A novel mesogen‐jacketed liquid crystalline electroluminescent polymer with both thiophene and oxadiazole in conjugated side chain

Mesogen‐jacketed liquid crystalline polymers (MJLCPs) with both electron‐transport oxadiazole and hole‐transport thiophene in the side chain were reported for their promising electroluminescent property. Monomers of 2,5‐bis{5‐[(4‐alkoxyphenyl)‐1,3,4‐oxadiazole]thiophen‐2‐yl}styrene (M‐Cm, m is the number of the carbons in the alkoxy groups, m = 8,10) were synthesized and confirmed by ¹H‐NMR, mass spectrometry, and elemental analysis. The corresponding polymers were successfully obtained and characterized by thermal analysis, optical spectroscopy, cyclic voltammetry, electroluminescent analysis, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD). The polymers exhibited high decomposition temperatures reaching 382 °C and high T_g's reaching 184 °C. The absorption spectra indicated that both the monomers and polymers had little aggregation in film than that in solution, and the absorption spectra of the polymers showed an obvious blue‐shift compared with those of the monomers. Both the monomers and the polymers had blue‐green emission, and the photoluminescence spectra of the polymers in film suggested the formation of excimer or exciplex. The polymers showed lower HOMO energy levels and LUMO energy levels than those of the MJLCPs containing oxadiazole unit reported before. Electroluminescence study with the device configuration of ITO/PEDOT/PVK/polymer/TPBI/Ca/Ag showed maximum brightness and current efficiency of 541 cd/m² and 0.10 cd/A, which proved that the introduction of directly connected electron‐ and hole‐transport units could greatly improve the EL property of side‐chain conjugated polymers. The phase structures of the polymers were confirmed to be smectic A phase through the results of PLM and WAXD. The annealed samples emitted polarized photoluminescence at room temperature, which indicated potential utility for practical applications in display. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1502–1515, 2010     

Thermomechanical modeling of the thermo-order-mechanical coupling behaviors in liquid crystal elastomers

Liquid crystal elastomer is a kind of anisotropic polymeric material, with complicated micro-structures and thermo-order-mechanical coupling behaviors. In this paper, we propose a method to systematically model these coupling behaviors. We derive the constitutive model in full tensor structure according to the Clausius-Duhem inequality. Two of the constitutive equations represent the mechanical equilibrium and the other two represent the phase equilibrium. Choosing the total free energy as the combination of the neo-classical free energy and the Landau-de Gennes nematic free energy, we obtain the Cauchy stress-deformation gradient relation and the order-mechanical coupling equations. We find the analytical homogeneous solutions of the deformation for the typical mechanical loadings, such as uniaxial stretch, and simple shear in any directions. We also compare the compression behavior of prolate liquid crystal elastomers with the stretch behavior of oblate liquid crystal elastomers. As a result, the stress, strain, temperature, order parameter, biaxiality and the direction of the director of liquid crystal elastomers couple with each other. When the prolate liquid crystal elastomer sample is stretched in the direction parallel to its director, the deviatoric stress makes the mesogens more order and increase the transition temperature. When the sample is sheared or stretched in the direction non-parallel to the director, the director of the liquid crystal elastomer will rotate, and the biaxiality will be induced. Because of the order-mechanical coupling, under infinitesimal deformation, liquid crystal elastomer has anisotropic Young’s modulus and zero shear modulus in the direction parallel or perpendicular to the director. While for the oblate liquid crystal elastomers, the stretch parallel to the director will cause the rotation of the director and induce the biaxiality.     

Synthesis and properties of phenothiazylene vinylene‐based polymers: New organic semiconductors for field‐effect transistors and solar cells

A series of new phenothiazylene vinylene‐based semiconducting polymers, poly[3,7‐(4′‐dodecyloxyphenyl)phenothiazylene vinylene] ( P1 ), poly[3,7‐(4′‐dodecyloxyphenyl)phenothiazylene vinylene‐alt‐1,4‐phenylene vinylene] ( P2 ), and poly[3,7‐(4′‐dodecyloxyphenyl)phenothiazylene vinylene‐alt‐2,5‐thienylene vinylene] ( P3 ), have been synthesized via a Horner‐Emmons reaction. FTIR and ¹H NMR spectroscopies confirmed that the configurations of the vinylene groups in the polymers were all‐trans (E). The weight‐averaged molecular weights (M_w) of P1 , P2 , and P3 were found to be 27,000, 22,000, and 29,000, with polydispersity indices of 1.91, 2.05, and 2.25, respectively. The thermograms for P1 , P2 , and P3 each contained only a broad glass transition, at 129, 167, and 155 °C, respectively, without the observation of melting features. UV–visible absorption spectra of the polymers showed two strong absorption bands in the ranges 315–370 nm and 450–500 nm, which arose from absorptions of the phenothiazine segments and the conjugated main chains. Solution‐processed field‐effect transistors fabricated from these polymers showed p‐type organic thin‐film transistor characteristics. The field‐effect mobilities of P1 , P2 , and P3 were measured to be 1.0 × 10^?4, 3.6 × 10^?5, and 1.0 × 10^?3 cm² V^?1 s^?1, respectively, and the on/off ratios were in the order of 10² for P1 and P2 , and 10³ for P3 . Atomic force microscopy and X‐ray diffraction analysis of thin films of the polymers show that they have amorphous structures. A photovoltaic device in which a P3 /PC₇₁BM (1/5) blend film was used as the active layer exhibited an open‐circuit voltage (V_OC) of 0.42 V, a short circuit current (J_SC) of 5.17 mA cm^?2, a fill factor of 0.35, and a power conversion efficiency of 0.76% under AM 1.5 G (100 mW cm^?2) illumination. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 635–646, 2010     

Organic soluble deoxyribonucleic acid (DNA) bearing carbazole moieties and its blend with phosphorescent Ir(III) complexes

A functionalized deoxyribonucleic acid (Cz‐DNA) was prepared with carbazolyl ammonium lipid as a triplet host material for phosphorescent material system. It is soluble in organic solvents, which facilitates the sample preparation for the absorption and luminescent properties in solid states. A highly soluble iridium complex, Ir(Cz‐ppy)₃ with carbazolyl‐substituted 2‐phenylpyridine ligands was employed for studying the phosphorescence in Cz‐DNA. There is a good overlap between the photoluminescence spectrum of Cz‐DNA and the metal‐to‐ligand charge transfer (MLCT) absorption bands of the iridium complex. This overlap enables efficient energy transfer from the excited state in the host to the MLCT band of Ir(Cz‐ppy)₃. In addition, photoluminescence quantum yield of Cz‐DNA was found to be relatively larger than the copolymer (PCzSt) with vinylcarbazole and styrene. Thus, Cz‐DNA was employed as a triplet host material for fabricating multilayered electrophosphorescence devices via modification of its property by doping 5,4‐tert‐butylhexyl‐1,3,4‐oxadiazole (PBD). After doping 30 wt % PBD and 10 wt % Ir(Cz‐ppy)₃ into Cz‐DNA, we achieved much improvement in electron injection/transport from an adjacent carrier transport layer, resulting in much improved device performances. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1913–1918, 2010     

Tracing the geographical origin of beefs being circulated in Korean markets based on stable isotopes

We have examined the carbon, nitrogen and oxygen isotopic compositions of American, Mexican, Australian, New Zealand and Korean beefs, which are currently being circulated in Korean markets, to check whether stable isotope ratios can identify their country of origin. Each beef exhibited statistically distinct isotopic compositions, especially in oxygen and carbon, because of the different isotopic compositions of their water and cattle feeds. Nevertheless, their isotopic compositions still showed some overlap, especially among USA, Australian, and Korean beefs, which sometimes resulted in significant misidentification when a single isotope was considered. However, the discrimination was generally successful when both the carbon and the oxygen isotopes were used. Copyright © 2009 John Wiley & Sons, Ltd.     

Chemoselective and enantioselective transfer hydrogenation of β,β-disubstituted nitroalkenes catalyzed by a water-insoluble chiral diamine–rhodium complex in water

Asymmetric transfer hydrogenation of β,β-disubstituted nitroalkenes catalyzed by a chiral diamine–rhodium complex in combination with HCO₂Na–HCO₂H as a hydrogen source in water was successfully realized with high reactivity, excellent chemoselectivity and good enantioselectivity. The metal precursor and pH value of the aqueous solution have a large influence on the reactivity and chemoselectivity. The substituents on the benzene rings and the sulfonyl groups of TsDPEN have significant effects on the enantioselectivity. This catalytic asymmetric transformation is one of the most practical pathways to obtain optically active nitroalkanes.