Langmuir and langmuir-blodgett films of polyfluorenes and their use in polymer light-emitting diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9'-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (Pi-A) and surface potential (Delta V-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.

Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

A 2D coordination polymer with brick-wall network topology based on the [Cu(NCS)(2)(pn)] monomer

The new complex [Cu(NCS)(2)(pn)] (1) (pn = 1,3-propanediamine) has been synthesized and characterized by elemental analysis, infrared and electronic spectroscopy. Single crystal X-ray diffraction studies revealed that complex 1 is made up of neutral [Cu(NCS)(2)(pn)] units which are connected by mu-1,3,3-thiocyanato groups to yield a 2D metal-organic framework with a brick-wall network topology. Intermolecular hydrogen bonds of the type NH...SCN and NH...NCS are also responsible for the stabilization of the crystal structure. (c) 2007 Elsevier B.V. All rights reserved.

A new method for extending the range of conductive polymer sensors for contact force

This paper describes a technique for extending the force range of thin conductive polymer force sensors used for measuring contact force. These sensors are conventionally used for measuring force by changing electrical resistance when they are compressed. The new method involves measuring change in electrical resistance when the flexible sensor, which is sensitive to both compression and bending, is sandwiched between two layers of spring steel, and the structure is supported on a thin metal ring. When external force is applied, the stiffened sensor inside the spring steel is deformed within the annular center of the ring, causing the sensor to bend in proportion to the applied force. This method effectively increases the usable force range, while adding little in the way of thickness and weight. Average error for loads between 10 N and 100 N was 2.2 N (SD = 1.7) for a conventional conductive polymer sensor, and 0.9 N (SD = 0.4) using the new approach. Although this method permits measurement of greater loads with an error less than 1 N, it is limited since the modified sensor is insensitive to loads less than 5 N. These modified sensors are nevertheless useful for directly measuring normal force applied against handles and tools and other situations involving forceful manual work activities, such as grasp, push, pull, or press that could not otherwise be measured in actual work situations.

Electrical percolation during gelation of lithium doped siloxane-poly(oxyethylene) hybrids

Gelation mechanisms of lithium-doped Siloxane-Poly(oxyethylene) (PEO) hybrids containing polymer of two different molecular weight (500 and 1900 g/mol) were investigated through the evolution of the electrical properties during the solgel transition. The results of electrical measurements, performed by in-situ complex impedance spectroscopy, were correlated with the coordination and the dynamical properties of the lithium ions during the process as shown by Li-7 NMR measurements. For both hybrids sols, a decrease of the conductivity is observed at the initial gelation stage, due to the existence of an inverted percolation process consisting of the progressive separation of solvent molecules containing conducting species in isolated islands during the solid network formation. An increase of conductivity occurs at more advanced stages of gelation and aging, attributed to the increasing connectivity between PEO chains promoted by the formation of crosslinks of siloxane particles at their extremities, favoring hopping motions of lithium ions along the chains.

Lithium thiazolidine-4-carboxylate: Synthesis, spectroscopic characterization and preliminary in vitro cytotoxic studies in human HeLa cells

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Development of metal oxide nanoparticles by soft chemical method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Developments in hot-filament metal oxide deposition (HFMOD)

Hot-filament metal oxide deposition (HFMOD) is a variant of conventional hot-filament chemical vapor deposition (HFCVD) recently developed in our laboratory and successfully used to obtain high-quality, uniform films of MOx WOx and VOx. The method employs the controlled oxidation of a filament of a transition metal heated to 1000 degrees C or more in a rarefied oxygen atmosphere (typically, of about 1 Pa). Metal oxide vapor formed on the surface of the filament is transported a few centimetres to deposit on a suitable substrate. Key system parameters include the choice of filament material and diameter, the applied current and the partial pressures of oxygen in the chamber. Relatively high film deposition rates, such as 31 nm min(-1) for MoOx, are obtained. The film stoichiometry depends on the exact deposition conditions. MoOx films, for example, present a mixture of MoO2 and MoO3 phases, as revealed by XPS. As determined by Li+ intercalation using an electrochemical cell, these films also show a colouration efficiency of 19.5 cm(2) C-1 at a wavelength of 700 nm. MOx and WOx films are promising in applications involving electrochromism and characteristics of their colouring/bleaching cycles are presented. The chemical composition and structure of VOx films examined using IRRAS (infrared reflection-absorption spectroscopy), RBS (Rutherford backscattering spectrometry) and XPS (X-ray photoelectron spectrometry) are also presented. (c) 2007 Elsevier B.V. All rights reserved.

Solid-state NMR, ionic conductivity, and thermal studies of lithium-doped siloxane-poly(propylene glycol) organic-inorganic nanocomposites

Hybrid organic-inorganic ionic conductors, also called ormolytes (organically modified electrolytes), were obtained by dissolution of LiClO 4 in siloxane-poly(propylene glycol) matrixes. The dynamic features of these nanocomposites were studied and correlated to their electrical properties. Solid-state nuclear magnetic resonance (NMR) spectroscopy was used to probe the effects of the temperature and nanocomposite composition on the dynamic behaviors of both the ionic species ( 7Li) and the polymer chains ( 13C). NMR, dc ionic conductivity, and DSC results demonstrate that the Li + mobility is strongly assisted by the segmental motion of the polymer chain above its glass transition temperature. The ac ionic conductivity in such composites is explained by use of the random free energy barrier (RFEB) model, which is agreement with their disordered and heterogenous structures. These solid ormolytes are transparent and flexible, and they exhibit good ionic conductivity at room temperature (up to 10 -4 S/cm). Consequently, they are very promising candidates for use in several applications such as batteries, sensors, and electrochromic and photoelectro-chemical devices.

Effect of lithium doping on the evolution of rheological and structural properties during gelation of siloxane-poly(oxypropylene) nanocomposites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Metal-insulator transition in Nd1-xEuxNiO 3 compounds

Polycrystalline Nd1-xEuxNiO3 (0≤x≤0.5) compounds were synthesized in order to investigate the character of the metal-insulator (MI) phase transition in this series. Samples were prepared through the sol-gel route and subjected to heat treatments at ∼1000 °C under oxygen pressures as high as 80bar. X-ray diffraction (XRD) and neutron powder diffraction (NPD), electrical resistivity ρ(T), and magnetization M(T) measurements were performed on these compounds. The NPD and XRD results indicated that the samples crystallize in an orthorhombic distorted perovskite structure, space group Pbnm. The analysis of the structural parameters revealed a sudden and small expansion of ∼0.2% of the unit cell volume when electronic localization occurs. This expansion was attributed to a small increase of ∼0.003 of the average Ni-O distance and a simultaneous decrease of ∼-0.5° of the Ni-O-Ni superexchange angle. The ρ(T) measurements revealed a MI transition occurring at temperatures ranging from TMI∼193 to 336K for samples with x ≤ 0 and 0.50, respectively. These measurements also show a large thermal hysteresis in NdNiO3 during heating and cooling processes, suggesting a first-order character of the phase transition at TMI. The width of this thermal hysteresis was found to decrease appreciably for the sample Nd 0.7Eu0.3NiO3. The results indicate that cation disorder associated with increasing substitution of Nd by Eu is responsible for changing the first-order character of the transition in NdNiO3. © 2006 IOP Publishing Ltd.

Toward pH-controllable bioelectrocatalysis for hydrogen peroxide based on polymer brushes

In the present work, a biosensor was built with smart material based on polymer brushes. The biosensor demonstrated a pH-sensitive on-off property, and it was further used to control or modulate the electrochemical responses of the biosensor. This property could be used to realize pH-controlled electrochemical reaction of hydrogen peroxide and HRP immobilized on polymer brushes. The composite film also showed excellent amperometric i-t response toward hydrogen peroxide in the concentration range of 0-13 μM. In future, this platform might be used for self-regulating targeted diagnostic, drug delivery and biofuel cell based on controllable bioelectrocatalysis. © 2013 Elsevier B.V.

A novel LTCC electrochemical cell construction and characterization: A detection compartment for portable devices

In this work we described for the first time the construction of a 25 μL electrochemical cell from low temperature co-fired ceramic (LTCC) material and carbon screen-printed electrode applicable in portable devices. Firstly, a carbon screen-printed electrode was prepared and characterized by cyclic voltammetry and scanning electron microscopy. Afterwards carbon polymeric film and metal pastes were dropped into the LTCC cell cavities in order to determine the device electrodes, and this arrangement was also electrochemically characterized. The great advantage of this promising device is the simple construction method and its widespread applicability in reusable portable devices. © 2013 The Royal Society of Chemistry.

Efeito do condicionamento ambiental nas propriedades de cisalhamento e viscoelásticas de compósitos híbridos metal-fibra

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Microwave-assisted hydrothermal synthesis of magnetite nanoparticles with potential use as anode in lithium ion batteries

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)