Investigation of New Ion Conducting Ormolytes Silica-Polypropyleneglycol

Two groups of hybrid organic-inorganic composites exhibiting ionic conduction properties, so called ORMOLYTES (organically modified electrolytes), have been prepared by the sol-gel process. The first group has been prepared from mixture of a lithium salt and 3-isocyanatopropyltriethoxysilane(IsoTrEOS),O,O′-bis(2-aminopropyl) polypropyleneglycol. These materials produce chemical bonds between the organic (polymer) and the inorganic (silica) phases. The second group has been prepared by an ultrasonic method from a mixture of tetraethoxysilane (TEOS), polypropyleneglycol and a lithium salt. The organic and inorganic phases are not chemically bonded in these samples. The Li+ ionic conductivity, σ, of all these materials has been studied by AC impedance spectroscopy up to 100°C. Values of σ up to 10-6 Ω-1·cm-1 have been found at room temperature. A systematic study of the effects of lithium concentration, polymer chain length and the polymer to silica weight ratio on σ shows that there is a strong dependence of σ on the preparation conditions. The dynamic properties of the Li+ ion and the polymer chains as a function of temperature between -100 and 120°C were studied using 7Li solid-state NMR measurements. The ionic conductivity of both families are compared and particular attention is paid to the nature of the bonds between the organic and inorganic components.

Hard X-ray photoemission study of the Fabre salts (TMTTF)(2)X (X = SbF6 and PF6)

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

A novel Mn-containing conducting metallopolymer obtained by electropolymerization in aqueous solution of a tetranuclear oxo-bridged manganese complex

The [Mn(4)(IV)O(5)(terpy)(4)(H(2)O)(2)](6+) complex shows great potential for electrode modification by electropolymerization using cyclic voltammetry. The electropolymerization mechanism was based on the electron transfer between dx(2)-y(2) orbitals of the metallic center and p pi orbital of the ligand.

Enzymeless Hydrogen Peroxide Sensor Based on Mn-containing Conducting Metallopolymer

The [(Mn4O5)-O-IV(terpy)(4)(H2O)(2)](6+) complex, show great potential for electrode modification by electropolymerization using cyclic voltammetry. The voltammetric behavior both in and after electropolymerization process were also discussed, where the best condition of electropolymerization was observed for low scan rate and 50 potential cycles. A study in glass electrode for better characterization of polymer was also performed. Electrocatalytic process by metal centers of the conducting polymer in H2O2 presence with an increase of anodic current at 0.85 V vs. SCE can be observed. The sensor showed great response from 9.9 x 10(-5) to 6.4 x 10(-4) mol L-1 concentration range with a detection limit of 8.8 x 10(-5) mol L-1, where the electrocatalytic mechanism was based on oxidation of H2O2 to H2O with consequently reduction of Mn-IV to Mn-III. After, the Mn-III ions are oxidized electrochemically to Mn-IV ions. (C) 2012 Elsevier Ltd .... Selection and/or peer-review under responsibility of the Symposium Cracoviense Sp. z.o.o.

Hyperfine interaction in Zn-Al layered double hydroxides intercalated with conducting polymers

Organic-inorganic hybrid materials based on the assembly between inorganic 2D host structure and polymer have received considerable attention in the last few years. This emerging class of materials presents several applications according to their structural and functional properties. Particularly, among others, layered double hydroxides (LDHs) provide the opportunity of preparing new organically modified 2D nanocomposites. Pyrrole carboxylic acid derivatives, namely 4-(lH-pyrrol-1-yl)benzoate, 3-(pyrrol-i-yl)-propanoate,7-(pyrrol-1-yl)-heptanoate, and aniline carboxylic acid derivative, namely 3-aminobenzoic acid, have been intercalated in LDHs of intralamellar composition Zn2Al(OH)(6). The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by powder X-ray diffraction patterns (PXRD), transmission electron microscopy (TEM) thermogravimetric analysis (TGA), and electron spin resonance (ESR). The basal spacing found by the PXRD technique gives evidence of the formation of bilayers of the intercalated anions. ESR spectra present a typical signal with a superhyperfine structure with 6 + 1 lines (g = 2.005 +/- 0.0004), which is assigned to the interaction between a carboxylate radical from the guest molecules and a nearby aluminium nucleus (I = 5/2) from the host structure. Additionally, the ESR data suggest that the monomers are connected to each other in limited number after thermal treatment. (c) 2007 Elsevier Ltd. All rights reserved.

A new route to obtain PVDF/PANI conducting blends

Electrically conductive poly(vinylidene fluoride)(PVDF) - polyaniline blends of different composition were synthesized by chemical polymerization of aniline in a mixture of PVDF and dimethylformamide (DMF) and studied by electrical conductivity measurement, UV-Vis-NIR and FTIR spectroscopy. The samples were obtained as flexible films by pressing the powder at 180 degrees C for 5 min. The electrical conductivity showed a great dependence on the syntheses parameters. The higher value of the electrical conductivity was obtained for the oxidant/aniline molar ratio equal to 1 and p-toluenesulfonic acid-TSA/aniline ratio between 3 and 6. UV-Vis-NIR and FTIR spectra of the blend are similar to the doped PANI, indicating that the PANI is responsible for the high electrical conductivity of the blend. The electrical conductivity of blend proved to be stable as a function of temperature decreasing about one order at temperature of 100 degrees C. The route used to obtain the polymer blend showed to be a suitable alternative in order to obtain PVDF/PANI-TSA blends with high electrical conductivity. (c) 2006 Elsevier Ltd. All rights reserved.

Strategic supplementation of calcium salts of polyunsaturated fatty acids to enhance reproductive performance of Bos indicus beef cows

Five experiments evaluated the effects of supplemental Ca salts of PUFA on reproductive function of Bos indicus beef cows. In Exp. 1, nonlactating and multiparous grazing cows (n = 51) were assigned to receive (as-fed basis) 0.1 kg of a protein-mineral mix + 0.1 kg of ground corn per cow/d, in addition to 0.1 kg per cow/d of 1) Ca salts of PUFA (PF), 2) Ca salts of SFA (SF), or 3) kaolin (control). Treatments were offered from d 0 to 20 of the estrous cycle. No treatment effects were detected on serum progesterone concentrations (P = 0.83), day of luteolysis (P = 0.86), or incidence of short cycles (P = 0.84). In Exp. 2, nonlactating and multiparous grazing cows (n = 43) were assigned to receive PF, SF, or control from d 0 to 8 of the estrous cycle. on d 6, all cows received (intramuscularly) 25 mg of PGF(2 alpha). No treatment effects were detected on serum progesterone concentrations on d 6 (P = 0.37), and incidence (P = 0.67) or estimated time of luteolysis (P = 0.44). In Exp. 3, twenty-seven lactating and multiparous grazing cows, approximately 30 to 40 d postpartum, were assigned to receive PF or control for 10 d beginning at the first postpartum ovulation. No treatment effects were detected (P = 0.85) on incidence of short cycles. In Exp. 4, lactating and multiparous grazing cows (n = 1,454), approximately 40 to 60 d postpartum, were assigned to receive 1 of the 7 treatments for 28 d after timed AI (TAI; d 0): 1) control from d 0 to 28, 2) SF from d 0 to 14 and then control, 3) PF from d 0 to 14 and then control, 4) SF from d 0 to 21 and then control, 5) PF from d 0 to 21 and then control, 6) SF from d 0 to 28, and 7) PF from d 0 to 28. Cows receiving PF for more than 21 d after TAI had greater (P < 0.01) pregnancy to TAI compared with all other treatments combined (50.4 vs. 42.4%, respectively). In Exp. 5, lactating and multiparous grazing cows (n = 501), approximately 40 to 60 d postpartum, were assigned to receive 1 of the 4 treatments for 21 d after TAI (d 0): 1) PF from d 0 to 14 and then control, 2) control from d 0 to 6 and then PF, 3) control from d 0 to 13 and then PF, and 4) PF from d 0 to 21. Cows receiving PF after d 14 of the experiment had greater (P = 0.02) pregnancy to TAI compared with cows not receiving PF during the same period (46.8 vs. 33.1%, respectively). In summary, supplemental Ca salts of PUFA during the expected time of luteolysis increased pregnancy to TAI in beef cows.

Effects of calcium salts of polyunsaturated fatty acids on productive and reproductive parameters of lactating Holstein cows

Two experiments evaluated milk production, serum progesterone and insulin, and reproductive performance of lactating Holstein cows receiving or not receiving Ca salts of polyunsaturated fatty acids (PUFA), or receiving Ca salts of PUFA at different daily frequencies. In experiment 1, 1,125 cows randomly distributed in 10 freestall barns were enrolled. Barns were assigned randomly to receive a high-concentrate diet containing (PI?) or not containing (control, CON) 1.1% (dry matter basis) Ca salts of PUPA. Diets were offered 6 times daily, whereas the Ca salts of PUFA were included in the PF treatment in the first feeding of the day. In experiment 2, 1,572 cows were randomly distributed in 10 freestall barns, which were assigned randomly to receive a diet similar to PF, but with Ca salts of PUFA included only in the first feeding of the day (PF1X), or equally distributed across all 6 feedings (PF6X). During both experiments, cows were artificially inseminated 12 h after the onset of estrus. Once per month, cows that did not conceive to artificial insemination were assigned to a fixed-time embryo transfer protocol. Pregnancy was determined via transrectal ultrasonography 28 and 60 d after expected ovulation. Pregnancy loss was considered in cows that were pregnant on d 28 but nonpregnant on d 60. During both experiments, feed intake, milk yield, and milk protein and fat content were recorded weekly. Blood samples were collected concurrently with embryo transfer. During experiment 1, feed intake was similar between treatments. Compared with CON, PF cows had greater milk yield (37.8 vs. 35.3 kg/d), and reduced milk fat content (3.41 vs. 3.55%). However, PF cows had reduced pregnancy losses per service compared with CON (12.6 vs. 18.3%). Serum progesterone was greater and serum insulin tended to be greater in primiparous cows receiving PF compared with CON cohorts (4.50 vs. 3.67 ng of progesterone/mL, and 10.4 vs. 7.5 mu UI of insulin/mL). During experiment 2, no treatment effects were detected for feed intake, milk yield, or milk fat, whereas PF1X cows tended to have reduced pregnancy losses per service compared with PF6X (14.4 vs. 18.4%). In summary, feeding Ca salts of PUFA to dairy cows increased milk production, did not alter feed intake, and reduced pregnancy losses per service. Further, the total daily amount of Ca salts of RITA should be fed during the first feeding of the day to optimize its benefits on pregnancy maintenance of dairy cows.

Phase Diagrams of the Aqueous Two-Phase Systems of Poly(ethylene glycol)/Sodium Polyacrylate/Salts

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

Formation of wakes by chiral conducting cosmic strings

Chiral cosmic strings are naturally produced at the end of D-term inflation and they present very interesting cosmological consequences. In this work, we investigate the formation and evolution of wakes by a chiral string. We show that, for cold dark matter, the mechanism of forming wakes by a chiral string is similar to the mechanism by an ordinary string.

Simultaneous observation of the magnetic and electric behavior in a correlated system near a metal-semiconductor transition: ESR in pellets of conducting polymers

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

Label-free DNA detection of hepatitis C virus based on modified conducting polypyrrole films at microelectrodes and atomic force microscopy tip-integrated electrodes

We present a new strategy for the label-free electrochemical detection of DNA hybridization for detecting hepatitis C virus based on electrostatic modulation of the ion-exchange kinetics of a polypyrrole film deposited at microelectrodes. Synthetic single-stranded 18-mer HCV genotype-1-specific probe DNA has been immobilized at a 2,5-bis(2-thienyl)-N-(3-phosphoryl-n-alkyl)pyrrole film established by electropolymerization at the previously formed polypyrrole layer. HCV DNA sequences (244-mer) resulting from the reverse transcriptase-linked polymerase chain reaction amplification of the original viral RNA were monitored by affecting the ion-exchange properties of the polypyrrole film. The performance of this miniaturized DNA sensor system was studied in respect to selectivity, sensitivity, and reproducibility. The limit of detection was determined at 1.82 x 10(-21) mol L-1. Control experiments were performed with cDNA from HCV genotypes 2a/c, 2b, and 3 and did not show any unspecific binding. Additionally, the influence of the spacer length of 2,5-bis(2-thienyl)-N-(3-phosphoryl-n-alkyl)pyrrole on the behavior of the DNA sensor was investigated. This biosensing scheme was finally extended to the electrochemical detection of DNA at submicrometer-sized DNA biosensors integrated into bifunctional atomic force scanning electrochemical microscopy probes. The 18-mer DNA target was again monitored by following the ion-exchange properties of the polypyrrole film. Control experiments were performed with 12-base pair mismatched sequences.

Asymmetrical penetration of microwave in a conducting media and determination of microwave conductivity for very thin samples using electron spin resonance

Dyson's theory of conduction electron spin resonance (CESR) has been used in the limit d less than or equal to delta (d being the thickness of the sample and delta the skin depth of the microwave field) to obtain the microwave conductivity from the (A/B) ratio of the CESR absorbed power derivative. In this work we calculate the CESR absorbed power derivative using Kaplan's approach and show that the (A/B) ratio can be enhanced if asymmetrical penetration of microwave is used, which means that the microwave field enters into the sample from one of the faces. Therefore, the determination of the microwave conductivity from the (A/B) ratio of the CESR line can be performed for thinner samples. Experimentally, asymmetrical penetration can be obtained if one of the sample's faces is covered with a thin gold layer. The determination of microwave conductivity in conducting polymers films is among the possible applications of this method. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Influence of the precursor salts in the synthesis of CaSnO3 by the polymeric precursor method

CaSnO3 was synthesized by the polymeric precursor method, using different precursor salts as (CH3COO)(2)Ca. H2O, Ca(NO3)(2). 4H(2)O, CaCl2. 2H(2)O and CaCO3, leading to different results. Powder precursor was characterized using thermal analysis. Depending on the precursor different thermal behaviors were obtained. Results also indicate the formation of carbonates, confirmed by IR spectra. After calcination and characterization by XRD, the formation of perovskite as single phase was only identified when calcium acetate was used as precursor. For other precursors, tin oxide was observed as secondary phase.