Weak ferromagnetism in poly(3-methylthiophene)(PMTh)

Ferromagnetic behaviour at 300 K has been observed from SQUID experiments in ClO4- doped PMTh, the samples were prepared electrochemically at 25 degreesC in acetonitrile with 0.1M LiClO4 and then partially reduced. Atomic absorption analysis discards magnetic particles contamination. Hysteresis curves were observed for pressed pellets in ail range of temperatures (300K-2K). The remanence at 300 K and pressed at 250 bar was around 8.06x10(-4) emu/g with coercitivity of 130 Oe. The influence of water content in the solvent during the sample synthesis and the pressure is shown. We discuss a model that explains our data in terms of the anisotropic superexchange Dziatoshinski-Moriya interaction giving rise to weak ferromagnetism.

Evidence of room temperature charge-density wave behavior and glass-like states in pressed pellets of lightly doped poly (3-methyl thiophene)

We show room temperature charge-density wave (CDW) characteristics in d.c. and a.c. electric data in pressed pellets of lightly doped poly(3-methylthiophene). The possibility of a Peierls glass is discussed and metastables states are observed. D.C. and A.C. data also show a state with negative differencial resistance.

Room temperature ferromagnetic behavior in pressed pellets of doped poly (3-methylthiophene)

Room temperature ferromagnetic behavior has been observed in pressed pellets of doped poly(3-methylthiophene). In this work we show that thermoremance data taken in two different ways favours the interpretation of data in terms of the Dzialoshinski-Moriya anisotropic superexchange interaction of the polarons via dopant anions giving rise to weak ferromagnetism.

Structure of magnetic poly(oxyethylene)-siloxane nanohybrids doped with Fe-II and Fe-III

Hybrid organic - inorganic nanocomposites doped with Fe-II and Fe-III ions and exhibiting interesting magnetic properties have been obtained by the sol - gel process. The hybrid matrix of these ormosils ( organically modified silicates), classed as di-ureasils and termed U( 2000), is composed of poly( oxyethylene) chains of variable length grafted to siloxane groups by means of urea crosslinkages. Iron perchlorate and iron nitrate were incorporated in the diureasil matrices, leading to compositions within the range 80 greater than or equal to n greater than or equal to 10, n being the molar ratio of ether-type O atoms per cation. The structure of the doped diureasils was investigated by small-angle X-ray scattering (SAXS). For Fe-II-doped samples, SAXS results suggest the existence of a two-level hierarchical structure. The primary level is composed of spatially correlated siloxane clusters embedded in the polymeric matrix and the secondary, coarser level consists of domains where the siloxane clusters are segregated. The structure of Fe-III-doped hybrids is different, revealing the existence of iron oxide based nanoclusters, identified as ferrihydrite by wide-angle X-ray diffraction, dispersed in the hybrid matrix. The magnetic susceptibility of these materials was determined by zero-field-cooling and field-cooling procedures as functions of both temperature and field. The different magnetic features between Fe-II- and Fe-III-doped samples are consistent with the structural differences revealed by SAXS. While Fe-II-doped composites exhibit a paramagnetic Curie-type behaviour, hybrids containing Fe-III ions show thermal and field irreversibilities.

Huge values of room-temperature dielectric constants in pellets of poly(3-methylthiophene)

Room temperature data of impedance and phase angle in pellets of electrochemically synthesized ClO4- doped poly(3-methylthiophene) (P3MT) were analyzed assuming the sample being represented by a parallel resistor-capacitor (RC) circuit or by a series RC circuit. The last assumption proved to be the correct one, and to confirm it we use the sample as the RC component of a resistor-capacitor-inductor series resonator. We discuss the possibility of this RC series behavior to be due to a charge-density wave characteristic also evidenced from the huge values of the low-frequency dielectric constant of the system.

Thermal diffusivity analysis of doped poly(methyl-methacrylate) with electron donor and acceptor molecules

A computer-assisted method for analysing photoacoustic spectra has been developed in the Windows(TM) environment with the use of an easy graphical interface, the computer simulation was carried out with the aim of using the entire expression of the Rosencwaig-Gersho theory, thus permitting multiple applications. The simulation was applied to a system that mimics the electron transfer process in which the concentration of octaethylporphin donor molecules was constant whereas the concentration of duroquinone and 2,3-dichloro-5,6-dicyano-1, l-benzoquinone acceptor molecules varied. The increment of the acceptor concentration influenced the photoacoustic amplitude and phase signals. In the phase signal a significant shift to smaller values was observed, denoting a faster heat generation. The analysis of the photoacoustic signal enabled the determination of the thermal diffusivity, the result obtained through the simulation was about (7 +/- 1) x 10(-7) m(2) s(-1) indicating that changes in the photoacoustic phase signals were due to the electron transfer process rather than changes in the thermal properties of the sample.

Influence of growth rate and length on fluoride detection in human nails

This study aimed to determine the lag time between increased fluoride (F) intake and F detection in human nails, as well as the influence of nails growth rate and length on this. Ten 20- to 35-year-old volunteers received 1.8 mg F daily, for 30 days. Nail growth rate and length were determined for all fingernails and toenails. Nail samples were collected at the beginning of the study and every 2 weeks (15 collections in all) and F concentrations were determined. The growth rate was statistically higher in fingernails than in toenails. No statistically significant differences were observed between right and left sides. Growth rate was significantly greater for big toenails than for the other toenails, but this pattern was not found for fingernails. The estimated mean lag times for F detection in fingernails and toenails were 101 and 123 days, respectively. An apparent increase in fingernail F concentrations was observed 84 days after the beginning of the study, although this was not statistically different from baseline. For toenails, statistically significant increases in F concentration in relation to baseline were observed 112 and 140 days after increased F ingestion. These increases occurred within the 95% confidence intervals for the calculated mean lag time for fluoride detection in nails. Considering the large amount of sample provided by the big toenails, together with their faster growth rate, as well as the fact that toenails are less prone to environmental contamination, our data suggest that big toenails are more suitable biomarkers of fluoride intake.

Structure and electrical properties of potassium-doped siloxane-poly(oxypropylene) ormolytes

The structure and the ionic conduction properties of siloxane-poly(oxypropylene) (PPO) hybrids doped with different potassium salts (KCF3SO3, KI, KClO4 and KNO2) are reported for two polymer molecular weights (300 and 4000 g/mol), labelled PPO300 and PPO4000, respectively. The doping concentration, related to the concentration of the ether type oxygen of the PPO chain, is the same whatever the salt and verifies [O]/[K] = 20. Ionic room temperature conductivity shows the highest value for the KCF3SO3 doped PPO4000 hybrid (4 x 10(-7)Omega(-1).cm(-1)). The structure of these hybrids was investigated by X-ray powder diffraction (XRPD) and X-ray absorption spectroscopy (EXAFS and XANES) at the potassium K-edge (3607 eV). XRPD results show that the hybrid matrix is always amorphous and the formation of secondary potassium phases is observed for all the samples, except for the KCF3SO3 doped PPO4000 hybrid. EXAFS results evidence a good correlation between the ionic conductivity and the presence of oxygen atoms as first neighbours around potassium.

Excited state dynamics of the Ho3+ ions in holmium singly doped and holmium, praseodymium-codoped fluoride glasses

The deactivation of the two lowest excited states of Ho3+ was investigated in Ho3+ singly doped and Ho3+, Pr3+-codoped fluoride (ZBLAN) glasses. We establish that 0.1-0.3 mol % Pr3+ can efficiently deactivate the first excited (I-5(7)) state of Ho3+ while causing a small reduction of similar to 40% of the initial population of the second excited (I-5(6)) state. The net effect introduced by the Pr3+ ion deactivation of the Ho3+ ion is the fast recovery of the ground state of Ho3+. The Burshstein model parameters relevant to the Ho3+-> Pr3+ energy transfer processes were determined using a least squares fit to the measured luminescence decay. The energy transfer upconversion and cross relaxation parameters for 1948, 1151, and 532 nm excitations of singly Ho3+-doped ZBLAN were determined. Using the energy transfer rate parameters we determine from the measured luminescence, a rate equation model for 650 nm excitation of Ho3+-doped and Ho3+, Pr3+-doped ZBLAN glasses was developed. The rate equations were solved numerically and the population inversion between the I-5(6) and the I-5(7) excited states of Ho3+ was calculated to examine the beneficial effects on the gain associated with Pr3+ codoping. (c) 2007 American Institute of Physics.

Influence of ionic interactions on the photoinduced Birefringence of poly[1-[4-(3-carboxy-4 hydroxyphenylazo) benzene sulfonamido]-1 2-ethanediyl, sodium salt] films

Electrostatic interactions govern most properties of polyelectrolyte films, as in the photoinduced bire-fringence of azo-containing polymers. In this paper we report a systematic investigation of optical storage characteristics of cast and layer-by-layer (LbL) films of poly[1 -[4-(3-carboxy-4 hydroxypheny-lazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). Birefringence was photoinduced faster in PAZO cast films prepared at high pHs, with the characteristic writing times decreasing almost linearly with the pH in the range between 4 and 9. This was attributed to an increased free volume for the azochromophores with the enhanced electrostatic repulsion in PAZO charged to a greater extent. In contrast, in LbL films of PAZO alternated with poly(allylamine hydrochloride) (PAH), the electrostatic interactions between the oppositely charged polymers hampered photoisomerization and molecular rearrangement, thus leading to a slower writing kinetics for highly charged PAH or PAZO.

Voltammetric sensor for sodium nitroprusside determination in biological fluids using films of poly-L-lysine

Sodium nitroprusside (NP), a commercial vasodilator, can be pre-concentrated on vitreous carbon electrode modified by films of 97.5%: 2.5% Poly-L-lysine (PLL): glutaraldehyde (GA). This coating gives acceptable anion exchange properties whilst giving the required improvement of adhesion to the glassy carbon electrode surface. Linear response range and detection limit on nitroprusside in B-R buffer pH 4.0, were 1 x 10(-6) to 2 x 10-(5) mol L-1 and 1 x 10(-7) mol L-1, respectively. The repeatability of the proposed sensor, evaluated in term of relative standard deviation, was measured as 4.1% for 10 experiments. The voltammetric sensor was directly applied to determination of nitroprusside in human plasma and urine samples and the average recovery for these samples was around 95-97% without any pre treatment.

Application of a glassy carbon electrode modified with poly(glutamic acid) in caffeic acid determination

Glassy carbon electrodes were coated with films of poly( glutamic acid) ( PG), and the modified electrode proved to be very effective in the oxidation of caffeic acid. The performance of the film was also tested with ascorbic acid, coumaric acid, ferulic acid, sinapic acid and chlorogenic acid. At pH 5.6, all the hydroxycinnamic acids yield a higher peak current intensity when oxidized after incorporation in the PG-modified electrode, and only the oxidation of ascorbic acid exhibits overpotential reduction. At pH 3.5 only caffeic and chlorogenic acid are incorporated in the modified electrode and exhibit a well-defined oxidation wave at +0.51 V and +0.48 V, which is the base for their determination. Linear calibration graphs were obtained from 9 x 10(-6) mol L-1 to 4 x 10(-5) mol L-1 caffeic acid by linear voltammetric scan and from 4 x 10(-6) mol L-1 to 3 x 10(-5) mol L-1 by square wave voltammetric scan. The method was successfully applied to the determination of caffeic acid in red wine samples without interference from other hydroxycinnamic acids or ascorbic acid.