Investigation of facilitated ion-transfer reactions at high driving force by scanning electrochemical Microscopy

The kinetics of facilitated ion-transfer (FIT) reactions at high driving force across the water/1,2-dichloroethane (W/DCE) interface is investigated by scanning electrochemical microscopy (SECM). The transfers of lithium and sodium ions facilitated by dibenzo-18-crown-6 (DB18C6) across the polarized W/DCE interface are chosen as model systems because they have the largest potential range that can be controlled externally. By selecting the appropriate ratios of the reactant concentrations (Kr c(M)+/c(DB18C6)) and using nanopipets as the SECM tips, we obtained a series of rate constants (k(f)) at various driving forces (Delta(O)(W) phi(ML+)(0') - Es, Delta(O)(W) phi(ML+)(0') is the formal potential of facilitated ion transfer and Es is the potential applied externally at the substrate interface) based on a three-electrode system. The FIT rate constants k(f) are found to be dependent upon the driving force. When the driving force is low, the dependence of 1n k(f) on the driving force is linear with a transfer coefficient of about 0.3. It follows the classical Butler-Volmer theory and then reaches a maximum before it decreases again when we further increase the driving forces. This indicates that there exists an inverted region, and these behaviors have been explained by Marcus theory.

Synthesis of PtNPs/AQ/Ru(bpy)(3)(2+) colloid and its application as a sensitive solid-state electrochemiluminescence sensor material

The facile synthesis of the novel platinum nanoparticles/Eastman AQ55D/ruthenium(II) tris( bipyridine) (PtNPs/ AQ/Ru(bpy)(3)(2+)) colloidal material for ultrasensitive ECL solid-state sensors was reported for the first time. The cation ion-exchanger AQ was used not only to immobilize ECL active species Ru(bpy)(3)(2+) but also as the dispersant of PtNPs. Colloidal characterization was accomplished by transmission electron microscopy (TEM), X-ray photoelectron spectrum (XPS), and UV-vis spectroscopy. Directly coating the as-prepared colloid on the surface of a glassy carbon electrode produces an electrochemiluminescence (ECL) sensor. The electronic conductivity and electroactivity of PtNPs in composite film made the sensor exhibit faster electron transfer, higher ECL intensity of Ru(bpy)(3)(2+), and a shorter equilibration time than Ru(bpy)(3)(2+) immobilized in pure AQ film. Furthermore, it was demonstrated that the combination of PtNPs and permselective cation exchanger made the sensor exhibite excellent ECL behavior and stability and a very low limit of detection (1 x 10(-15) M) of tripropylamine with application prospects in bioanalysis. This method was very simple, effective, and low cost.

Effects of chain flexibility on polymer conformation in dilute solution studied by lattice Monte Carlo simulation

Effects of chain flexibility on the conformation of homopolymers in good solvents have been investigated by Monte Carlo simulation. Bond angle constraint coupled with persistence length of polymer chains has been introduced in the modified eight-site bond fluctuation simulation model. The study about the effects of chain flexibility on polymer sizes reveals that the orientation of polymer chains under confinement is driven by the loss of conformation entropy. The conformation of polymer chains undergoing a gradual change from spherical iso-diametric ellipsoid to rodlike iso-diametric ellipsoid with the decrease of polymer chain flexibility in a wide region has been clearly illustrated from several aspects. Furthermore, a comparison of the freely jointed chain (FJC) model and the wormlike chain (WLC) model has also been made to describe the polymer sizes in terms of chain flexibility and quasi-quantitative boundary toward the suitability of the models.

Solvent-induced novel morphologies in diblock copolymer blend thin films

We report the morphology and phase behaviors of blend thin films containing two poly styrene-b-poly (methyl methacrylate) (PS-b-PMMA) diblock copolymers with different blending compositions induced by a selective solvent for the PMMA block, which were studied by transmission electron microscopy (TEM). The neat asymmetric PS-b-PMMA diblock copolymers employed in this study, respectively coded as a(1) and a(2), have similar molecular weights but different volume fractions of PS block (f(PS) = 0.273 and 0.722). Another symmetric PS-b-PMMA diblock copolymer, coded as s, which has a PS block length similar to that of a(1), was also used. For the asymmetric a(1)/a(2) blend thin films, circular multilayered structures were formed. For the asymmetric a(1)/symmetric s blend thin films, inverted phases with PMMA as the dispersed domains were observed, when the weight fraction of s was less than 50%. The origins of the morphology formation in the blend thin films via solvent treatment are discussed. Combined with the theoretical prediction by Birshtein et al. (Polymer 1992, 33, 2750), we interpret the formation of these special microstructures as due to the packing frustration induced by the difference in block lengths and the preferential interactions between the solvent and PMMA block.

Growth of cationic lipid toward bilayer, lipid membrane by solution spreading: scanning probe microscopy study

The growth of cationic lipid dioctadecyldimethylammonium bromide (DODAB) toward bilayer lipid membrane (BLM) by solution spreading on cleaved mica surface was studied by atomic force microscopy (AFM). Bilayer of DODAB was formed by exposing mica to a solution of DODAB in chloroform and subsequently immersing into potassium chloride solution for film developing. AFM studies showed that at the initial stage of the growth, the adsorbed molecules exhibited the small fractal-like aggregates. These aggregates grew up and expanded laterally into larger patches with time and experienced from monolayer to bilayer, finally a close-packed bilayer film (5.4 +/- 0.2 nm) was approached. AFM results of the film growth process indicated a growth mechanism of nucleation, growth and coalescence of dense submonolayer, it revealed the direct information about the film morphology and confirmed that solution spreading was an effective technique to prepare a cationic bilayer in a short time.

A wide-bandgap semiconducting polymer for ultraviolet and blue light emitting diodes

A novel wide-bandgap conjugated polymer (PDHFSCHD) consisting of alternating dihexylfluorene and rigidly twisted biphenyl units has been synthesized. The new fluorene-based copolymer composed of rigid twisting segments in the main-chain exhibits an optical bandgap of as high as 3.26 eV, and a highly efficient ultraviolet emission with peaks at 368 nm and 386 nm. An electroluminescence device from PDHFSCHD neat film as an active layer shows UV emission which peaks at 395 nm with a turn on voltage below 8 V By optimizing the device conditions, a peak EL quantum efficiency of 0.054% and brightness of 10 cd.m(-2) was obtained. Furthermore, blending a poly(dihexylfluorene) in the PDHFSCHD host gave pure blue emission peaking at 417 nm, and 440 nm without long wavelength emission from aggregated species. Efficient energy transfer from PDHFSCHD to PDHF was demonstrated in these blended systems. Depressed chain-aggregation of PDHF in the PDHFSCHD host can correspond to pure blue emission behaviors.

Formation of regular hole pattern in polymer films

Ordered macroporous materials recently have attracted much attention. A method that utilizes the condensation of monodisperse water droplets on a polymer solution is proposed for the preparation of honeycomb microporous films. Our results show that it is a general method that can be used for patterning a wide range of polymers. The presence of water vapor and polymer is necessary for the formation of regular holes in films. The formation of hexagonal packing instead of other kinds of packing takes place because the hexagonal packing has the lowest free energy. The formation mechanisms of regular hole pattern and imperfections in the hexagonal packing are proposed.

Pressure effects on the thermodynamics of trans-decahydronaphthalene/polystyrene polymer solutions: Application of the Sanchez-Lacombe lattice fluid theory

The cloud-point temperatures (T-cl's) of trans-decahydronaphthalene(TD)/polystyrene (PS, (M) over bar (w) = 270 000) solutions were determined by light scattering measurements over a range of temperatures (1-16degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol.-% polymer). The system phase separates upon cooling and T-cl was found to increase with rising pressure for constant composition. In the absence of special effects, this finding indicates positive excess volume for the mixing. Special attention was paid to the demixing temperatures as a function of pressure for different polymer solutions and the plots in the T-phi plane (where phi signifies volume fractions). The cloud-point curves of polymer solutions under different pressures were observed for different compositions, which demonstrated that pressure has a greater effect on the TD/PS solutions when far from the critical point as opposed to near the critical point. The Sanchez-Lacombe lattice fluid theory (SLLFT) was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalpy of mixing, and the volume changes of mixing. The calculated results show that modified PS scaling parameters can describe the thermodynamics of the TD/PS system well. Moreover the SLLFT describes the experimental results well.

What has brought on the effects of number-average molecular weight on the spinodals in polymer mixtures?

On the basis of the thermodynamics of Gibbs, the spinodal for the quasibinary system was derived in the framework of the Sanchez-Lacombe lattice fluid theory. All of the spinodals were calculated based on a model polydisperse polymer mixture, where each polymer contains three different molecular weight subcomponents. According to our calculations, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights, whereas that of the z-average molecular weight is invisible. Moreover, the extreme of the spinodal decreases when the polydispersity index (eta = (M) over bar (w)/(M) over bar (n)) of the polymer increases. The effect of polydispersity on the spinodal decreases when the molecular weight gets larger and can be negligible at a certain large molecular weight. It is well-known that the influence of polydispersity on the phase equilibrium (coexisting curve, cloud point curves) is much more pronounced than on the spinodal. The effect of M, on the spinodal is discussed as it results from the infuluence of composition temperatures, molecular weight, and the latter's distribution on free volume. An approximate expression, which is in the assumptions of v* v(1)* = v(2)* and 1/r --> 0 for both of the polymers, was also derived for simplification. It can be used in high molecular weight, although it failed to make visible the effect of number-average molecular weight on the spinodal.

Synthesis and characterization of poly(beta-hydroxybutyrate) and poly(epsilon-caprolactone) copolyester by transesterification

To synthesize the copolyester of poly(beta-hydroxybutyrate) (PHB) and poly(epsilon-caprolactone) (PCL), the transesterification of PHB and PCL was carried out in the liquid phase with stannous octoate as the catalyzer. The effects of reaction conditions on the transesterification, including catalyzer concentration, reaction temperature, and reaction time, were investigated. The results showed that both rising reaction temperature and increasing reaction time were advantageous to the transesterification. The sequence distribution, thermal behavior, and thermal stability of the copolyesters were investigated by C-13 NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, wide-angle X-ray diffraction, optical microscopy, and thermogravimetric analysis. The transesterification of PHB and PCL was confirmed to produce the block copolymers. With an increasing PCL content in the copolyesters, the thermal behavior of the copolyesters changed evidently. However, the introduction of PCL segments into PHB chains did not affect its crystalline structure. Moreover, thermal stability of the copolyesters was little improved in air as compared with that of pure PHB.

Study of electron-transfer reactions across an externally polarized water/1,2-dichloroethane interface by scanning electrochemical microscopy

A novel method to study electron-transfer (ET) reactions between ferrocene in 1,2-dichloroethane (DCE) and a redox couple of K3Fe(CN)(6) and K4Fe(CN)(6) in water using scanning electrochemical microscopy (SECM) with a three-electrode setup is reported. In this work, a water droplet that adheres to the Surface of a platinum disk electrode is immersed in a DCE solution. The aqueous redox couple serves both as a reference electrode on the platinum disk and as an electron donor/acceptor at the polarized liquid/liquid inter-face. With the present experimental approach, the liquid/liquid interface can be polarized externally, while the electron-transfer reactions between the two phases can be monitored independently by SECM. The apparent heterogeneous rate constants for the ET reactions were obtained by fitting the experimental approach curves to the theoretical values. These rate constants obey the Butler-Volmer theory i.e., them, are found to be potential dependent.

Plasticizer effect on the ionic conductivity of PEO-based polymer electrolyte

The effects of plasticizer ethylene carbonate (EC) on the AC impedance spectra and the ionic conductivity are reported. With increasing of EC concentration the semicircle in high frequency disappears, and the slope of the straight line in low frequency decreases. The data obtained from impedance experiments can be explained using an equivalent circuit proposed. On the other hand, the room temperature conductivity increases with EC concentration because of the increase of the segmental flexibility of PEO. For lower EC concentration samples, the temperature dependence of conductivity in low temperature range follows Arrhenius type, but when EC concentration is larger than 20%, the temperature dependence of conductivity obeys the Vogel-Tamman-Fulcher (VTF) equation in all temperature ranges.

Effect of physical aging on the microstructure and the crystallization of amorphous poly(aryl ether ether ketone ketone) (PEEKK)

Physical aging of poly(aryl ether ether ketone ketone) (PEEKK) has been investigated. Heat flow responses were measured after annealing the amorphous samples obtained by quenching the melt into an ice-water bath close to, but below, the glass transition temperature. The extent of aging is related to the supercooling from the glass transition temperature and to the aging time. The activation energy of the aging process, which was estimated by a Williams-Watt expression, is similar in magnitude to that obtained for the cold crystallization for the aged samples. The quenched glass is a metastable glass. The conformation of molecular chains rearranges with physical aging which results in the formation of a denser packing in the amorphous phase. The dense amorphous phase may form an initial nucleus for crystallization. Isothermal cold crystallization of the aged samples was carried out. The Avrami equation was used to determine the kinetic parameters, and the Avrami constant n is about 2. An Arrhenius expression was used to evaluate the activation energy of relaxation upon physical aging and the activation energy of transportation upon isothermal crystallization. The activation energy of relaxation is similar in magnitude to that of crystallization for aged samples. Results obtained are interpreted as kinetic effects associated with the glass formation process.

Synthesis and characterization of novel crosslinkable side-chain liquid crystalline polyesters

Crosslinkable side-chain liquid crystalline polyesters PCn from N-[n-(4-(4-nitrophenylazo)phenyloxy)alkyl]diethanolamine (Cn, n = 3, 5, 6, 10) as mesogenic monomers and maleic anhydride were synthesized and characterized. The thermal properties of PCn's were studied by means of DSC, polarized optical microscopy (POM) and wide angle X-ray diffraction (WAXD), and the results showed that all the polymers studied exhibit enantiotropic liquid crystallinity. In the molar mass independent region, the relatively high content of cis -CH=CH- groups in the polymer backbone of PC3 causes an increase of the melting temperature (T-m) and a decrease of T-g and isotropisation temperature (T-i). The crosslinking of PCn in the radical polymerization with styrene was confirmed by FTIR spectroscopy. The absorption band at 1300 cm(-1) attributed to the in-plane C-H-bending vibration of trans -CH=CH- in the polymer backbone disappeared after crosslinking, indicating that the trans -CH=CH- functions are consumed in the crosslinking polymerization of styrene.

Compatibilizing effect of polystyrene-block-poly(4-vinylpyridine) for poly(2,6-dimethyl-1,4-phenyleneoxide) chlorinated polyethylene blends

The compatibilizing effect and mechanism of compatibilization of the diblock copolymer polystyrene-block-poly(4-vinylpyridine) P(S-b-4VPy) on immiscible blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)/chlorinated polyethylene (CPE) were studied by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC), mechanical properties and FTIR measurements. The block copolymer was synthesized by sequential anionic polymerization and melt-blended with PPO and CPE. The results show that the P(S-b-4VPy) added acts as an effective compatibilizer, located at the interface between the PPO and the CPE phase, reducing the interfacial tension, and improving the interfacial adhesion. The tensile strength and modulus of all blends increase with P(S-b-4VPy) content, whereas the elongation at break increases for PPO-rich blends, but decreases for CPE-rich blends. The polystyrene block of the diblock copolymer is compatible with PPO, and the poly(4-vinylpyridine) block and CPE are partially miscible.