Effect of salt nature on structure and ionic conductivity of sodium-doped siloxane-PPO ormolytes

Siloxane-polyoxypropylene (PPO) hybrids obtained by the sol-gel process and containing short polymer chain have been doped with different sodium salts NaX (X = ClO4, BF4 or I). The effect of the counter-ion (X) on the chemical environment of the sodium ions and on the ionic conductivity of these hybrids was investigated by Na-23 NMR, small angle X-ray scattering (SAXS), complex impedance, Raman spectroscopy and differential scanning calorimetry (DSC). Results reveal that the different sodium salts have essentially the same effect on the nanoscopic structure of the hybrids. The formation of immobile Na+ cations involved in NaCl-like species could be minimized by using a low amount of HCl as hydrolytic catalyst. The differences in the ionic conductivity of hybrids doped with different sodium salts were correlated with the proportion of Na ions solvated by ether-type oxygen of the polymeric chains and by the carboxyl oxygen located in the urea groups of the PPO chain extremities. (c) 2005 Elsevier Ltd. All rights reserved.

The Strengths and Difficulties Questionnaire overseas: Evaluations and applications of the SDQ beyond Europe

Background During the few years that have passed since it became available, the Strengths and Difficulties Questionnaire (SDQ) has been extensively evaluated and widely applied to assess behaviour disorders of children and adolescents in European countries. In contrast, relatively few reports have published SDQ results obtained in other parts of the world, although its briefness and availability in over 40 languages make this instrument particularly attractive for international collaborations and cross-cultural comparisons concerning clinical and epidemiological issues. Objectives This initial overview summarises some of these non-European experiences with the SDQ by presenting a selection of projects that have either psychometrically evaluated this novel questionnaire, applied it to screen for behaviour disorders, or employed its parent-, teacher- or self-rated versions as research tools. Since a large part of the mentioned studies are ongoing or have only recently been completed, much of the work reported here is still unpublished. Conclusions Across a huge variety of cultures and languages, experience gained with the SDQ in other continents has supported European evidence of good psychometric properties and clinical utility of this questionnaire. Since worldwide usage of the SDQ can be expected to increase in the future, more international coordination is encouraged, in order to fully exploit the promising potentials of this versatile assessment tool and systematically investigate cross-cultural differences and similarities in child and adolescent behaviour.

Nonadiabatic calculations of the oscillator strengths for the helium atom in the hyperspherical adiabatic approach

Energies and wavefunctions are calculated for the bound states of the helium atom in the hyperspherical adiabatic approach by the full inclusion of nonadiabatic couplings. We show that the use of appropriate asymptotic radial boundary conditions not only allows the efficient calculation of energies accurate up to a few ppm for the ground state but also gives increasingly precise results for high-lying excited states with a unique set of equations. The accuracy of the wavefunctions is demonstrated by the calculation of oscillator strengths in the length form for transitions between stares ii S-1(e) and (n + 1) P-1(0) up to n = 29, in agreement with variational calculations.

Multi-scale structural description of siloxane-PPO hybrid ionic conductors doped by sodium salts

Alkaline metal doped organic - inorganic hybrids have potential applications in the field of portable energy sources. Attractive sol - gel derived urea cross-linked polyether, siloxane - PPO ( poly( propylene oxide)) hybrids doped with sodium salts ( NaClO4 and NaBF4) were examined by multi-spectroscopic approach that includes complex impedance, X-ray powder diffraction (XRPD), small angle X-ray scattering (SAXS), Si-29 and Na-23 magic-angle spinning nuclear magnetic resonance (NMR/MAS), Na K-edge X-ray absorption near edge structure (XANES) and Raman spectroscopies. The goals of this work were to determine which cation coordinating site of the host matrix ( ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the thermal and electrical properties. The main conclusion derived from this study is that the NaBF4 salt has a much lower solubility in the hybrid matrix than the NaClO4 salt. Furthermore, the addition of a large amount of salt plays a major role in the hybrid nanostructure and electrical properties, modifying the PPO chain conformation, weakening or breaking the hydrogen bond of the polyether - urea associations and changing the polycondensation and aggregation processes involving the siloxane species.

Langmuir-Blodgett films incorporating an ionic europium complex

Langmuir-Blodgett (LB) technique is a powerful tool to fabricate ultrathin films with highly ordered structures and controllable molecular array for efficient energy and electron transfer, allowing the construction of devices at molecular level. One method to obtain LB films consists in the mixture of classical film-forming molecules, for example Stearic Acid (SA) and functional metal complex. In this work NH(4)[Eu(bmdm)(4)], where the organic ligand bmdm is (butyl methoxy-dibenzoyl-methane) or (1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione) was used to build up Langmuir and LB films. Langmuir isotherms were obtained from (i) NH(4)[Eu(bmdm)(4)] complex and (ii) NH(4)[Eu(bmdm)(4)]/SA (1:1). Results indicated that (i) form multilayer structure; however the surface pressure was insufficient to obtain LB films, and (ii) can easily reproduce and build LB films. The dependence of number of layers in the UV absorption spectra suggest that the complex did not hydrolyze or show decomposition, UV spectral differences observed between the solution and the LB film indicate that the complex has a highly ordered arrangement in the film and the complex has an interaction with SA. Excitation spectra confirm a ligand-europium energy transfer mechanism. The transition lines of Eu(3+) ion were observed in emission spectra of all films, the photoluminescence spectra indicate a fluorescence enhanced effect with the number of LB layers. (C) 2009 Elsevier B.V. All rights reserved.

Lanthanum-lithium-sodium double chromates as ionic conductors

Lanthanum-lithium-sodium double chromates Li1-xNaxLa(CrO4)2 were prepared and analysed by means of admittance spectroscopy. Their a.c. conductivity parameters are correlated with structural details of high and low temperature forms of pure lanthanum-lithium double chromates. Lithium compounds show the lowest conductivity values and the highest activation energy for ion motion, while the sample Li0.5Na0.5La(CrO4)2 exhibits the highest conductivity 10-5 S cm-1 and the lowest activation energy 0.58 eV.

Tensile bond strengths of hard chairside reline resins as influenced by water storage

Due to gradual resorption of the edentulous ridge bone, removable prostheses often require denture base relines to improve fit and stability. This research evaluated the bond strength between one heat-cured acrylic resin (Lucitone 550®) and two hard chairside reline resins, after two different periods of storage in water (50 h and 30 days). The bond strength was evaluated using a tensile test. The mode of failure, adhesive or cohesive, was also recorded. The results submitted to the Kruskal-Wallis test indicated that the highest tensile strengths were achieved with intact Lucitone 550® denture base resin in both periods of storage in water. After 50 h of storage in water, Duraliner II® reline material exhibited the highest bond strength to the denture base resin. After 30 days of storage in water, Duraliner II® reline resin demonstrated a significant reduction in adhesion, showing lower tensile bond strength than Kooliner® material. Both hard chairside reline materials failed adhesively across Lucitone 550® denture base resin, in both periods of time. © 1999 Blackwell Science Ltd.

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.

Correlation between local structure and ionic conductivity of potassium-doped siloxane poly(propyleneoxyde) ormolytes

The local order around K for K(CF3SO3) doped Siloxane-Poly(propyleneoxide) hybrids at different doping concentration was investigated by x-ray absorption spectroscopy (EXAFS and XANES) at the potassium K-edge. The results indicate that the use of HCl as hydrolytic catalyst for gelation induces the precipitation of KCl. The ionic conductivity is strongly related to the presence of oxygen atoms as first neighbours around potassium and to the amount of KCl precipitate. © Physica Scripta 2005.

Effect of microwave disinfection procedures on torsional bond strengths of two hard chairside denture reline materials

Purpose: This study evaluated the potential effects of denture base resin water storage time and an effective denture disinfection method (microwave irradiation at 650 W for 6 minutes) on the torsional bond strength between two hard chairside reline resins (GC Reline and New Truliner) and one heat-polymerizing denture base acrylic resin (Lucitone 199). Materials and Methods: Cylindrical (30 x 3.9 mm) denture base specimens (n = 160) were stored in water at 37°C (2 or 30 days) before bonding. A section (3.0 mm) was removed from the center of the specimens, surfaces prepared, and the reline materials packed into the space. After polymerization, specimens were divided into four groups (n = 10): Group 1 (G1) - tests performed after bonding; Group 2 (G2) - specimens immersed in water (200 ml) and irradiated twice (650 W for 6 minutes); Group 3 (G3) - specimens irradiated daily until seven cycles of disinfection; Group 4 (G4) - specimens immersed in water (37°C) for 7 days. Specimens were submitted to a torsional test (0.1 Nm/min), and the torsional strengths (MPa) and the mode of failure were recorded. Data from each reline material were analyzed by a two-way analysis of variance, followed by Neuman-Keuls test (p = 0.05). Results: For both Lucitone 199 water storage periods, before bonding to GC Reline resin, the mean torsional strengths of G2 (2 days - 138 MPa; 30 days - 132 MPa), G3 (2 days - 126 MPa; 30 days - 130 MPa), and G4 (2 days - 130 MPa; 30 days - 137 MPa) were significantly higher (p < 0.05) than G1 (2 days - 108 MPa; 30 days - 115 MPa). Similar results were found for Lucitone 199 specimens bonded to New Truliner resin, with G1 specimens (2 days - 73 MPa; 30 days - 71 MPa) exhibiting significantly lower mean torsional bond strength (p < 0.05) than G2 (2 day - 86 MPa; 30 days - 90 MPa), G3 (2 days - 82 MPa; 30 days - 82 MPa), and G4 specimens (2 days - 78 MPa; 30 days - 79 MPa). The adhesion of both materials was not affected by water storage time of Lucitone 199 (p > 0.05). GC reline showed a mixed mode of failure (adhesive/cohesive) and New Truliner failed adhesively. Conclusions: Up to seven microwave disinfection cycles did not decrease the torsional bond strengths between the hard reline resins, GC Reline and New Truliner to the denture base resin Lucitone 199. The effect of additional disinfection cycles on reline material may be clinically significant and requires further study. Copyright © 2006 by The American College of Prosthodontists.

Comparison of the shear bond strengths of conventional mesh bases and sandblasted orthodontic bracket bases

This study aimed to compare in vitro the shear bond strength between metallic brackets (Abzil) with conventional mesh bases and metallic brackets with bases industrially sandblasted with aluminum oxide using three adhesive systems, in order to assess the influence of sandblasting on adhesiveness and to compare 3 different bonding systems. Two hundred and forty bovine incisors were used and randomly divided into 6 groups (40 teeth in each group), according to the bracket base and to the bonding system. The brackets were direct-bonded in bovine teeth with 3 adhesive systems: System A - conventional Transbond™ XT (3M -Unitek); System B - Transbond™ Plus Self Etching Primer + Transbond™ XT (3M - Unitek) and System C - Fuji ORTHO LC resin-reinforced glass ionomer cement in capsules (GC Corp.). Shear bond strength tests were performed 24 hours after bonding, in a DL-3000 universal testing machine (EMIC), using a load cell of 200 kgf and a speed of 1 mm/min. The results were submitted to statistical analysis and showed no significant difference between conventional and sandblasted bracket bases. However, comparison between the bonding systems presented significantly different results. System A (14.92 MPa) and system C (13.24 MPa) presented statistically greater shear bond strength when compared to system B (10.66 MPa). There was no statistically significant difference between system A and system C.

The electrochemical reduction of the purines guanine and adenine at platinum electrodes in several room temperature ionic liquids

The reduction of guanine was studied by microelectrode voltammetry in the room temperature ionic liquids (RTILs) N-hexyltriethylammonium bis (trifluoromethanesulfonyl) imide [N6,2,2,2][N(Tf)2], 1-butyl-3-methylimidazolium hexafluorosphosphate [C4mim][PF6], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide [C4mpyrr][N(Tf)2], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4mim][N(Tf)2], N-butyl-N-methyl-pyrrolidinium dicyanamide [C4mpyrr][N(NC)2] and tris(P-hexyl)-tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P14,6,6,6][FAP] on a platinum microelectrode. In [N6,2,2,2][NTf2] and [P14,6,6,6][FAP], but not in the other ionic liquids studied, guanine reduction involves a one-electron, diffusion-controlled process at very negative potential to produce an unstable radical anion, which is thought to undergo a dimerization reaction, probably after proton abstraction from the cation of the ionic liquid. The rate of this subsequent reaction depends on the nature of the ionic liquid, and it is faster in the ionic liquid [P14,6,6,6][FAP], in which the formation of the resulting dimer can be voltammetrically monitored at less negative potentials than required for the reduction of the parent molecule. Adenine showed similar behaviour to guanine but the pyrimidines thymine and cytosine did not; thymine was not reduced at potentials less negative than required for solvent (RTIL) decomposition while only a poorly defined wave was seen for cytosine. The possibility for proton abstraction from the cation in [N6,2,2,2][NTf2] and [P14,6,6,6][FAP] is noted and this is thought to aid the electrochemical dimerization process. The resulting rapid reaction is thought to shift the reduction potentials for guanine and adenine to lower values than observed in RTILs where the scope for proton abstraction is not present. Such shifts are characteristic of so-called EC processes where reversible electron transfer is followed by a chemical reaction. © 2009 Elsevier B.V.

Characterization of a tannase from Emericela nidulans immobilized on ionic and covalent supports for propyl gallate synthesis

The extracellular tannase from Emericela nidulans was immobilized on different ionic and covalent supports. The derivatives obtained using DEAE-Sepharose and Q-Sepharose were thermally stable from 60 to 75 °C, with a half life (t50) >24 h at 80 °C at pH 5. 0. The glyoxyl-agarose and amino-glyoxyl derivatives showed a thermal stability which was lower than that observed for ionic supports. However, when the stability to pH was considered, the derivatives obtained from covalent supports were more stable than those obtained from ionic supports. DEAE-Sepharose and Q-Sepharose derivatives as well as the free enzyme were stable in 30 and 50 % (v/v) 1-propanol. The CNBr-agarose derivative catalyzed complete tannic acid hydrolysis, whereas the Q-Sepharose derivative catalyzed the transesterification reaction to produce propyl gallate (88 % recovery), which is an important antioxidant. © 2012 Springer Science+Business Media Dordrecht.

Strongly luminescent, highly ionic europium in a lanthanum diphenylphosphinate matrix

A series of insoluble, chemically inert and thermally stable compounds La1-xEux(DPP)3 (x = 0.50, 0.20, 0.10, and 0.050; DPP = diphenylphosphinate) was synthesized and characterized by elemental and thermogravimetric analysis, FT Infrared spectroscopy and X-ray powder diffraction. Luminescence spectroscopy at both 77 and 298 K showed changes in the intensity of the hypersensitive transition 5D 0 → 7F2 of Eu3+ which are dependent of the excitation wavelength, suggesting that the europium occupies two different sites in the compounds. The large quantum efficiency and quantum yield, as well as the long radiative lifetime of the 5D0 Eu3+ level of the series of compounds, which are desirable qualities for light-conversion molecular devices, are discussed in terms of the interactions and the energy transfer process between the ligands and the metal ion. © 2012 Elsevier B.V. All rights reserved.