Liquid crystalline and light emitting polyacetylenes: Synthesis and properties of biphenyl-containing poly(1-alkynes) with different functional bridges and spacer lengths

Biphenyl- (Biph-) containing 1-alkynes (3 and 4) and their polymers (1 and 2) with varying bridge groups and spacer lengths were synthesized and the effects of the structural variation on their properties, especially their mesomorphism and photoluminescence behaviors, were studied. The acetylene monomers 3(3) [HCdropC(CH2)(3)O-Biph-OCO(CH2)(10)CH3] and 4(m) [HCdropC(CH2)(m)OCO-Biph-OCO(CH2)(10)-CH3, m = 3, 4] were prepared by sequential etherization and esterification reactions of 1-alkynes. While 3(3) exhibits enantiotropic crystal E and SmB mesophases, its structural cousin 4(3) displays only a monotropic SmB phase. Enantiotropic SmA and SmB mesophases are, however, developed when the spacer length is increased to 4. Polymerizations of the monomers are effected by Mo-, W-, Rh-, and Fe-based catalysts, with the WCl6-Ph4Sn catalyst giving the best results (isolation yield up to 85% and M-w up to 59000). The polymers were characterized by IR, UV, NMR, TGA, DSC, POM, XRD, and PL analyses. Compared to 1(3), 2(3) shows a red-shifted absorption, a higher T-i, and a better packed interdigitated bilayer SmA(d) structure, while the mesophase of 2(4) involves monolayer-packing arrangements of the mesogens. Upon photoexcitation, 1(3) emits almost no light but 2(m) gives a strong ultraviolet emission (lambda(max) similar to 350 nm), whose intensity increases with the spacer length.

A mica-modified quartz resonator for a quartz crystal microbalance study

Mica, as a bridge of the study for combining between quartz crystal microbalance (QCM) and atomic force microscope (AFM), was successfully modified onto the piezoelectric quartz crystal (PQC). This mica-modified piezoelectric quartz crystal (mica-PQC) can be stably oscillated with a shift frequency of +/-1 Hz per half an hour in air. Using this mica-PQC, the processes of DNA adsorbed onto the mica surface were studied in liquid phase. The results show that a bivalent cation, such as Mn2+, can be used as an ionic bridge to immobilize DNA on mica surface. The image of DNA on the mica surface was also obtained by AFM. Mica-PQC gives the possibility of a combination between QCM and AFM in situ.

Synthesis and thermotropic liquid crystalline behaviour of novel poly(aryl ether ketone)s with a lateral methoxy group

Novel poly(aryl ether ketone)s containing a lateral methoxy group were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and methoxyhydroquinone with 1,4-bis(4-fluorobenzoyl)benzene in a sulfolane solvent in the presence of anhydrous potassium carbonate. Their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques, e.g. differential scanning calorimetry (DSC), polarized light microscopy and temperature-dependent FTIR. Thermotropic liquid crystalline behaviour was observed in the copolymers containing 30-80 mol-% mexthoxyhydroquinone. Both melting (T-m) and isotropization (T-i) transitions appeared in the DSC curves. The polarized light microscopy study of the liquid crystalline copolymers suggested their ordered smectic structures. As expected, the copolymers had lower melting transitions than the biphenol-based homopoly(aryl ether ketone)s because of the copolymerization effect of the crystal-disrupting monomer methoxyhydroquinone.

Self-organization of BaF2 single crystal film under a compressed Langmuir monolayer

Self-organization of BaF2 single crystal film under a compressed monolayer of behenic acid (BA) has been investigated by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The experimental results indicated the (100)-oriented single crystal film of BaF2 was formed under the BA monolayer. The relation between the BaF2 single crystal and the monolayer was discussed.

Homoepitaxial crystallization in films of a thermotropic liquid crystalline chloro-poly(aryl ether ketone)

The homoepitaxial crystallization in the films of a thermotropic liquid crystalline chloro-ply(aryl ether ketone) is studied by transmission electron microscopy (TEM) and electron diffraction (ED). The homoepitaxy takes place in the temperature range 330-320 degreesC, in which a highly-ordered smectic crystalline phase of the copolymer with a single-crystal-like banded structure is formed during the cooling process from the isotropic melt. The homoepitaxial crystallizations with angles of 32 degrees and 122 degrees between the two b axes are the major populations observed, and possess epitaxial contact planes of (100)(I)-(210)(II) and (010)(I)-(210)(II); respectively.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 7. Phase structures in a series of copolyethers containing odd and even numbers of methylene units of different compositions

A series of liquid crystalline copolyethers have been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,12-dibromododecene [coTPPs(7/12)], which represents copolyethers containing both odd and even numbers of methylene units. The molar ratio of odd to even methylene units in this series ranges from 1/9 to 9/1. The coTPPs(7/12) exhibit multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. For all these thermal transitions, a small undercooling and superheating dependence is observed upon cooling and heating at different rates. Three types of phase behaviors can be classified in coTPPs(7/12) on the basis of the structural analyses by wide-angle X-ray diffraction on powder and fiber samples and by electron diffraction experiments in transmission electron microscopy. At room temperature, highly ordered smectic and smectic crystal (SC) phases are identified in coTPPs(7/12: 1/9 and 2/8), which is similar to the homopolymer TPP(m = 12). The coTPPs(7/12: 3/7, 4/6, and 5/5) possess a hexagonal columnar (Phi(H)) phase in which the molecular and columnar axes are parallel to the fiber direction and perpendicular to the hexagonal lateral packing. The coTPPs(7/12: 6/4, 7/3, and 8/2) possess a tilted hexagonal columnar (Phi(TH)) phase with a single tilt angle which increases with the increasing composition of the seven-numbered methylene units. However, in coTPP(7/12: 9/1), a Phi(TH) phase with multiple tilt angles is found. Upon heating, phase structures in most coTPPs(7/12) involving the columnar phases enter directly into the nematic (N) phase, while the coTPP(7/12: 1/9) exhibits a highly ordered smectic F (S-F) phase before it reaches the N phase. One exception is found in coTPP(7/12: 2/8), wherein the transformation from the S-F to Phi(H) occurs prior to the N phase. Combining the copolymer phase behaviors observed with the corresponding homopolymers TPP(n = 7) and TPP(m = 12), a phase diagram describing transition temperatures with respect to the composition can be constructed.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Novel morphology in ring-banded spherulites from single-phase mixtures of poly(epsilon-caprolactone) with poly(styrene-co-acrylonitrile)

Novel morphology of ring-banded spherulites in the surface of poly(epsilon-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends was discovered and studied by SEM and TEM. The ring-banded spherulites separate into those exhibiting a very dark contrast, of relatively regular bundles of lamellae and others appearing with a much brighter intensity, of a coarse and irregular aggregates of lamellae. The origin of the novel morphology is not due to different crystalline structures as in the case of isotactic polypropylene because only one crystal structure exists in PCL/SAN blends. The formation may reflect whether spherulites in PCL/SAN blends are nucleated at the bottom surface or at the top (free) surface.

The synthesis and thermotropic liquid crystalline behaviour of novel main chain poly(aryl ether ketone)s containing a lateral phenyl group

Novel main chain poly(aryl ether ketone)s containing a lateral phenyl group were synthesized by nucleophilic substitution reactions of 4,4'-biphenol and phenylhydroquinone with either 4,4'-difluorobenzophenone or 1,4-bis(4-fluorobenzoyl)benzene and their thermotropic liquid crystalline properties were characterized by a variety of experimental techniques. Thermotropic liquid crystalline behaviour was observed in the copolymers containing 50 and 70mol% biphenol. Melting (T-m) and isotropization (T-i) transitions both appeared on the DSC thermograms. A banded texture was formed after shearing the sample in the liquid crystalline nematic state. As expected, each of the copolymers had a relatively lower melting transition than the biphenol-based homopoly(aryl ether ketone)s because of the copolymerization effect of the crystal-disrupting monomer phenylhydroquinone.

Electrochemical quartz crystal microbalance study of the electrochemical behavior of riboflavin at gold electrodes

The electrochemical and adsorption behaviors of riboflavin (RF) at gold electrodes has ken studied by using an electrochemical quartz crystal microbalance (EQCM). Useful information is obtained not only about electrochemical behavior but also about mass changes on the electrode surface. The electrochemical properties and frequency shifts were investigated in RF solutions at different pH values, concentrations and scan rates. Reversible voltammograms were observed for pH less than or equal to 9.71. There was no electrochemical reaction for pH > 9.71. The maximum current response was obtained at about pH 8. The current response was proportional to the square root of scan rates when the concentration of RF was lower than 1.0 x 10(-4) mol L-1 (pH 6.92). On the contrary, at concentrations higher than 1.0 x 10(-4) mol L-1 (pH 6.92), it was proportional to the scan rates.

Crystallization kinetics in mixtures of poly(epsilon-caprolactone) and poly(styrene-co-acrylonitrile)

Isothermal crystallization kinetics in the miscible mixtures of poly(epsilon-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) have been investigated as a function of the composition and the crystallization temperature by optical microscopy. The radial growth rates of the spherulites have been described by a kinetic equation including the interaction parameter and the free energy for the formation of secondary crystal nuclei. Fold surface free energies decrease slightly with the increase of SAN content. The experimental findings show that the influence of the glass transition temperature of the mixture, which is related to the chain mobility, on the rate of crystallization predominates over the influence of the surface free energies. This indicates that the glass transition temperature of the mixture should be of more importance, so that the growth rates decrease when the content of the noncrystallizable component increases. In addition, the Flory-Huggins interaction parameter obtained by fitting the kinetic equation with experimental data is questionable.

Electrochemical behavior of FAD at a gold electrode studied by electrochemical quartz crystal microbalance

The electrochemical behavior of flavine adenine dinucleotide (FAD) at a gold electrode involving adsorption of the reduced form FADH(2) and desorption of the oxidized form FAD has been studied by using electrochemical quartz crystal microbalance (EQCM). EQCM can present information not only about the electrochemical behavior but also about the mass changes on the electrode surface. The electrochemical properties and frequency shifts were investigated in FAD solutions at different pH values, concentrations and scan rates. Reversible voltammograms were observed when pH<4.5 and irreversible voltammograms were found when pH greater than or equal to 4.5. It is found to be a diffusion controlled process when the concentration of FAD is lower than 2x10(-4) moll(-1) (pH 1.5). On the contrary, at concentrations higher than 2x10(-4) moll(-1) (pH 1.5), it is found to be an adsorption controlled process.

STATISTICAL THERMODYNAMICS OF POLYDISPERSE POLYMER MIXTURES

A statistical thermodynamics theory of polydisperse polymer blends based on a lattice model description of a fluid is formulated. Characterization of a binary polydisperse polymer mixture requires a knowledge of the pure polymer system and the interaction energy. It is assumed that the intrinsic and interactive properties of polymer (for example, T*, P*, rho*, and epsilon(ij)*) are independent of molecular size. Thermodynamic properties of ternary and higher order mixtures are completely defined in terms of the pure fluid polymer parameters and the binary interaction energies. Thermodynamic stability criteria for the phase transitions of a binary mixture are shown. The binodal and spinodal of general binary systems and of special binary systems are discussed.

CRYSTALLIZATION KINETICS OF MIXTURES OF POLY(EPSILON-CAPROLACTONE) AND POLY(STYRENE-CO-ACRYLONITRILE)

The crystallization kinetics in mixtures of poly(epsilon-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) has been investigated as the function of composition and crystallization temperature. The isothermal growth rates of PCL spherulites decrease with increasing concentration of SAN. Because of the miscibility of PCL/SAN mixtures, the radial growth rates of the spherulites are described by a kinetic equation including the interaction parameter and the free energy for the formation of crystal nuclei. The interaction parameter obtained from the fitting of the kinetic equation with experimental data is in good agreement with that obtained from melting point depression. Folding surface free energies decrease with the increase of SAN concentration. In light of these results, it is suggested that, for the PCL/SAN mixtures, the noncrystallizable SAN polymer reduces the mobility of crystallizable PCL polymer so that the growth rates decrease with the increase of noncrystallizable component fraction.

ELECTROCHEMICAL INVESTIGATION OF LIQUID/LIQUID SYSTEMS USING VARIOUS ORGANIC SOLVENTS

The potential windows of the system water/pure solvent (W/P) and water/solvent mixtures(W/S) have been investigated by cyclic voltammetry with solvents whose dielectric constants lie between 5.87 and 34.82. In the presence of LiCI in the aqueous phase and tetrabutytammoniumtetraphenylborate(TBATPB) in the organic phase, the systems water/allyl iso-thiocyanate (W/AIT) and water/nitrobensene (W/NB) show a same wide epotential window. thermodynamic parameters of ion transfer W/AIT interface were determined. In systems of W/P and V/S the influence solvent effect on the standard gibbs energies of transfer of was discussed.