Spin-orbit coupling in the superconducting phase and DDW states of high-T-c cuprates

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Antioxidant Properties of Plant Extracts: an EPR and DFT Comparative Study of the Reaction with DPPH, TEMPOL and Spin Trap DMPO

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

Correlation between the mobility of spin-labeled peptide chains and resin solvation: An approach to optimize the synthesis of aggregating sequences

Resin solvation properties affect the efficiency of the coupling reactions in solid-phase peptide synthesis. Here we report a novel approach to evaluate resin solvation properties, making use of spin label electron paramagnetic resonance (EPR) spectroscopy. The aggregating VVLGAAIV and ING sequences were assembled in benzhydrylamine-resin with different amino group contents (up to 2.6 mmol/g) to examine the extent of chain association within the beads. These model peptidyl-resins were first labeled at their N-terminus with the amino acid spin label 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (Toac). Their solvation properties in different solvents were estimated, either by bead swelling measurement or by assessing the dynamics of their polymeric matrixes through the analysis of Toac EPR spectra, and were correlated with the yield of the acylation reaction. In most cases the coupling rate was found to depend on bead swelling. Comparatively, the EPR approach was more effective. Line shape analysis allowed the detection of more than one peptide chain population, which influenced the reaction. The results demonstrated the unique potential of EPR spectroscopy not only for improving the yield of peptide synthesis, even in challenging conditions, but also for other relevant polymer-supported methodologies in chemistry and biology.

Determination of site-site distance and site concentration within polymer beads: A combined swelling-electron paramagnetic resonance study

[GRAPHICS]This work proposes a combined swelling-electron paramagnetic resonance (EPR) approach aiming at determining some unusual polymer solvation parameters relevant for chemical processes occurring inside beads. Batches of benzhydrylamine-resin (BHAR), a copolymer of styrene-1% divinylbenzene containing phenylmethylamine groups were, labeled with the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amine-4-carboxylic acid (TOAC), and their swelling properties and EPR spectra were examined in DCM and DMF. By taking into account the BHARs labeling degrees, the corresponding swelling values, and some polymer structural characteristics, it was possible to calculate polymer swelling parameters, among them, the volume and the number of sites per bead, site-site distances and site concentration. The latter values ranged from 17 to 170 angstrom and from 0.4 to 550 mM, respectively. EPR spectroscopy was applied to validate the multistep calculation strategy of these swelling parameters. Spin-spin interaction was detected in the labeled resins at site-site distances less than approximately 60 A or probe concentrations higher than approximately 1 x 10(-2) M, in close agreement with the values obtained for the spin probe free in solution. Complementarily, the yield of coupling reactions in different resins indicated that the greater the inter-site distance or the lower the site concentration, the faster the reaction. The results suggested that the model and the experimental measurements developed for the determination of solvation parameters represent a relevant step forward for the deeper understanding and improvement of polymer-related processes.

Fmoc-POAC: [(9-fluorenylmethyloxycarbonyl)-2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid]: A novel protected spin labeled beta-amino acid for peptide and protein chemistry

The stable free radical 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (TOAC) is the only spin labeled amino acid that has been used to date to successfully label peptide sequences for structural studies. However, severe difficulty in coupling the subsequent amino acid has been the most serious shortcoming of this paramagnetic marker. This problem stems from the low nucleophilicity of TOAC's amine group towards the acylation reaction during peptide chain elongation. The present report introduces the alternative beta -amino acid 2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid (POAC), potentially useful in peptide and protein chemistry. Investigations aimed at addressing the stereochemistry of this cyclic molecule through X-ray diffraction measurements of crystalline and bulk samples revealed that it consists only of the trans conformer. The 9-fluorenylmethyloxyearbonyl group (Fmoc) was chosen for temporary protection of the POAC amine function, allowing insertion of the probe at any position in a peptide sequence. The vasoactive octapeptide angiotensin II (AII, DRVYIHPF) was synthesized by replacing Pro(7) with POAC. The reaction of Fmoc-POAC with the peptidyl-resin occurred smoothly, and the coupling of the subsequent amino acid showed a much faster reaction when compared with TOAC. POAC(7)-AII was obtained in good yield, demonstrating that, in addition to TOAC, POAC is a convenient amino acid for the synthesis of spin labeled peptide analogues. The present findings open the possibility of a wide range of chemical and biological applications for this novel beta -amino acid derivative, including structural investigations involving its differentiated bend-inducing characteristics.

Differential scanning calorimetry, x-ray diffraction and F-19 nuclear magnetic resonance investigations of the crystallization of InF3-based glasses

Results of differential scanning calometry (DSC), x-ray diffraction (XRD), and F-19 nuclear magnetic resonance (NMR) of InF3-based glasses, treated at different temperatures, ranging from glass transition temperature (T-g) to crystallization temperature (T-c), are reported. The main features of the experimental results are as follows. DSC analysis emphasizes several steps in the crystallization process. Heat treatment at temperatures above T-g enhances the nucleation of the first growing phases but has little influence on the following ones. XRD results show that several crystalline phases are formed, with solid state transitions when heated above 680 K, the F-19 NMR results show that the spin-lattice relaxation, for the glass samples heat treated above 638 K, is described by two time constants. For samples treated below this temperature a single time constant T-1 was observed. Measurements of the F-19 spin-lattice relaxation time (T-1), as a function of temperature,made possible the identification of the mobile fluoride ions. The activation energy, for the ionic motion, in samples treated at crystallization temperature was found to be 0.18 +/- 0.01 eV. (C) 1998 American Institute of Physics.

Direct electron paramagnetic resonance monitoring of the peptide synthesis coupling reaction in polymeric support

This work demonstrates, for the first time. a time-resolved electron paramagnetic resonance (EPR) monitoring of a chemical reaction occurring in a polymeric structure. The progress of the coupling of a N-alpha-tert-butyloxycarbonyl-2.2.6.6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (Boc-TOAC) spin probe to a model peptide-resin was followed through EPR spectra. Progressive line broadening of EPR peaks was observed, indicative of an increased population of immobilized spin probe molecules attached to the solid support. The time for spectral stabilization of this process coincided with that determined in a previous Coupling study. thereby validating this in situ quantitative monitoring of the reaction. In addition, the influence of polymer swelling degree and solvent viscosity, as well as of the steric hindrance within beads. on the rate of coupling reaction was also addressed. A deeper evaluation of the latter effect was possible by determining unusual polymer parameters such as the average site-site distance and site-concentration within resin beads in each solvent system. (c) 2006 Elsevier Ltd. All rights reserved.

Exciton formation in dye doped OLEDs using electrically detected magnetic resonance

Electrically Detected Magnetic Resonance (EDMR) was used to investigate the influence of dye doping molecules on spin-dependent exciton formation in Aluminum (III) 8-hydroxyquinoline (Alq(3)) based OLEDs with different device structures and temperature ranges. 4-(dicyanomethylene)-2-methyl-6-{2-[(4-diphenylamino-phenyl]ethyl}-4H-pyran (DCM-TPA) and 5,6,11,12-tetraphenylnaphthacene (Rubrene) were used as dopants. A strong temperature dependence have been observed for doped OLEDs, with a decrease of two orders of magnitude in EDMR signal for temperatures above similar to 200 K. The signal temperature dependence were fitted supposing different spin-lattice relaxation processes. The results suggest that thermally activated vibrations of dopants molecules induce spin pair dissociation, reducing the signal.

Polarized structure functions of the nucleon in the resonance region

We present predictions for the spin structure functions of the proton in the framework of a unitary isobar model for one-pion photo- and electroproduction. Our results are compared with recent experimental data from SLAC. The first moments of the calculated structure functions fullfil the Gerasimov-Drell-Hearn and Burkhardt-Cottingham sum rules within an error of typically 5-10%.

Spin-resolved local density of states for an Anderson adatom in a ferromagnetic island

In this work, we investigate theoretically the spin-resolved local density of states (SR-LDOS) of a ferromagnetic (FM) island hybridized with an adatom, which is described by the Single Impurity Anderson Model (SIAM). Our results are comparable with Scanning Tunneling Microscope (STM) experimental data. © 2012 Springer Science+Business Media, LLC.

Técnicas avançadas para caracterização de processos de transporte dependente do Spin

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electrically detected magnetic resonance modeling and fitting: An equivalent circuit approach

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Measuring the solubility product constant of paramagnetic cations using time-domain nuclear magnetic resonance relaxometry

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

Nuclear magnetic relaxation for the spin-degenerate Anderson model

A renormalization-group calculation of the temperature-dependent nuclear spin relaxation rate for a magnetic impurity in a metallic host is reported. The calculation follows a simplified procedure, which produces accurate rates in the low-temperature Fermi-liquid regime, although yielding only qualitatively reliable results at higher temperatures. In all cases considered, as the temperature T diminishes, the rates peak before decaying linearly to zero in the Fermi-liquid range. For T → 0, the results agree very well with Shiba's expression relating the low-temperature coefficient of the relaxation rate to the squared zero-temperature susceptibility. In the Kondo limit, the enhanced susceptibility associated with the Kondo resonance produces a very sharp peak in the relaxation rate near the Kondo temperature. © 1991.

Estudos de acoplamento spin-órbita em dinâmica do sistema solar

Pós-graduação em Física - FEG