well to investigate the unsteady pressure fields in a circular cascade diffuser of a transonic centrifugal compressor. Moreover, the time response of PSP becomes clear as a problem to be overcome for the present.     

Dynamic and subjective responses of seated subjects exposed to simultaneous vertical and fore-and-aft whole-body vibration: The effect of the phase between the two single-axis components

Subjective and dynamic responses of seated subjects exposed to simultaneous vertical and fore-and-aft sinusoidal whole-body vibration were investigated. The effect of the phase difference between the vertical and the fore-and-aft vibration on the responses was of a particular interest in this study. Fifteen subjects were exposed to dual-axis vibrations at six frequencies (2.5-8 Hz) and at eight phases between the two single-axis components (0-315°). The magnitude of vibration in each axis was constant at 0.7 m s⁻² rms. Discomfort caused by vibration was measured by the method of magnitude estimation. The motion of the body were measured at the head and three locations along the spine with accelerometers attached to the body surface. The most significant effect of the phase between the two single-axis components on the discomfort was observed at 5 Hz: about 40% difference in the median discomfort estimate caused by changing the phase. The transmissibilities from vertical seat vibration to vertical motions of the spine varied from 0.5 to 2.0 by changing the phase between the two single-axis components at frequencies from 2.5 to 5 Hz. The effect of the phase observed in the dynamic response was not predicted by the superposition of the responses to each single-axis vibration. The discomfort caused by the dual-axis vibration tended to be correlated better with the combinations of the dynamic responses measured in the two axes than with the dynamic responses in a single axis.     

Surface-enhanced Raman scattering from oleate-stabilized silver colloids at a liquid/liquid interface.

Oleate-stabilized silver colloids of 5-nm-diameter were adsorbed to a toluene/water interface, and surface enhanced Raman scattering (SERS) spectra from these colloids were measured under the total internal reflection (TIR) condition. From the observed spectra, we examined the states of oleate ions and toluene molecules on silver colloids at the liquid/liquid interfacial region. The TIR-SERS spectra of oleate ions showed stronger peaks of the carboxylate group and the ethylene group than those of alkyl chains. From these results, it was found that the oleate ions were adsorbed on the silver surface in two different ways at the liquid/liquid interface; the carboxylate group adsorbed in the organic phase side, while the ethylene group adsorbed in the aqueous phase side. The shifts of the toluene in the interfacial SERS spectra were identical to those of bulk toluene, though the relative intensities among the peaks were not same. This result suggested that the toluene was adsorbed with a weak interaction, but was significantly enhanced by the local electromagnetic field at the colloid surface.     

High-throughput characterization of local conductivity of Nd0.9Ca0.1Ba2Cu3O7−δ thin film by the low-temperature scanning microwave microscope

We developed a scanning microwave microscope (SμM) designed for high-throughput electric-property screening as well as for rapid construction of electronic phase diagrams at low temperatures. As a sensor probe, we used a high-Qλ/4 coaxial cavity resonator to which a thin needle with ball-tip end was attached. The sensor module was mounted on the low-temperature XYZ stage, which allowed us to map out the change of resonance frequency and quality factor due to the local tip-sample interaction at low temperatures. From the measurements of combinatorial thin films, such as Ti_1−xCo_xO_2−δ and Nd_0.9Ca_0.1Ba₂Cu₃O_7−δ (NCBCO), it was demonstrated that this SμM system has enough performance for the high-throughput characterization of sample conductance under variable temperature conditions.     

Novel dinucleoside phosphotriester unit conjugated with an intercalative moiety in a stereospecific manner enhances thermal stability of an alternate-stranded triple helix

A novel phosphoramidite synthon of a dinucleoside phosphotriester unit bearing an intercalative moiety at its internucleotide linkage in a stereospecific manner was prepared and successfully incorporated into the middle portion of α-β chimeric oligoDNA. One of the resulting stereoisomeric chimera DNAs strongly enhances the thermal stability of an alternate-stranded triplex formed between the chimera and a double-stranded DNA.