Phase structure change and ER effect in liquid crystalline polymer/dimethylsiloxane blends

The mechanism of the electrorheological (ER) effect in two types of liquid crystalline polymer (LCP)/dimethylsiloxane (DMS) blends was investigated by rheological measurements and by structure observation under electric field and shear flow. The results show that the phase structures of these immiscible blends can be categorized into slipping (low viscosity) and non-slipping (high viscosity) states. In the non-slipping state, higher viscosity LCP domains connect the electrodes. In the slipping state, on the other hand, LCP domains do not connect the electrodes and the shear is mainly confined in the lower viscosity DMS domains. The ER effect (electrically induced viscosity increase) originates from the electrically induced slipping to non-slipping transition. In one of the blends, the ER effect occurs only at high shear rate, since this blend is in non-slipping state even under no field if the shear rate is low. Received: 29 April 1997 Accepted: 3 November 1997     

π–π Stacking Interaction in an Oxidized CuII–Salen Complex with a Side-Chain Indole Ring: An Approach to the Function of the Tryptophan in the Active Site of Galactose Oxidase

In order to gain new insights into the effect of the π–π stacking interaction of the indole ring with the Cu^II–phenoxyl radical as seen in the active form of galactose oxidase, we have prepared a Cu^II complex of a methoxy-substituted salen-type ligand, containing a pendent indole ring on the dinitrogen chelate backbone, and characterized its one-electron-oxidized forms. The X-ray crystal structures of the oxidized Cu^II complex exhibited the π–π stacking interaction of the indole ring mainly with one of the two phenolate moieties. The phenolate moiety in close contact with the indole moiety showed the characteristic phenoxyl radical structural features, indicating that the indole ring favors the π–π stacking interaction with the phenoxyl radical. The UV/Vis/NIR spectra of the oxidized Cu^II complex with the pendent indole ring was significantly different from those of the complex without the side-chain indole ring, and the absorption and CD spectra exhibited a solvent dependence, which is in line with the phenoxyl radical–indole stacking interaction in solution. The other physicochemical results and theoretical calculations strongly support that the indole ring, as an electron donor, stabilizes the phenoxyl radical by the π–π stacking interaction.     

Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.     

Hysteresis of ruby fluorescent line by pressure and annealing effect

Abstract

Accuracy of hydrostatic pressure measurement in a diamond-anvil cell (DAC) depends on the reproducibility of ruby RI fluorescent measurement. The larger scatter in R, fluorescent wavelength shift than the reproducibility of spectroscopic measurement was observed among appropriately mirror-finished ruby plates before setting up in DAC. The characteristics of the scatter changed after loading DAC up to pressure over hydrostatic limit. They vanished by annealing the ruby plates. These phenomena are presumably due to the appearance and disappearance of the residual stress in the ruby crystal. Such hysteresis of ruby fluorescent wavelength shift by pressure and its annealing effect are discussed.     

α- and γ-Regiocontrol and Enantiospecificity in the Copper-Catalyzed Substitution Reaction of Propargylic Phosphates with Grignard Reagents

The regioselectivity (r.s.) and enantiospecificity (e.s.) of the substitution reactions of secondary propargylic alcohol derivatives using reagents derived from ArMgBr and Cu salts were studied. First, the picolinate, 3-methylpicolinate, and diethylphosphonate derivatives of Ph(CH₂)₂CH(OH)C≡CTMS were reacted with PhMgBr/CuCN in ratios of 2.5:2.7–2.5:0.25. The use of 2.5:0.25 ratio in THF/DME (6:1) at 0 °C for 1 h afforded the α-substitution product from the phosphate with ≥98 % r.s. and 99 % e.s. CuBr⋅Me₂S gave similar selectivity. The reaction system was then applied to phosphates derived from R¹CH(OH)C≡CR² and ArMgBr to obtain synthetically sufficient r.s. and e.s. values with R²=TMS, Ph, whereas iPr was borderline in terms of size as an R¹ substituent. The presence of a substituent at the o-position of Ar marginally affected the selectivity. We also found that the use of PhMgBr/Cu(acac)₂ in a 2:1 ratio in THF produced the γ-substitution products (allenes) with high r.s. and e.s.     

Hybrid EuIII Coordination Luminophore Standing on Two Legs on Silica Nanoparticles for Enhanced Luminescence

In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent Ln^III-silica nanomaterials. A novel Eu^III-silica hybrid nanoparticle was developed by using a doubly binding TPPO−Si(OEt)₃ (TPPO: triphenyl phosphine oxide) linker. The TPPO−Si(OEt)₃ was confirmed by ¹H, ³¹P, ²⁹Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)₃ and Eu(tfc)₃ moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO−Si(OEt)₃-modified silica nanoparticles, producing Eu(hfa)₃(TPPO−Si)₂-SiO₂ and Eu(tfc)₃(TPPO−Si)₂-SiO₂, respectively. Eu(hfa)₃(TPPO−Si)₂−SiO₂ exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported Eu^III-based hybrid materials. Eu(tfc)₃(TPPO−Si)₂−SiO₂ showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)₃(TPPO−Si(OEt)₃)₂ was found to be 39 %. These results confirmed that the TPPO−Si(OEt)₃ linker is a promising candidate for development of Eu^III-based luminescent materials.     

Three-dimensional visualization of columnar vortices in rotating Rayleigh–Bénard convection

Journal of Visualization -  To enrich the three-dimensional experimental details of vortex structures in rotating Rayleigh–Bénard convection, we established a technique...     

Thiol-terminated hydroxy-functional polymer as a transtab toward polymer latex particles

Hydroxy-functional macrodisulfides have been synthesized by atom transfer radical polymerization of 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate in 2-propanol. Mean degrees of polymerization of the polymer chains beside the disulfide were fixed at 30, 60, and 90; since ATRP has reasonably good living character, the molecular weight distribution is relatively narrow. Furthermore, the macrodisulfides were reduced to synthesize corresponding thiol-terminated polymers with relatively narrow molecular weight distributions. ¹H nuclear magnetic resonance and gel permeation chromatography were used to characterize the macrodisulfides and thiol-terminated polymers in terms of their chemical structure, molecular weight, and polydispersity, respectively. Dispersion polymerizations of styrene using the thiol-terminated hydroxy-functional polymers as a transtab (chain transfer agent + colloidal stabilizer) in ethanol resulted in colloidally stable submicrometer-sized polystyrene latex particles. Scanning electron microscopy, Fourier transform infrared spectroscopy, and elemental microanalysis were used to characterize the particles in terms of their morphologies, particle sizes and their distributions, and chemical compositions.     

Synthesis of poly(ethylene glycol)‐based hydrogels and their swelling/shrinking response to molecular recognition

To synthesize the novel molecular‐ and pH‐stimulus‐responsive hydrogel, we prepared poly(ethylene glycol)‐based hydrogel containing ionic groups. We evaluated the fundamental swelling/shrinking properties of the hydrogels synthesized by various conditions. Decreasing the molecular weight of a crosslinker provided the increasing of the equilibrium swelling ratio. Also, the equilibrium swelling ratio was changed by the introduction of functional ionic monomers and its compositions. Furthermore, the swelling/shrinking behaviors of the hydrogels were affected by the environmental condition of aqueous solution, in fact the hydrogels were considerably shrunk (to one‐fifth volume) using a di‐ionic solute in the aqueous solution through the ionic interactions between the hydrogel and the solutes. Additionally, the specific shrinking to diamine compounds was also observed in response to pH change. These results clearly show the swelling/shrinking responsibility of the hydrogels toward the molecular recognitions and its pH conditions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3153–3158