Influences of local polymer-solvent π-π-interaction on dynamics of phenyl ring rotation and its role on photophysics of conjugated polymer

In this report, the role of local polymer-solvent π-π-interaction on rotational dynamics of phenyl rings of poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylenevinylene] (MEH-PPV) is examined by utilizing nuclear magnetic resonance (NMR) spectroscopy. We have found that an aromatic solvent can couple strongly with the phenyl rings via favorable local π-π-interaction, causing a restriction of the ring rotation. The dynamic process takes place at much faster rate in a non-aromatic solvent. NMR line shape analysis indicates the existence of two side chain configurations with relatively long life-time in toluene and pyridine while a single time-averaged configuration is detected in chloroform and tetrahydrofuran. Addition of chloroform or cyclohexane to a solution of MEH-PPV in toluene is accompanied by an increase of the rotational dynamics. This indicates that the expansion or collapse of main chain upon varying solvent quality play a minor role on the rotational dynamics. The relationship between the dynamics of ring rotation and photophysics of MEH-PPV in solution is discussed.     

Synthesis of side chain liquid crystalline copolymers and characterization of their polar structure

A series of side chain liquid crystalline copolymers having different spacer lengths, copolymer compositions, and chromophore types were synthesized and characterized both in the bulk and at the gas‐water interface. Liquid crystalline properties were identified by differential scanning calorimetry (DSC), optical microscopy, and X‐ray diffraction (XRD). Copolymer with spacer lengths 4, 5, 10, and 11 showed smectic A (S_A) phases with a bâtonnet texture. The liquid crystalline (LC) phase stabilized as the spacer increased. Copolymers with different compositions were investigated both as monolayers and transferred films. The isotherms suggest nanodomain formation at the gas‐water interface in copolymers with high nitrobiphenyl (NBP) content. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1057–1070, 1999     

Versatile route for tuning optical properties of poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene)

In this contribution, we report a versatile method for tuning optical properties of poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene) (MEH‐PPV) in its solution with 1,2‐dichloroethane, accomplished by reacting with pyridinium formate (PF), a volatile organic salt. We can systematically control the positions of absorption and photoluminescent (PL) spectra of MEH‐PPV by adjusting the concentration of PF in the solution. The addition of 10 vol % PF caused a blue‐shift in the absorption spectra by about 65 nm. When the concentration of PF decreased to 0.1 vol %, the blue‐shift occurred to a lesser extent, about 25 nm. The measurements of PL spectra showed similar behaviors. The λ_max shifted from 558 nm to 546 and 552 nm when 10 and 0.1 vol % of PF were added, respectively. The changes of PL colors from orange to yellow and green, respectively, were observed by naked eyes. Structural investigation by nuclear magnetic resonance and Fourier‐transformed infrared spectroscopy indicated that the changes of the optical properties were due to chemical modifications along the main chain and the side groups of MEH‐PPV. These results implied a simple route for engineering the HOMO–LUMO energy gap of MEH‐PPV, which could be utilized in advanced applications such as organic light‐emitting devices and solar cells. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 696–705, 2009     

Electrospinning of polystyrene/poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene) blends

Ultrafine polystyrene (PS)/poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene) (MEH‐PPV) fibers were successfully prepared by electrospinning of PS/MEH‐PPV solutions in chloroform, 1,2‐dichloroethane, and tetrahydrofuran (THF). Three concentrations of the solutions were prepared: 8.5, 16, and 23.5% (w/v), with the compositional weight ratios between PS and MEH‐PPV being 7.5:1, 15:1, and 22.5:1, respectively. Smooth fibers only observed from 23.5% (w/v) PS/MEH‐PPV solution in chloroform. Improvement in the electrospinnability of 8.5% (w/v) PS/MEH‐PPV solution in chloroform was achieved by addition of an organic salt, pyridinium formate (PF), or by addition of a minor solvent with a high dielectric constant value. The average diameters of the as‐spun PS/MEH‐PPV fibers were between 0.30 and 5.11 μm. Last, photoluminescence of 8.5% (w/v) solutions of PS/MEH‐PPV in a mixed solvent system of chloroform and 1,2‐dichloroethane of various volumetric compositions and the resulting as‐spun fibers was investigated and compared. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1881–1891, 2005     

Functionalized diacetylenes for nonlinear optical applications: Synthesis,characterization, and the properties of their monolayers

Synthesis and characterization of DA(8/1)OMe (14-{4′-[(methoxy)methoxy] biphenyl}-10,12-tetradecadiynoic acid) and DA(8/1)NBP (14-{4′-[(nitro)methoxy] biphenyl}-10,12-tetradecadiynoic acid ) are presented. Monolayers of DA(8/1)OMe at gas-water interface were investigated. It does not form a stable monolayer nor does it undergo polymerization at the gas-water interface. However, the Ba²⁺ and Cd²⁺ salts formed stable monolayer that polymerized. Polymerization was confirmed by Raman spectroscopy. The diacetylene analog with the more polar tail group, DA(8/1)NBP, does not form a monolayer and undergo polymerization regardless of the subphase condition. A mixed monolayer of DA(8/1)OMe and DA(8/1)NBP forms a true monolayer if the composition of DA(8/1)NBP is 50% or less. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1771–1779, 1999     

Preparation and photoinduced isomerization study of a homopolymer and a copolymer based on 4′‐(6‐acryloxy)hexyloxy‐4‐methoxyazobenzene and acrylic acid

The synthesis and characterization of a copolymer based on 4′‐(6‐acryloxy)hexyloxy‐4‐methoxyazobenzene (MAB6) and acrylic acid (AA) are reported. A reaction was carried out by free‐radical polymerization, yielding an MAB6 homopolymer and an AA–MAB6 copolymer with an MAB6 concentration of 16–80%. A nematic phase was observed in the copolymer when the MAB6 content was 44% or higher. Both nematic and smectic phases were observed in the MAB6 homopolymer. All of the polymers were investigated for trans–cis–trans isomerization in a solid film. The samples were irradiated with nonpolarized ultraviolet light (385 nm) before absorption measurements were taken with an ultraviolet–visible spectrometer. The copolymer and homopolymer exhibited a thermal cis–trans isomerization, which could be described by a double‐exponential relaxation process (fast and slow). The relaxation experiment suggested that the hydrogen bonding may have hindered the slow process but had no effect on the fast process. A film of a copolymer sample with a high MAB6 content could be optically aligned by the exposure of the sample to polarized light (385 nm). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 4017–4024, 2003     

Polydiacetylene–inorganic clay nanocomposites

Two new diacetylenes, 14-amino-10,12-tetradiynoic acid (a diacetylenic aminoacid) and 10,12-docosadiyndiamine (diacetylenic diamine), were successfully synthesized via Eglinton and Cadiot–Chodkiewicz coupling. These two diacetylenes and 10,12-pentacosadiynyl amine (monoamine) were intercalated in mica-type layered silicates, montmorillonite and vermiculite, via a cationic exchange reaction. The intercalation process was confirmed by X-ray diffraction and Fourier transform infrared spectroscopy. The interlayer spacing and polymerizability of the intercalated diacetylene were found to depend upon the length of the diacetylene molecule, the layer charge density of the clay and the solvent treatment. The X-ray diffraction pattern of vermiculite–diacetylene showed evidence of the in-plane packing of the diacetylene. The polymerization of the intercalated diacetylene was confirmed by Raman spectra. © 1998 John Wiley & Sons, Ltd.     

A polymer surface for antibody detection by using surface plasmon resonance via immobilized antigen

A polymer substrate based surface plasmon resonance (SPR) technique was developed for detection of specific monoclonal antibody 10B2 (MAb 10B2) against bacterium Acidovorax avenae subsp. citrulli (Aac). The monolayer of Aac antigen was physically immobilized on 95:5 polystryrene – copoly acrylic acid (95PSMA) for detection of antibody. The amount of antigen–antibody binding was found to depend on the surface density of immobilized Aac on the sensor surface and the antibody concentration. The detection limit was 5 μg/ml which was lower than the required concentration during the normal production of the antibody at 10–100 μg/ml. This suggests a possible use of surface for the antibody screening. Moreover, an application in antibody screening was explored by combination of surface plasmon resonance imaging (SPR imaging) and antibody detection assay on the 95PSMA surface. Two antigens of bovine serum albumin (BSA) and Aac were used as a model system for antibody screening. The result shows that both antibodies can be distinguished using the immobilized antigens on the 95PSMA surface based SPR imaging technique.     

Effects of chain conformation and chain length on degree of aggregation in assembled particles of conjugated polymer in solvents–nonsolvent: A spectroscopic study

This article explores photophysical properties and aggregation behaviors of conjugated polymer, poly[2‐methoxy, 5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene](MEH?PPV), in various solvent–nonsolvent systems by utilizing UV/vis absorption and photoluminescence (PL) spectroscopy. The isolated chains of MEH‐PPV dispersed in solvents including dichloromethane, chloroform, and tetrahydrofuran adopt either extended or collapsed conformations depending on local polymer–solvent interactions. Aggregation of the MEH‐PPV in these solvents is induced by addition of a poor solvent, cyclohexane. The formation of aggregates is indicated by the appearance of distinct red‐shift peaks in the absorption and PL spectra. The degree of aggregation in each solvent–nonsolvent system is compared by means of absorbance and PL intensity of the aggregate bands. In early stage of the aggregation, the amount of aggregates in system is controlled by the solubility of polymer. When the polymer chains are forced to densely pack within assembled particles by increasing ratio of cyclohexane to 99 v/v %, the conformation of individual chain plays important role. We have found that the extended chains facilitate the aggregation in the assembled particles. Increasing chain length of polymer promotes the aggregation in early stage and densely packed particles. Size distribution of the assembled particles is also found to depend on the choice of solvent. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 894–904, 2010