PIV and LDA measurements of secondary flow in a meandering channel for overbank flow

Secondary flow in a compound meandering channel with straight floodplain banks for overbank was investigated by a visualization method and velocity measurement using three-component laser Doppler anemometor (LDA). The secondary flow in a cross section was visualized by the neutral buoyant tracer method with a submergible video camera. Secondary flow vectors in a cross section were obtained by using PIV software with captured frames from video source through PC and also by LDA measurements. From the comparison of the PIV and LDA results, it is found that PIV data show good agreement in quality with LDA measurements when the secondary flow is strong and stable as shown in this paper.     

Polymerization of bisdithiafulvenes with conjugated spacers using oxidative dimerization

Novel vinylogous tetrathiafulvalene (TTF) containing polymers ( 13 and 14 ) were prepared by the oxidative dimerization polymerization of bisdithiafulvenes. The obtained polymers were soluble in common organic solvents such as CHCl₃. The structures of the polymers were confirmed by ¹H NMR and cyclic voltammetry analysis. The number‐average molecular weights of 13 and 14 were estimated from gel permeation chromatography to be 3600 and 3800, respectively. Through the introduction of phenylene or phenylene–vinylene spacers, distortion between dialkoxybenzene and vinylogous TTF units was effectively prevented according to ultraviolet–visible analysis. The polymers exhibited a strong electron‐donating property investigated by cyclic voltammetry analysis. Chemical doping by CF₃SO₃H gave doped polymers having a cationic radical and a dication of a vinylogous TTF unit. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2027–2033, 2006     

Synthesis and characterization of cis‐polybutadiene‐block‐syn‐polystyrene copolymers with a cyclopentadienyl titanium trichloride/modified methylaluminoxane catalyst

This article reports a practical method for preparing cis‐polybutadiene‐block‐syn‐polystyrene (cis‐PB‐b‐syn‐PS) copolymers with long crystallizable syndiotactic polystyrene (syn‐PS) segments chemically bonded with high cis‐1,4‐polybutadiene segments through the addition of styrene (ST) to a cis‐specific 1,3‐butadiene (BD) living catalyst composed of cyclopentadienyl titanium trichloride (CpTiCl₃) and modified methylaluminoxane (MMAO). The incorporation of ST into the living polybutadiene (PB) precursor remarkably depended on the polymerization temperature. A low temperature (?20 °C) suppressed the rate of ST incorporation, but a high temperature (50 °C) tended to decompose the livingness of the active species and enhance the rate of the aspecific ST polymerization initiated by MMAO. Consequently, temperatures of 0–25 °C seemed to be best for this copolymerization system. Because of the absence of ST livingness, the final products contained not only the block copolymer but also the homopolymers. Attempts to isolate the block copolymer were carried out with common solvent fractionation techniques, but the results were not sufficient. Cross‐fractionation chromatography was, therefore, used for the isolation of the cis‐PB‐b‐syn‐PS copolymer. The presence of long syn‐PS segments was confirmed by the observation of a strong endothermic peak at 260 °C in the differential scanning calorimetry curve. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2698–2704, 2004     

Development of a surface-reaction system in a nanoliter droplet made by an ink-jet microchip.

A surface-reaction system in a nanoliter water pool using an ink-jet microchip was developed. The reaction system in the nanodroplets formed on a poly(dimethylsiloxane) (PDMS) coated glass slide increased the diffusion-controlled reaction without using a nano-pump, specialized connector or highly sensitive detector. When nanoliter droplets were placed on the PDMS surface with a distance of 100 microm between them by the ink-jet microchip, the repeatabilities of the fluorescence intensity were 2.9% RSD (n = 7). The used ink-jet microchip had 4 different injection ports, and the distance between the ports was 0.995 mm. It was necessary to correct the distance in order to mix or dilute samples in a small droplet. The correction was successfully performed by moving the X-Y stage using inhouse-made software. A linear relationship was obtained between the Resorufin concentrations and the fluorescence intensity. We applied this system to an enzyme-linked immunosorbent assay (ELISA) for immunoglobulin A (IgA), and observed a difference in the fluorescence intensity derived from the amount of IgA (blank, 6.25 ng/mL, 12.5 ng/mL). These results show the usefulness of the open-type micro-analytical systems proposed by us.     

Synthesis and properties of photocurable biodegradable multiblock copolymers based on poly(ε‐caprolactone) and poly(L‐lactide) segments

Photocurable biodegradable multiblock copolymers were synthesized from poly(ε‐caprolactone) (PCL) diol and poly(L ‐lactide) (PLLA) diol with 4,4′‐(adipoyldioxy)dicinnamic acid (CAC) dichloride as a chain extender derived from adipoyl chloride and 4‐hydroxycinnamic acid, and they were characterized with Fourier transform infrared and ¹H NMR spectroscopy, gel permeation chromatography, wide‐angle X‐ray diffraction, differential scanning calorimetry, and tensile tests. The copolymers were irradiated with a 400‐W high‐pressure mercury lamp from 30 min to 3 h to form a network structure in the absence of photoinitiators. The gel concentration increased with time, and a concentration of approximately 90% was obtained in 90–180 min for all the films. The photocuring hardly affected the crystallinity and melting temperature of the PCL segments but reduced the crystallinity of the PLLA segments. The mechanical properties, such as the tensile strength, modulus, and elongation, were significantly affected by the copolymer compositions and gel concentrations. Shape‐memory properties were determined with cyclic thermomechanical experiments. The CAC/PCL and CAC/PCL/PLLA (75/25) films photocured for 30–120 min showed good shape‐memory properties with strain fixity rates and recovery rates of approximately 100%. The formation of the network structure and the crystallization and melting of the PCL segments played very important roles for the typical shape‐memory properties. Finally, the degradation characteristics of these copolymers were investigated in a phosphate buffer solution at 37 °C with proteinase‐k and Pseudomonas cepacia lipase. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2426–2439, 2005     

Crystallographic report: Dichloro[bis(1‐methylimidazole‐2)disulfide]zinc(II)

The Zn center in [ZnCl₂(L‐S‐S‐L)], where L‐S‐S‐L = bis(1‐methylimidazole‐2)disulfide, adopts a tetrahedral configuration defined by two Cl atoms and two N atoms from L‐S‐S‐L, which was obtained by in situ oxidation of 1‐methylimidazole‐2‐thione. Copyright © 2005 John Wiley & Sons, Ltd.     

Anomalous enhancement of DD reaction in Pd and Au/Pd/PdO heterostructure targets under low-energy deuteron bombardment

Yields of protons emitted in the D+D reaction in Pd, Au/Pd/PdO, Ti, and Au foils are measured by a d E-E counter telescope for bombarding energies between 2.5 and 10 keV. The experimental yields are compared with those predicted from a parametrization of the cross section and stopping power at higher energies. It is found that for Ti and Au target the enhancement of the D(d,p)T reaction is similar to that observed with a deuterium gas target (several tens of eV). The dependence of the yields on the bombarding energy corresponds well to the screening potential parameters U _s=250±15 eV for Pd and 601 ±23 eV for Au/Pd/PdO. Possible models of the enhancement obtained are discussed. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 11, 785–790 (10 December 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Effects of cation- or oxide ion-defect on conductivities of apatite-type La–Ge–O system ceramics

A series of apatite-type La–Ge–O ceramics were prepared and their cation-defect at the 4f+6h sites and oxide ion-defect at 2a site were investigated. In La_xGe₆O_12+1.5x ceramics of x=6–12, the higher conductivities were obtained in the region of apatite composition, La_x(GeO₄)₆O_1.5x−12 (x=8–9.33), and the highest conductivity was achieved for La₉(GeO₄)₆O_1.5 (x=9), where the number of cation (La³⁺) occupying the 4f+6h sites is 9 and the number of oxide ion occupying the 2a site is 1.5. The ceramics with cation- and oxide ion-defects were La_9−0.66xSr_x(GeO₄)₆O_1.5 (x=0–1), La_9−1.33xZr_x(GeO₄)₆O_1.5 (x=0–1), La_9−xSr_x(GeO₄)₆O_1.5−0.5x (x=0–3), La_9−xZr_x(GeO₄)₆O_1.5+0.5x (x=0–1), La_x(GeO₄)_3x−21(AsO₄)_27−3xO_1.5 (x=0–3), La_x(GeO₄)_33−3x(AlO₄)_3x−27O_1.5 (x=0–3), La₉(GeO₄)_6−x (AlO₄)_xO_1.5−0.5x (x=0–3), La₉(GeO₄)_6−x(AsO₄)_xO_1.5+0.5x (x=0–1), La_9.33−xSr_x(GeO₄)₆O_2−0.5x (x=0–1.2) and La_x(GeO₄)_4.5(AlO₄)_1.5O_1.5x−12.75 (x=8.8–9.83), which were prepared by the partial substitution of La³⁺and GeO₄⁴⁻of the basic apatite La₉(GeO₄)₆O_1.5 with Sr²⁺ or Zr⁴⁺ and AlO₄⁵⁻ or AsO₄³⁻. Such substitutions lowered the conductivity of La₉(GeO₄)₆O_1.5. These results were discussed by the electrostatic interaction between Sr²⁺, Zr⁴⁺, AlO₄⁵⁻ or AsO₄³⁻ and oxide ion as a conductive species.     

Copolymerization of 3‐buten‐1‐ol and propylene with an isospecific zirconocene/methylaluminoxane catalyst

The copolymerization of propylene and 3‐buten‐1‐ol protected with alkylaluminum [trimethylaluminum (TMA) or triisobutylaluminum] was conducted with an isospecific zirconocene catalyst [rac‐dimethylsilylbis(1‐indenyl)zirconium dichloride], combined with methylaluminoxane as a cocatalyst, in the presence of additional TMA or H₂ as the chain‐transfer reagent if necessary. The results indicated that end‐hydroxylated polypropylene was obtained in the presence of the chain‐transfer reagents because of the formation of dormant species after the insertion of the 3‐buten‐1‐ol‐based monomer followed by chain‐transfer reactions. The selectivity of the chain‐transfer reactions was influenced by the alkylaluminum protecting the comonomer and the catalyst structure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5600–5607, 2004     

Synthesis of (±)-penlanfuran

The title compound was efficiently synthesized from 3-furoic acid and 3-bromoanisole via the Birch reduction.