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.

Characterization of BaTi1-xZrxO3 thin films obtained by a soft chemical spin-coating technique

Single-phase perovskite structure BaZrxTi1-xO3 (BZT) (0.05less than or equal toxless than or equal to0.25) thin films were deposited on Pt-Ti-SiO2-Si substrates by the spin-coating technique. The structural modifications in the thin films were studied using x-ray diffraction and micro-Raman scattering techniques. Lattice parameters calculated from x-ray data indicate an increase in lattice (a axis) with the increasing content of zirconium in these films. Such Zr substitution also result in variations of the phonon mode wave numbers, especially those of lower wave numbers, for BaZrxTi1-xO3 thin films, corroborate to the structural change caused by the zirconium doping. on the other hand, Raman modes persist above structural phase transition, although all optical modes should be Raman inactive in the cubic phase. The origin of these modes must be interpreted as a function of a local breakdown of the cubic symmetry, which could be a result of some kind of disorder. The BZT thin films exhibited a satisfactory dielectric constant close to 181-138, and low dielectric loss tan delta<0.03 at the frequency of 1 kHz. The leakage current density of the BZT thin films was studied at elevated temperatures and the data obey the Schottky emission model. Through this analysis the Schottky barrier height values 0.68, 1.39, and 1.24 eV were estimated to the BZT5, BZT15, and BZT25 thin films, respectively. (C) 2004 American Institute of Physics.

A Bethe ansatz solution for the closed U-q[sl(2)] Temperley-Lieb quantum spin chains

We solve the spectrum of the closed Temperley-Lieb quantum spin chains using the coordinate Bethe ansatz. These models are invariant under the quantum group U-q[sl(2)].

GIGAHERTZ CONDUCTIVITY OF PRESSED PELLETS OF CLO4--DOPED POLY(3-METHYLTHIOPHENE) OBTAINED FROM ELECTRON-SPIN-RESONANCE MEASUREMENTS

Gigahertz conductivity of pressed pellets of ClO4--doped poly( 3-methylthiophene) can be readily obtained from the asymmetry ratio (A / B) of the electron spin resonance line using Dyson's theory. The measurements were performed in three different frequencies, 1.3, 9.4, and 35 GHz. The temperature dependence of the gigahertz conductivity is sensitive to the heating rate, probably due to the ordering of the randomly assembled anions. (C) 1994 Academic Press, Inc.

CONTINUED-FRACTION FORMALISM APPLIED TO THE SPIN-1/2 XYZ MODEL

In this paper, we evaluate the correlation functions of the spin-1/2 XYZ model for some particular cases by using the Mori continued-fraction formalism. The results are exactly the same as those well-known ones. This removes any doubt about the convergence of the continued fraction recently raised by some authors.

GREEN-FUNCTION FOR A SPIN-1/2 PARTICLE IN AN EXTERNAL PLANE-WAVE ELECTROMAGNETIC-FIELD

The Green function for a spin-1/2 charged particle in the presence of an external plane wave electromagnetic field is calculated by algebraic techniques in terms of the free-particle Green function.

CHOLESTEROL MODULATION OF LIPID PROTEIN INTERACTIONS IN LIVER MICROSOMAL MEMBRANE - A SPIN LABEL STUDY

ESR spectra of spin probes were used to monitor lipid-protein interactions in native and cholesterol-enriched microsomal membranes. In both systems composite spectra were obtained, one characteristic of bulk bilayer organization and another due to a motionally restricted population, which was ascribed to lipids in a protein microenvironment. Computer spectral subtractions revealed that cholesterol modulates the order/mobility of both populations in opposite ways, i.e., while the lipid bilayer region gives rise to more anisotropic spectra upon cholesterol enrichment, the spectra of the motionally restricted population become indicative of increased mobility and/or decreased order. These events were evidenced by measurement of both effective order parameters and correlation times. The percentages of the motionally restricted component were invariant in native and cholesterol-enriched microsomes. Variable temperature studies also indicated a lack of variation of the percentages of both spectral components, suggesting that the motionally restricted one was not due to protein aggregation. The results correlate well with the effect of cholesterol enrichment on membrane-bound enzyme kinetics and on the behavior of fluorescent probes [Castuma & Brenner (1986) Biochemistry 25, 4733-4738]. Several hypothesis are put forward to explain the molecular mechanism of the cholesterol-induced spectral changes.

Comments on spin operators and spin-polarization states of 2+1 fermions

In this brief article we discuss spin-polarization operators and spin-polarization states of 2 + 1 massive Dirac fermions and find a convenient representation by the help of 4-spinors for their description. We stress that in particular the use of such a representation allows us to introduce the conserved covariant spin operator in the 2 + 1 field theory. Another advantage of this representation is related to the pseudoclassical limit of the theory. Indeed, quantization of the pseudoclassical model of a spinning particle in 2 + 1 dimensions leads to the 4-spinor representation as the adequate realization of the operator algebra, where the corresponding operator of a first-class constraint, which cannot be gauged out by imposing the gauge condition, is just the covariant operator previously introduced in the quantum theory.

Two-phase separation observed in thermally treated pellets of ClO4- doped poly(3-methylthiophene) from electron spin resonance measurements

A pressed pellet of CIO (-)(4) poly (3-methylthiophene) (P3MT) was heated for two hours at 85 degrees C and suddenly dropped in liquid nitrogen. A change was observed around 220 K in the Electron Spin Resonance (ESR) spectra when the sample was slowly cooled from room temperature. ESR line asymmetry parameter (A/B) showed two spatially separated phases. One was identified as a small metallic-like phase. The other phase, the larger one, makes a transition to a semiconducting Charge-Density Wave (CDW) state.

Magnetic susceptibility of an exactly solvable anisotropic spin ladder system

We investigate the thermodynamics of an integrable spin ladder model which possesses a free parameter besides rung and leg couplings. The model is exactly solvable by means of the Bethe ansatz and exhibits a phase transition between a gapped and a gapless spin excitation spectrum. The magnetic susceptibility is obtained numerically and its dependence on the anisotropy parameter is determined. The spin gap obtained from the susceptibility curve and the one obtained from the Bethe ansatz equations are in very good agreement. Our results for the magnetic susceptibility fit well the experimental data for the organometallic compounds (5IAP)(2)CuBr4 . 2H(2)O (Landee C. P. et al., Phys. Rev. B, 63 (2001) 100402(R)) Cu-2(C5H12N2)(2)Cl-4 (Hayward C. A., Poilblanc D. and Levy L. P., Phys. Rev. B, 54 (1996) R12649, Chaboussant G. et al., Phys. Rev. Lett., 19 ( 1997) 925; Phys. Rev. B, 55 ( 1997) 3046.) and (C5H12N)(2)CuBr4 (Watson B. C. et al., Phys. Rev. Lett., 86 ( 2001) 5168) in the strong-coupling regime.

Use of spin label EPR spectra to monitor peptide chain aggregation inside resin beads.

An EPR approach to monitor peptide chain aggregation inside resin beads is introduced. Model low and highly peptide-loaded resins containing an aggregating sequence were labeled with a paramagnetic amino acid derivative and studied with regard to their solvation behavior in different solvent systems. For the first time in the peptide synthesis, EPR spectroscopic has allowed the detection of differentiated levels of peptide chain aggregation as a function of solvent and resin loading. (C) 1997, Elsevier B.V. Ltd. All rights reserved.

Spin, charge, and orbital correlations in the one-dimensional t(2g)-orbital Hubbard model

We present the zero-temperature phase diagram of the one-dimensional t(2g)-orbital Hubbard model, obtained using the density-matrix renormalization group and Lanczos techniques. Emphasis is given to the case of the electron density n=5 corresponding to five electrons per site, while several other cases for electron densities between n=3 and 6 are also studied. At n=5, our results indicate a first-order transition between a paramagnetic (PM) insulator phase, with power-law slowly decaying correlations, and a fully polarized ferromagnetic (FM) state by tuning the Hund's coupling. The results also suggest a transition from the n=5 PM insulator phase to a metallic regime by changing the electron density, either via hole or electron doping. The behavior of the spin, charge, and orbital correlation functions in the FM and PM states are also described in the text and discussed. The robustness of these two states against varying parameters suggests that they may be of relevance in quasi-one-dimensional Co-oxide materials, or even in higher dimensional cobaltite systems as well.

Role of oxygen vacancies in the magnetic and dielectric properties of the high-dielectric-constant system CaCu3Ti4O12: An electron-spin resonance study

We report experiments of electron spin resonance (ESR) of Cu2+ in polycrystalline samples of CaCu3Ti4O12 post-annealed in different atmospheres. After being synthesized by solid state reaction, pellets of CaCu3Ti4O12 were annealed for 24 h at 1000 degrees C under air, Ar or O-2. Our temperature dependent ESR data revealed for all samples nearly temperature independent g value (2.15(1)) and linewidth for T > T-N approximate to 25 K. However, the values of ESR linewidth are strongly affected by the oxygen content in the sample. For instance, argon post-annealed samples show a much larger linewidth than the O-2 or air post-annealed samples. We attribute this broadening to an increase of the dipolar homogeneous broadening of the Cu2+ ESR lines due to the presence of oxygen vacancies which induce an S=1/2 spin inside the TiO6 octahedra. Correlation between a systematic dependence of the ESR linewidth on the oxygen content and the high dielectric constant of these materials is addressed. Also, ESR, magnetic susceptibility, and specific heat data for a single crystal of CaCu3Ti4O12 and for polycrystals of CdCu3Ti4O12 are reported.

Analytical attitude propagation with non-singular variables and gravity gradient torque for spin stabilized satellite

An analytical approach for the spin stabilized satellite attitude propagation is presented using the non-singular canonical variables to describe the rotational motion. Two sets of variables were introduced for Fukushima in 1994 by a canonical transformation and they are useful when the angle between z-satellite axis of a coordinate system fixed in artificial satellite and the rotational angular momentum vector is zero or when the angle between Z-equatorial axis and rotation angular momentum vector is zero. Analytical solutions for rotational motion equations and torque-free motion are discussed in terms of the elliptic functions and by the application of some simplification to get an approximated solution. These solutions are compared with a numerical solution and the results show a good agreement for many rotation periods. When the mean Hamiltonian associated with the gravity gradient torque is included, an analytical solution is obtained by the application of the successive approximations' method for the satellite in an elliptical orbit. These solutions show that the magnitude of the rotation angular moment is not affected by the gravity gradient torque but this torque causes linear and periodic variations in the angular variables, long and short periodic variations in Z-equatorial component of the rotation angular moment and short periodic variations in x-satellite component of the rotation angular moment. The goal of this analysis is to emphasize the geometrical and physical meaning of the non-singular variables and to validate the approximated analytical solution for the rotational motion without elliptic functions for a non-symmetrical satellite. The analysis can be applied for spin stabilized satellite and in this case the general solution and the approximated solution are coincidence. Then the results can be used in analysis of the space mission of the Brazilian Satellites. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.