LCST-type liquid-liquid phase separation behaviour of poly(ethylene oxide) derivatives in an ionic liquid

We present a new series of polymer-ionic liquid solutions exhibiting LCST-type liquid-liquid phase separation behaviour, and reveal their phase behaviour and intermolecular interactions based on phase diagrams and NMR analysis.     

Surface-enhanced infrared absorption spectroscopic studies of adsorbed nitrate, nitric oxide, and related compounds 2: Nitrate ion adsorption at a platinum electrode

The adsorbed species formed from the nitrate ion were examined using surface-enhanced infrared absorption spectroscopy (SEIRAS). The main band was observed at 1547-1568 cm-1 at 0.2 V in 0.01 M NaNO3 + 0.1 M HClO4. Although this band is close to that assigned to the adsorbed NO in the literature, it is assigned to the N=O stretching vibration of the chelating bidentate form of nitrate for the following reasons. (i) Nitrate gives a single band, while NO has three bands independent of the coverage. (ii) The band intensity remained constant in the potential range from 0.1 to 0.6 V, while that of the bridged NO at around 1600 cm-1 decreased in this range. (iii) The rate constants for the reduction and/or desorption at negative potentials are about 3 times higher than those of the bridged NO. (iv) The adsorbed species from nitrate is replaced with CO more easily than the bridged NO.     

Mechanical characteristics of hydrogenated natural rubber vulcanizates

Mechanical properties of partially hydrogenated natural rubber (HNR) vulcanizates were evaluated regarding their chemical structure and crystallizable nature of HNR, and are reported here, to the best of our knowledge, for the first time. HNRs of three levels of hydrogenation (20.6, 29.0, and 40.6 mol%) were successfully prepared by the chemical modification of natural rubber (NR) latex using N₂H₄ and H₂O₂ as reagents, in a sufficient amount for preparing sulfur‐crosslinked samples to be subjected to mechanical and structural measurements. The three HNR vulcanizates were found to be crystallizable upon stretching; it is noted that even 40.6 mol% hydrogenation did not prevent HNR vulcanizates from crystallization upon stretching, while their onset strain of crystallization was higher than that of NR vulcanizate. The hysteresis loss and residual strain up to a stretching ratio of 2 for the HNR vulcanizates tended to become larger with the increase in the degree of the hydrogenation. Tensile and dynamic mechanical properties of 20.6 mol% hydrogenated HNR vulcanizate were comparable to those of NR vulcanizate. From differential scanning calorimetry and temperature dispersion of dynamic modulus or loss, the glass transition temperatures of HNR vulcanizates were found to be almost the same as that of NR vulcanizate, which is also notable. The thermal stability of HNR vulcanizates was better than that of NR vulcanizate. Thus, this chemical modification seems to give a promising NR derivative whose properties can be equivalent or even better than the mother polymer. Copyright © 2008 John Wiley & Sons, Ltd.     

Infrared transmission of (R2O OR R’O)–(TiO2, Nb2O5 OR Ta2O5)-Al2O3 glasses

The new families of aluminate glasses obtained by the present authors from their melts in the systems K₂O–Ta₂O₅–Al₂O₃, Na₂O–K₂O–Ta₂O₅–Al₂O₃, K₂O –Cs₂O– Ta₂O₅–Al₂O₃, K₂O–Nb₂O₅–Al₂O₃, Na₂Oz.sbnd;K₂O–TiO₂–Al₂O₃, BaO–TiO₂–Al₂O₃, BaO–ZrO₂–TiO₂–Al₂O₃ and Na₂O–K₂O–BaO–ZrO₂–Ta₂O₅–TiO₂ –Al₂O₃ showed high transmissions of visible and infrared (IR) radiation ranging from 0.4 to about 6 μm, as well as high refractive indices up to 2.0. Their physical and chemical properties such as glass-forming ability, softening temperature, hardness and hygroscopicity were comparable to conventional silicate glasses. These properties are useful for IR applications. The cause of the high IR transmission of the aluminate glasses was interpreted in terms of the masses of the constituent cations and the single bond strengths of the cations with oxygen ions.     

The Steric Effect in Preparations of Vanadium(II)/(III) Dinitrogen Complexes of Triamidoamine Ligands Bearing Bulky Substituents

The reactions of newly designed lithiated triamidoamines Li₃L^R (R = iPr, Pen, and Cy₂) with VCl₃(THF)₃ under N₂ yielded dinitrogen–divanadium complexes with a μ-N₂ between vanadium atoms [{V(L^R)}₂(μ-N₂)] (R = iPr (1) and Pen (2)) for the former two, while not dinitrogen–divanadium complexes but a mononuclear vanadium complex with a vacant site, [V(L^Cy2)] (R = Cy₂ (3)), were obtained for the third ligand. The V–N_N2 and N–N distances were 1.7655(18) and 1.219(4) Å for 1 and 1.7935(14) and 1.226(3) Å for 2, respectively. The ν(¹⁴N–¹⁴N) stretching vibrations of 1 and 2, as measured using resonance Raman spectroscopy, were detected at 1436 and 1412 cm^–1, respectively. Complex 3 reacted with potassium metal in the presence of 18-crown-6-ether under N₂ to give a hetero-dinuclear vanadium complex with μ-N₂ between vanadium and potassium, [VK(L^Cy2)(μ-N₂)(18-crown-6)] (4). The N–N distance and ν(¹⁴N–¹⁴N) stretching for 4 were 1.152(3) Å and 1818 cm⁻¹, respectively, suggesting that 4 is more activated than complexes 1 and 2. The complexes 1, 2, 3, and 4 reacted with HOTf and K[C₁₀H₈] to give NH₃ and N₂H₄. The yields of NH₃ and N₂H₄ (per V atom) were 47 and 11% for 1, 38 and 16% for 2, 77 and 7% for 3, and 80 and 5% for 4, respectively, and 3 and 4, which have a ligand L^Cy2, showed higher reactivity than 1 and 2.     

Stereo- and Enantioselective Synthesis of Propionate-Derived Trisubstituted Alkene Motifs

We report a new method for constructing propionate-derived trisubstituted alkene motifs in a stereoselective manner. 1-Substituted 1,1-di(pinacolatoboryl)-(E)-alk-2-enes are generated in situ from 1-substituted 1,1-di(pinacolatoboryl)alk-3-enes through ruthenium(II)-catalyzed double-bond transposition. These species undergo a chiral phosphoric acid catalyzed allylation reaction of aldehydes to produce the E isomers of anti-homoallylic alcohols. On the other hand, the corresponding Z isomers of anti-homoallylic alcohols are obtained when a dimeric palladium(I) complex is employed as the catalyst for this double-bond transposition. Thus, both E and Z isomers can be synthesized from the same starting materials. A B−C(sp²) bond remaining with the allylation product undergoes the Suzuki–Miyaura cross-coupling reaction to furnish a propionate-derived trisubstituted alkene motif in a stereo-defined form. The present method to construct the motifs with (E)- and (Z)-alkenes are successfully applied to the syntheses of (+)-isotrichostatic acid, (−)-isotrichostatin RK, and (+)-trichostatic acid, respectively.     

Nonlinear piezoelectricity in PZT ceramics for generating ultrasonic phase conjugate waves

We have succeeded in the generation of acoustic phase conjugate waves with nonlinear PZT piezoelectric ceramics and applied them to ultrasonic imaging systems. Our aim is to make a phase conjugator with 100% efficiency. For this purpose, it is important to clarify the mechanism of acoustic phase conjugation through nonlinear piezoelectricity. The process is explained by the parametric interaction via the third-order nonlinear piezoelectricity between the incident acoustic wave at angular frequency omega and the pump electric field at 2 omega. We solved the coupling equations including the third-ordered nonlinear piezoelectricity and theoretically derived the amplitude efficiency of the acoustic phase conjugation. We compared the efficiencies between the theoretical and experimental values for PZT ceramics with eight different compositions. Pb[(Zn1/3Nb2/3)(1 - x)Tix]O3 (X = 0.09, PZNT91/9) piezoelectric single crystals have been investigated for high-performance ultrasonic transducer application, because these have large piezoelectric constants, high electrical-mechanical coupling factors and high dielectric constants. We found that they have third-order nonlinear piezoelectric constants much larger than PZT and are hopeful that the material as a phase conjugator has over 100% efficiency.     

Alternating copolymer based on sulfonamide‐substituted phenylmaleimide and vinyl monomers as polymer electrolyte membrane

The alternating copolymerization of phenylmaleimide (PMI) with a pendant sulfonamide acid group (sa‐PMI) and n‐butyl vinyl ether (BVE) as the aliphatic vinyl monomer afforded proton‐conducting polymer electrolytes—sa‐PMI‐BVEs—and their properties were compared with those of sa‐PMI‐STs that were synthesized from sa‐PMI and styrene. The ion exchange capacities (IECs) can be easily controlled by partly replacing sa‐PMI with unsubstituted PMI. sa‐PMI‐BVE is more flexible than sa‐PMI‐ST, and therefore, forms thin membranes even at high IECs, while sa‐PMI‐ST membranes are rigid and brittle. However, sa‐PMI‐BVE exhibits rather low thermal and oxidative stability. To realize polymer electrolyte membranes with reliable mechanical strength and a high IEC, gel‐filled membranes were prepared by polymerization in the presence of a small amount of a crosslinker, divinylbenzene, in porous polytetrafluoroethylene membranes. By using the gel‐filled membrane, H₂/O₂ fuel cells could be operated at 80 °C with reasonable performance. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013