Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Vacuum‐driven fluid manipulation by a piezoelectric diaphragm micropump for microfluidic droplet generation with a rapid system response time

Recently, we developed a convenient microfluidic droplet generation device based on vacuum‐driven fluid manipulation with a piezoelectric diaphragm micropump. In the present study built on our previous work, we investigate the influence of settings applied to the piezoelectric pump, such as peak‐to‐peak drive voltage (V_p‐p) and wave frequency, on droplet generation characteristics. Stepwise adjustments to the drive voltage in ±10‐V_p‐p increments over the range of 200?250 V_p‐p during droplet creation revealed that the droplet generation rate could be reproducibly controlled at a specific drive voltage. The droplet generation rate switched within <0.5 s after the input of a new voltage. Although the droplet generation rate depended on the drive voltage, this setting had almost no influence on droplet size. The frequency over the selected range (50?60 Hz) did not markedly influence the droplet generation rate or droplet size. We show that the current fluid manipulation system can be conveniently used for both droplet generation and for rapid droplet reading, which is required in many microfluidic‐based applications.     

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     

Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

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.     

Silicon-Based Integrated Optic Pressure Sensor Using Intermodal Interference between TM-Like and TE-Like Modes

In this paper, a silicon-based integrated optic pressure sensor using an intermodal interference between the fundamental TM-like and TE-like modes is described. The sensor consists of a micromachined rectangular diaphragm and a straight polystyrene optical waveguide passing over the diaphragm. Its sensitivity is theoretically known to be strongly dependent on the position of the waveguide over the diaphragm. To experimentally investigate such dependence, we fabricated a sensor with a 1.2 mm ×10 mm ×20 μm diaphragm, over which waveguides were placed at 50 μm intervals. The measured phase sensitivity was 98 mrad/kPa for the waveguide nearest to the diaphragm edge. The measurement was also carried out for the other waveguides. As theoretically expected, the largest sensitivity was obtained for the waveguide nearest to the edge.     

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.