Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether, lithium perchlorate, and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Raman spectra of polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) with LiClO(4), PEGdME/LiClO(4), and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, PEGdME/[bmim]PF(6), are compared. Raman spectroscopy suggests stronger interactions in PEGdME/LiClO(4) than PEGdmE/[bmim]PF(6), thus corroborating previous results obtained by molecular dynamics simulations. Quantum Chemistry methods have been used to calculate vibrational frequencies and the equilibrium structure of segments of the polymer chain around the cation. A consistent picture has been obtained from Raman spectroscopy, density functional theory (DFT) calculations, and molecular dynamics simulations for these polymer electrolytes. (C) 2010 Elsevier B.V. All rights reserved.

Nanostructured thin films obtained by electrodeposition over a colloidal crystal template: applications in electrochemical devices

Colloidal particles have been used to template the electrosynthesis of several materials, such as semiconductors, metals and alloys. The method allows good control over the thickness of the resulting material by choosing the appropriate charge applied to the system, and it is able to produce high density deposited materials without shrinkage. These materials are a true model of the template structure and, due to the high surface areas obtained, are very promising for use in electrochemical applications. In the present work, the assembly of monodisperse polystyrene templates was conduced over gold, platinum and glassy carbon substrates in order to show the electrodeposition of an oxide, a conducting polymer and a hybrid inorganic-organic material with applications in the supercapacitor and sensor fields. The performances of the resulting nanostructured films have been compared with the analogue bulk material and the results achieved are depicted in this paper.

Polaron liquid-gas crossover at the orthorhombic-rhombohedral transition of manganites

High-resolution synchrotron x-ray powder diffraction in La(0.7)Ca(0.3)MnO(3) shows in detail a first-order structural phase transition from orthorhombic (space-group Pnma) to rhombohedral (space-group R (3) over barc) crystal structures near T(S)=710 K. Magnetic susceptibility measurements show that the rhombohedral phase strictly obeys the Curie-Weiss law as opposed to the orthorhombic phase. A concomitant change in the electrical resistivity behavior, consistent with an alteration from nonadiabatic to adiabatic small polaron hopping regimes, was also observed at T(S). The simultaneous change in transport and magnetic properties are identified as a transition from a correlated polaron liquid for TT(S), driven by the change in the crystal symmetry.

Three-dimensional fabrication of optically active microstructures containing an electroluminescent polymer

Microfabrication via two-photon absorption polymerization is a technique to design complex microstructures in a simple and fast way. The applications of such structures range from mechanics to photonics to biology, depending on the dopant material and its specific properties. In this paper, we use two-photon absorption polymerization to fabricate optically active microstructures containing the conductive and luminescent polymer poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV). We verify that MEH-PPV retains its optical activity and is distributed throughout the microstructure after fabrication. The microstructures retain the emission characteristics of MEH-PPV and allow waveguiding of locally excited fluorescence when fabricated on top of low refractive index substrates. (C) 2009 American Institute of Physics. [doi: 10.1063/1.3232207]

Determination of fluoxetine and norfluoxetine enantiomers in human plasma by polypyrrole-coated capillary in-tube solid-phase microextraction coupled with liquid chromatography-fluorescence detection

A sensitive, selective, and reproducible in-tube polypyrrole-coated capillary (PPY) solid-phase microextraction and liquid chromatographic method for fluoxetine and norfluoxetine enantiomers analysis in plasma samples has been developed, validated, and further applied to the analysis of plasma samples from elderly patients undergoing therapy with antidepressants. Important factors in the optimization of in-tube SPME efficiency are discussed, including the sample draw/eject volume, draw/eject cycle number, draw/eject flow-rate, sample pH, and influence of plasma proteins. Separation of the analytes was achieved with a Chiralcel OD-R column and a mobile phase consisting of potassium hexafluorophosphate 7.5 mM and sodium phosphate 0.25 M solution, pH 3.0, and acetonitrile (75:25, v/v) in the isocratic mode, at a flow rate of 1.0 mL/min. Detection was carried out by fluorescence absorbance at Ex/Em 230/290 nm. The multifunctional porous surface structure of the PPY-coated film provided high precision and accuracy for enantiomers. Compared with other commercial capillaries, PPY-coated capillary showed better extraction efficiency for all the analytes. The quantification limits of the proposed method were 10 ng/mL for R- and S-fluoxetine, and 15 ng/mL for R- and S-norfluoxetine, with a coefficient of variation lower than 13%. The response of the method for enantiomers is linear over a dynamic range, from the limit of quantification to 700ng/mL, with correlation coefficients higher than 0.9940. The in-tube SPME/LC method can therefore be successfully used to analyze plasma samples from ageing patients undergoing therapy with fluoxetine. (C) 2009 Elsevier B.V. All rights reserved.

Liquid crystalline cellulosic elastomers: free standing anisotropic films under stretching

The structure and local ordering of 1,6-hexamethylenediisocyanate-(acetoxypropy1) cellulose (HDI-APC) liquid crystalline elastomer thin films are investigated by using X-ray diffraction and scattering techniques. Optical microscopy and mechanical essays are performed to complement the investigation. The study is performed in films subjected or not to an uniaxial stress. Our results indicate that the film is constituted by a bundle of helicoidal fiber-like structure, where the cellobiose block spins around the axis of the fiber, like a string-structure in a smectic-like packing, with the pitch defined by a smectic-like layer. The fibers are in average perpendicular to the smectic-like planes. Without the stretch, these bundles are warped, only with a residual orientation along the casting direction. The stretch orients the bundles along it, increasing the smectic-like and the nematic-like ordering of the fibers. Under stress, the network of molecules which connects the cellobiose blocs and forms the cellulosic matrix tends to organize their links in a hexagonal-like structure with lattice parameter commensurate to the smectic-like structure.

Effect of Eu(2)O(3) doping on Ta(2)O(5) crystal growth by the laser-heated pedestal technique

High energy band gap hosts doped with lanthanide ions are suitable for optical devices applications To study the potential of Ta(2)O(5) as a host compound pure and Eu(2)O(3)-doped Ta(2)O(5) crystal fibers were grown by the laser-heated pedestal growth technique in diameters ranging from 250 to 2600 pm and in lengths of up to 50 mm The axial temperature gradient at the solid/liquid interface of pure Ta(2)O(5) fibers revealed a critical diameter of 2200 gm above which the fiber cracks X-ray diffraction measurements of the pure Ta(2)O(5) single crystals showed a monoclinic symmetry and a growth direction of [1 (1) over bar 0] An analysis of the pulling rate as a function of the fiber diameter for Eu(2)O(3)-doped Ta(2)O(5) fibers indicated a well defined region in which constitutional supercooling is absent Photoluminescence measurements of pure Ta(2)O(5) crystals using excitation above the band gap (3 8 eV) were dominated by a broad unstructured green band that peaked at 500 nm Three Eu(3+)-related optical centers were identified in the doped samples with nominal concentrations exceeding 1 mol% Two of these centers were consistent with the ion in the monoclinic phase with different oxygen coordinations The third one was visible in the presence of the triclinic phase (C) 2010 Elsevier B V All rights reserved

Crystal structures and thermal behavior of alkaline earth tricyanomethanides

The alkaline earth tricyanomethanides Mg(tcm)(2) center dot 2H(2)O, Ca(tcm)(2), Sr(tcm)(2) - H2O and Ba(tcm)(2) center dot 2H(2)O were prepared from aqueous solutions of the respective chlorides and silver tricyanomethanide. Their IR spectra and thermal behavior are described. The crystal structures of Ca(tcm)(2) and Ba(tcm)(2) center dot 2H(2)O were determined by single crystal X-ray diffraction. The structure of Ca(tcm)(2) is of the type found for several transition metal tricyanomethanides [1], containing two independent interpenetrating networks. Ba(tcm)(2) center dot 2H(2)O has a unique crystal structure corresponding to a three-dimensional coordination polymer with nine fold coordinated Ba atoms connected by water molecules and tricyanomethanide anions.

NMR and conductivity study of gelatin-based polymer electrolytes

Nuclear Magnetic Resonance spectroscopy (NMR) and complex impedance spectroscopy have been used to study gelatin-based polymer electrolytes plasticized with glycerol and containing lithium perchlorate. The studied samples were prepared with salt concentration of 7.9 wt% and 10.3 wt%. Ionic conductivity of about 10(-5) S/cm was obtained at room temperature for both samples. Lithium (Li-7) and proton (H-1) lineshapes and spin-lattice relaxation times were measured as a function of temperature. The Li-7 NMR relaxation results indicate that the ionic mobility in this system is comparable to those found in other plasticized polymer electrolytes.

Nitric oxide sensing by cytochrome c bonded to a conducting polymer modified glassy carbon electrode

A nitric oxide biosensor based on cytochrome c (an heme protein) covalently immobilized to poly(5-amino-1-naphthol) by using cyanuric chloride as a bridge was developed. The immobilization was studied by cyclic voltammetry and quartz crystal microbalance. The nitric oxide detection as a function of poly(5-amino-1-naphthol) amount was recorded, and the best result was obtained with the electrode prepared by 70 cycles. The sensitivity and detection limit were 0.015 mu A cm(-2)/mu mol L(-1) and 2.85 mu mol L(-1), respectively. (C) 2009 Elsevier B.V. All rights reserved.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Microwave-Assisted Derivatization of Cellulose in an Ionic Liquid: An Efficient, Expedient Synthesis of Simple and Mixed Carboxylic Esters

Microwave (MW)-assisted cellulose dissolution in ionic liquids (ILs) has routinely led either to incomplete biopolymer solubilization, or its degradation. We show that these problems can be avoided by use of low-energy MW heating, coupled with efficient stirring. Dissolution of microcrystalline cellulose in the IL 1-allyl-3-methylimidazolium chloride has been achieved without changing its degree of polymerization; regenerated cellulose showed pronounced changes in its index of crystallinity, surface area, and morphology. MW-assisted functionalization of MCC by ethanoic, propanoic, butanoic, pentanoic, and hexanoic anhydrides has been studied. Compared with conventional heating, MW irradiation has resulted in considerable decrease in dissolution and reaction times. The value of the degree of substitution (DS) was found to be DS(ethanoate) > DS(propanoate) > DS(butanoate). The values of DS(pentanoate) and DS(hexanoate) were found to be slightly higher than DS(ethanoate). This surprising dependence on the chain length of the acylating agent has been reported before, but not rationalized. On the basis of the rate constants and activation parameters of the hydrolysis of ethanoic, butanoic, and hexanoic anhydrides in aqueous acetonitrile (a model acyl transfer reaction), we suggest that this result may be attributed to the balance between two opposing effects, namely, steric crowding and (cooperative) hydrophobic interactions between the anhydride and the cellulosic surface, whose lipophilicity has increased, due to its partial acylation. Four ethanoate-based mixed esters were synthesized by the reaction with a mixture of the two anhydrides; the ethanoate moiety predominated in all products. The DS is reproducible and the IL is easily recycled. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 134-143, 2010

Application of 1-Allyl-3-(1-butyl)imidazolium Chloride in the Synthesis of Cellulose Esters: Properties of the Ionic Liquid, and Comparison with Other Solvents

The ionic liquid (IL), 1-allyl-3-(1-butyl)imidazolium chloride (AlBuImCl), has been synthesized and its properties determined. Increase in the temperature increased its conductivity and decreased its density, polarity, and viscosity. Microcrystalline cellulose (MCC), dissolves in thisIL by heating at 80 degrees C; this did not affect its degree of polymerization, decreased its index of crystallinity (Ic), and changed in morphology after regeneration. Convenient acylation of MCC was achieved by using 50% excess anhydride at 80 degrees C, for 24 or 48 h for acetic and butyric anhydride, respectively. The composition of the mixed esters depended on the initial ratio of the anhydrides, and their order of addition.

Tailored Media for Homogeneous Cellulose Chemistry: Ionic Liquid/Co-Solvent Mixtures

Co-solvents can minimize two of the major problems associated with the use of ionic liquids (ILs) as solvents for homogeneous derivatization of cellulose: high viscosity and limited miscibility with non-polar reagents or reaction products. Thus, the effects of 18 solvents and 3 binary solvent mixtures on cellulose solutions in three ILs were systematically studied with respect to the solution phase behavior. The applicable limits of these mixtures were evaluated and general guidelines for the use of co-solvents in cellulose chemistry could be advanced: Appropriate co-solvents should have EN T values (normalized empirical polarity) > 0.3, very low ``acidity`` (alpha < 0.5), and relatively high ""basicity`` (beta >= 0.4). Moreover, novel promising co-solvents and binary co-solvent mixtures were identified.

Synthesis and characterization of mono and polymeric cyclopalladated compounds: Crystal and molecular structure of [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (pz = pyrazine)

In the treatment of cyclometallated dimer [Pd(dmba)(mu-Cl)](2) (dmba = N,N-dimethylbenzylamine) with AgNO(3) and acetonitrile the result was the monomeric cationic precursor [Pd(dmba)(NCMe)(2)](NO(3)) (NCMe=acetonitrile) (1). Compound 1 reacted with m-nitroaniline (m-NAN) and pirazine (pz), originating [Pd(dmba)(ONO(2))(m-NAN)] (2) and [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (3), respectively. These compounds were characterized by elemental analysis, IR and NMR spectroscopy. The IR spectra of (2-3) display typical bands of monodentade O-bonded nitrate groups, whereas the NMR data of 3 are consistent with the presence of bridging pyrazine ligands. The structure of compound 3 was determined by Xray diffraction analysis. This packing consists of a supramolecular chain formed by hydrogen bonding between the water molecule and nitrato ligands of two consecutive [Pd(2)(dmba)(2)(ONO(2))2(mu-pz)] units. (c) 2008 Elsevier Ltd. All rights reserved.