Enhanced Proton Conduction in Polymer Electrolyte Membranes as Synthesized by Polymerization of Protic Ionic Liquid-Based Microemulsions

Proton-conducting membranes were prepared by polymerization of microemulsions consisting of surfactant-stabilized protic ionic liquid (PIL) nanodomains dispersed in a polymerizable oil, a mixture of styrene and acrylonitrile. The obtained PIL-based polymer composite membranes are transparent and flexible even though the resulting vinyl polymers are immiscible with PIL cores. This type of composite membranes have quite a good thermal stability, chemical stability, tunability, and good mechanical properties. Under nonhumidifying conditions, PIL-based membranes show a conductivity up to the order of 1 x 10(-1) S/cm at 160 degrees C, due to the well-connected PIL nanochannels preserved in the membrane. This type of polymer conducting membranes have potential application in high-temperature polymer electrolyte membrane fuel cells.

Kinetic study for hopping conduction through deoxyribonucleic acid molecules

Recent experiments indicated that disorder effect in deoxyribonucleic acid (DNA) may lead to a transition of the electronic hole transport mechanism from band resonant tunneling to thermally activated hopping. In this letter, based on Mott's variable-range hopping theory, we present a kinetic study for the hole transport properties of DNA molecules. Beyond the conventional argument in large-scale systems, our numerical study for finite-size DNA molecules reveals a number of unique features for: (i) the current-voltage characteristics, (ii) the temperature and length dependence, and (iii) the transition from conducting to insulating behaviors. (c) 2005 American Institute of Physics.

A partially incoherent rate theory of long-range charge transfer in deoxyribose nucleic acid

A quantum chemistry based Green's function formulation of long-range charge transfer in deoxyribose nucleic acid (DNA) double helix is proposed. The theory takes into account the effects of DNA's electronic structure and its incoherent interaction with aqueous surroundings. In the implementation, the electronic tight-binding parameters for unsolvated DNA molecules are determined at the HF/6-31G* level, while those for individual nucleobase-water couplings are at a semiempirical level by fitting with experimental redox potentials. Numerical results include that: (i) the oxidative charge initially at the donor guanine site does hop sequentially over all guanine sites; however, the revealed rates can be of a much weaker distance dependence than that described by the ordinary Ohm's law; (ii) the aqueous surroundings-induced partial incoherences in thymine/adenine bridge bases lead them to deviate substantially from the superexchange regime; (iii) the time scale of the partially incoherent hole transport through the thymine/adenine pi stack in DNA is about 5 ps. (C) 2002 American Institute of Physics.

Synthesis and characterisation of novel functional polyolefin containing sulfonic acid groups

The strong polar group, sulfonic acid, has successfully been introduced into ethylene/allylbenzene copolymers without degradation or crosslinking via chlorosulfonation reaction with chlorosulfonic acid as a chlorosulforiating agent in 1, 1,2,2-tetrachloroethane followed by hydrolysis. The degree of sulforiation (DS) can be easily controlled by changing the ratio of chlorosulfonic acid to the pendant phenyls of the copolymer. The microstructure of sulfonated copolymers were unambiguously revealed by H-1 NMR and H-1-H-1 COSY spectral analyses, which indicates that all the sulforiation reactions exclusively took place at the para-position of the aromatic rings.

Effect of Poly (3-hexylthiophene) Nanofibrils on Charge Separation and Transport in Polymer Bulk Heterojunction Photovoltaic Cells

Crystalline poly (3-hexylthiophene) (P3HT) nanofibrils are introduced into the P3HT: [6, 6]-phenyl C61-butyric acid methyl ester (PCBM) composite films via P3HT preaggregation in solution by adding a small amount of acetone, and the correlation of P3HT nanofibrils and the optoelectronic properties of P3HT:PCBM bulk heterojunction photovoltaic cells is investigated. It is found that the optical absorption and the hole transport or the resulted P3HT:PCBM composite films increase with the increase of the amount of P3HT nanofibrils due to the increased P3HT crystallinity and highly interconnected nanofibrillar P3HT networks. However, it is also found that high contents of crystalline P3HT nanofibrils may restrain PCBM molecules from demixing with the P3HT component that forms electron traps in the active layer. and hence reduce the charge collection efficiency. Small contents of P3HT nanofibrils not only improve the demixing between P3HT and PCBM components, but also enhance the hole transport via crystalline P3HT nanofibrillar networks, resulting in efficient charge collection.

Polyelectrolyte complexes of chitosan and phosphotungstic acid as proton-conducting membranes for direct methanol fuel cells

Polyelectrolyte complexes (PECs) of chitosan and phosphotungstic acid have been prepared and evaluated as novel proton-conducting membranes for direct methanol fuel cells. Phosphotungstic acid can be fixed within PECs membranes through strong electrostatic interactions, which avoids the decrease of conductivity caused by the dissolving of phosphotungstic acid as previously reported. Scanning electron microscopy (SEM) shows that the PECs membranes are homogeneous and dense. Fourier transform infrared spectroscopy (FTIR) demonstrates that hydrogen bonding is formed between chitosan and phosphotungstic acid. Thermogravimetric analysis (TGA) shows that the PECs membranes have good thermal stability up to 210 degrees C. The PECs membranes exhibit good swelling properties and low methanol permeability (P, 3.3 x 10(-7) cm(2) s(-1)). Proton conductivity (sigma) of the PECs membranes increases at elevated temperature, reaching the value of 0.024 S cm(-1) at 80 degrees C.

Phenylene vinylene-based electroluminescent polymers with electron transport block in the main chain

We report a new route for the design of soluble phenylene vinylene (PV) based electroluminescent polymers bearing electron-deficient oxadizole (OXD) and triazole (TZ) moieties in the main chains with the aryloxy linkage. Both series of the PV-based polymers were prepared by Wittig reaction. By properly adjusting the OXD and/or TZ content through copolymerization, we can achieve an enhanced balance of hole- and electron injections, such that the device efficiency is significantly improved. Light-emitting diodes fabricated from P1, P2, P3, P4, P5, P6, and P7 with the configuration of Indium-Tin Oxide (ITO)/Poly (styrene sulfonic acid) doped poly (ethylenedioxythiophene) (PEDOT)/polymer/Ca/Al, emit bright green light with the maximum peak around 500 nm. For the device using the optimal polymer (P4) as emitting layer, a maximum brightness of 1300 cd/m(2) at 20 V and a maximum luminance efficiency of 0.325 cd/A can be obtained.

Transport property of polyaniline and its molecular weight dependence

The electrical conductivity of polyaniline doped with camphor sulfonic acid (PAn-CSA) was studied. The results indicate that there is a critical temperature (T-c) and the temperature dependence of PAn-CSA conductivity shows metallic and semiconductor characteristics above and below T-c, respectively. The higher the molecular weight of PAn, the lower the T-c. The conductivity was enhanced remarkably when PAn-CSA film was stretched, its room temperature conductivity is up to 750 S/cm when elogonation is 60%; however, T-c was independent of elongation.

Gas separation properties of aromatic polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 3,5-diaminobenzic acid or its esters

The gas transport properties of a series polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) with 1,3-phenylenediamine or 3,5-diaminobenzic acid (DBA) or its esters are reported. The effects of carboxylic group (-COOH) and carboxylic ether groups (-COOR), at five positions of 1,3-phenylenediamine moiety, on H-2, CO2, O-2, and N-2 permeability, diffusivity, and solubility of the polyetherimides were investigated. The gas permeability, diffusion, and solubility coefficients of the polyetherimides containing COOR are bigger than those of HQDPA-PDA, but the ideal separation factors and ideal diffusivity selectivity factors are much smaller than that of HQDPA-PDA because COOR decreases chain segmental packing efficiency and increases chain segmental mobility. The permeability coefficients of HQDPA-DBA to H-2, CO2, and O-2 are bigger than those of HQDPA-PDA; the ideal separation factors for gas pairs H-2/N-2, CO2/N-2, and O-2/N-2 are also much bigger than those of HQDPA-PDA. Both the diffusion coefficients of CO2 and O-2 and the ideal diffusivity selectivity factors for CO2/N-2 and O-2/N-2 are bigger than those of HQDPA-PDA because COOH decreases both chain segmental packing efficiency and chain segmental mobility. The copolyimides, which were prepared from 3,5-diaminobenzic acid and 3,5-diaminobenzic esters, have both high permeability and high permselectivity. (C) 1997 John Wiley & Sons, Inc.

Necessity of dietary lecithin and eicosapentaenoic acid for growth, survival, stress resistance and lipoprotein formation in gilthead sea bream Sparus aurata

The substitution of dietary docosahexaenoic acid (DHA) with eicosapentaenoic acid (EPA) reduces larval growth in gilthead sea bream. However, the value of EPA when dietary DHA is able to meet the requirements of the larvae has not been sufficiently studied. Dietary phosphoacylgliceride levels also affect fish growth and it has been suggested that they enhance lipid transport in developing larvae. The present experiment was carried out to further study the effect of dietary lecithin and eicosapentaenoic acid on growth, survival, stress resistance,. larval fatty acid composition and lipid transport, when DHA is present in the microdiets of gilthead:sea bream. Eighteen thousand gilt-head sea bream larvae of 4.99+/-0.53 mm total length were fed three microdiets tested by triplicate: a control diet [2% soybean lecithin (SBL) and 2.89% EPA], a low EPA diet,(2% SBL and 1.63% EPA) and a no SBL diet (0% SBL and 2.71% EPA). Handling, temperature and salinity tests determined larval resistance to stress. The results show that when dietary DHA levels are high, but dietary arachidonic acid (ARA) levels are about 0.2%, EPA is necessary to improve larval growth, and survival. Larval EPA content, but not DHA or ARA, was affected by dietary EPA levels. Increased dietary EPA improved larval stress resistance to handling and temperature tests, which could be related to its possible role as a regulator of cortisol production whereas it did not affect stress resistance after salinity shock. Larvae fed the no SBL diet showed a lower lipid content characterized by a low proportion of saturated and monounsaturated fatty acids, together with a significant reduction in the appearance of lipoprotein particles in the lamina propria and in the size of such particles, denoting a critical reduction in dietary lipid transport and utilization, and lower larval growth and survival rates.