Precise synthesis of a series of poly(4‐n‐alkylstyrene)s and their glass transition temperatures

Poly(4‐n‐alkylstyrene)s with six kinds of n‐alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and octyl groups covering wide molecular weight range from around 5 k to over 100 k were precisely synthesized by living anionic polymerizations. It was confirmed that all the polymers obtained have narrow molecular weight distribution, that is, M_w/M_n is all less than 1.1, by SEC. T_gs of all the polymers were estimated by DSC measurements and it turned out to be clear that their molecular weight dependence was well described by the Fox–Flory equations. Furthermore, it is evident that T_g monotonically decreases as a number of carbon atoms of n‐alkyl group is increased, though T_g values are all 20 K or more higher than those reported previously for the same polymer series. This is because backbone mobility increases by introducing longer n‐alkyl side groups with high mobility, while T_g difference in between this work and the previous one may due to the experimental conditions and also to the molecular weight range adopted. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 757–763     

Alkyl side chain length dependent compatibility of poly(4‐n‐alkylstyrene)s and 1,4‐rich polyisoprene blends

We investigated the compatibility of blends of 1,4‐rich polyisoprene (1,4‐PI) and poly(4‐n‐alkylstyrene)s with six kinds of n‐alkyl side groups, that is, methyl, ethyl, propyl, butyl, hexyl, and octyl focusing on carbon number of alkyl groups. Poly(4‐methylstyrene)/1,4‐PI blend was turned out to be immiscible at all temperature range adopted in this work and poly(4‐ethylstyrene)/1,4‐PI blend revealed UCST type phase behavior, while the others were found to be compatible. The phase diagrams of poly(4‐ethylstyrene)/1,4‐PI blends were obtained by optical microscopy, and the temperature dependence of the Flory‐Huggins interaction parameter χ has been estimated to be χ = ?0.036 + 24/T by applying lattice theory, where T is the absolute temperature. From this relationship χ value at room temperature (298 K) was calculated to be 0.045, the value is reasonably low for miscible polymers system. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1791–1797     

Triggered single-photon emission and cross-correlation properties in InAlAs quantum dot

Triggered single-photon generation from InAlAs quantum dot (QD) was demonstrated for the first time. Emitted photon energy coincides with high detection efficiency range of Si single-photon detectors, which is highly suitable for free-space communication. Single-QD spectroscopy and crossed photon correlation measurements unambiguously revealed that several emitting lines observed in a single mesa structure originated from the identical QD, and two temporary competing decay processes associated with neutral states and charged states were identified. Presence of the competing process is also inferred from an analysis of steady-state photoluminescence intensities. Formation process of charged exciton in QD is also discussed.     

Assessment of fluoroalkyltin compounds as fluorous Lewis acid catalysts

The synthesis of a variety of organotin compounds with 1H, 1H, 2H, 2H‐perfluorooctyl groups is reported, together with an improved method for the corresponding distannoxane. Unique properties of this compound are disclosed in terms of fluorophilicity and activity as a Lewis acid catalyst in comparison with other mono‐nuclear derivatives. A new criterion for obtaining high solubility in fluorocarbon solvents is presented. Copyright © 2003 John Wiley & Sons, Ltd.     

A non‐linear k–ε model with realizability for prediction of flows around bluff bodies

The incompressible flow around bluff bodies (a square cylinder and a cube) is investigated numerically using turbulence models. A non‐linear k–ε model, which can take into account the anisotropy of turbulence with less CPU time and computer memory then RSM or LES, is adopted as a turbulence model. In tuning of the model coefficients of the non‐linear terms are adjusted through the examination of previous experimental studies in simple shear flows. For the tuning of the coefficient in the eddy viscosity (=C_μ), the realizability constraints are derived in three types of basic 2D flow patterns, namely, a simple shear flow, flow around a saddle and a focal point. C_μ is then determined as a function of the strain and rotation parameters to satisfy the realizability. The turbulence model is first applied to a 2D flow around a square cylinder and the model performance for unsteady flows is examined focussing on the period and the amplitude of the flow oscillation induced by Karman vortex shedding. The applicability of the model to 3D flows is examined through the computation of the flow around a surface‐mounted cubic obstacle. The numerical results show that the present model performs satisfactorily to reproduce complex turbulent flows around bluff bodies. Copyright © 2003 John Wiley & Sons, Ltd.     

A descent method for submodular function minimization

We show a descent method for submodular function minimization based on an oracle for membership in base polyhedra. We assume that for any submodular function f: ?→R on a distributive lattice ?⊆2 ^V with ?,V∈? and f(?)=0 and for any vector x∈R ^V where V is a finite nonempty set, the membership oracle answers whether x belongs to the base polyhedron associated with f and that if the answer is NO, it also gives us a set Z∈? such that x(Z)>f(Z). Given a submodular function f, by invoking the membership oracle O(|V|²) times, the descent method finds a sequence of subsets Z ₁,Z ₂,···,Z _k of V such that f(Z ₁)>f(Z ₂)>···>f(Z _k )=min{f(Y) | Y∈?}, where k is O(|V|²). The method furnishes an alternative framework for submodular function minimization if combined with possible efficient membership algorithms. Received: September 9, 2001 / Accepted: October 15, 2001?Published online December 6, 2001     

The effects of the homogeneity of non-crystalline Pb---Ti---O gels on the complex thermal processes leading to PbTiO3 formation

The effects of the homogeneity of precursor non-crystalline Pb---Ti---O gels on their transformation to crystalline PbTiO₃ were studied. Hydrous gels were prepared via two different routes, i.e., (i) mixing two unitary sols (MS), and (ii) co-precipitation (CP). Mechanical pretreatment was also carried out, primarily for the purpose of homogenization. The local homogeneity was evaluated by elementary microanalysis using a transmission electron microscope. The process of ball-milling the MS gel for 3 h improved its homogeneity only slightly. However, the homogeneity of the ball-milled MS gel suddenly increased to that of the CP gel on subsequent heating to a temperature as low as 483 K. This type of thermal homogenization was not observed for the unground MS gel. The evaporation of lead monoxide on further heating to 1023 K was also suppressed by preliminary ball-milling. All these results suggest that the ionic migration and the formation of Pb---O---Ti bonds in the gels take place during the mechanical activation with the aid of OH groups.     

Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles

Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3‐cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16π conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO–LUMO gap and enhanced the near IR absorption property.     

Fabrication of column chip made of PMMA for μFIA

We proposed a low cost fabrication procedure of a poly(methylmethacrylate) (PMMA) column chip. 3D microchannel structure consisting of four columns in a chip for a mother die was fabricated using dry film photoresist and photolithography technique. Electroforming was applied to the mother die in order to obtain a Ni mold, then, the pattern was transferred to PMMA by hot press. The column had a dam structure to keep enzyme-immobilized microbeads with volume of 640 nL. The column chip was applied for a micro flow injection analysis (μFIA) system. For a demonstration, we measured lactose using two columns in series. One column was set on upper stream and filled with chitosan microbeads immobilized with β-galactosidase, the other was on downstream and filled with the beads immobilized with glucose oxidase. The lactose detection was accomplished less than 90s after the sample injection. The biosensing system also showed a high performance for lactose detection in wide range of 1 μM to 1mM. These results show that the column chip and our microfluidic biosensing system have the potential to assist minuaturization with small sample volume and short determination time for a sequential analysis.