Spin-Probe ESR Studies on Nanocomposite Polymer Electrolytes

The possibility of using spin-probe electron spin resonance (ESR) as a tool to study glass transition temperature, T g, of polymer electrolytes is explored in 4 hydroxy 2,2,6,6 tetramethylpiperidine N oxyl (TEMPOL) doped composite polymer electrolyte (PEG)46LiClO4 dispersed with nanoparticles of hydrotalcite. The T g is estimated from the measured values of T 50G, the temperature at which the extrema separation 2A zz of the broad powder spectrum decreases to 50 G. In another method, the correlation time τc for the spin probe dynamics was determined by computer simulation of the ESR spectra and T g has been identified as the temperature at which τc begins to show temperature dependence. While both methods give values of T g close to those obtained from differential scanning calorimetry, it is concluded that more work is required to establish spin-probe ESR as a reliable technique for the determination of T g.

Vitrification, relaxation and free volume in glycerol-water binary liquid mixture:Spin probe ESR studies

Glass transition and relaxation of the glycerol-water (G-W) binary mixture system have been studied over the glycerol concentration range of 5-85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition,sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.

Structural, optical and EPR studies on ZnO:Cu nanopowders prepared via low temperature solution combustion synthesis

Cu (0.1 mol%) doped ZnO nanopowders have been successfully synthesized by a wet chemical method at a relatively low temperature (300 degrees C). Powder X-ray diffraction (PXRD) analysis, scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier transformed infrared (FTIR) spectroscopy, UV-Visible spectroscopy, Photoluminescence (PL) and Electron Paramagnetic Resonance (EPR) measurements were used for characterization. PXRD results confirm that the nanopowders exhibit hexagonal wurtzite structure of ZnO without any secondary phase. The particle size of as-formed product has been calculated by Williamson-Hall (W-H) plots and Scherrer's formula is found to be in the range of similar to 40 nm. TEM image confirms the nano size crystalline nature of Cu doped ZnO. SEM micrographs of undoped and Cu doped ZnO show highly porous with large voids. UV-Vis spectrum showed a red shift in the absorption edge in Cu doped ZnO. PL spectra show prominent peaks corresponding to near band edge UV emission and defect related green emission in the visible region at room temperature and their possible mechanisms have been discussed. The EPR spectrum exhibits a broad resonance signal at g similar to 2.049, and two narrow resonances one at g similar to 1.990 and other at g similar to 1.950. The broad resonance signal at g similar to 2.049 is a characteristic of Cu2+ ion whereas the signal at g similar to 1.990 and g similar to 1.950 can be attributed to ionized oxygen vacancies and shallow donors respectively. The spin concentration (N) and paramagnetic susceptibility (X) have been evaluated and discussed. (C) 2011 Elsevier B. V. All rights reserved.

Ferromagnetic Resonance Force Microscopy

A new approach to magnetic resonance was introduced in 1992 based upon detection of spin-induced forces by J. Sidles [1]. This technique, now called magnetic resonance force microscopy (MRFM), was first demonstrated that same year via electron paramagnetic resonance (EPR) by D. Rugar et al. [2]. This new method combines principles of magnetic resonance with those of scanned probe technology to detect spin resonance through mechanical, rather than inductive, means. In this thesis the development and use of ferromagnetic resonance force microscopy (FMRFM) is described. This variant of MRFM, which allows investigation of ferromagnetic samples, was first demonstrated in 1996 by Z. Zhang et al. [3]. FMRFM enables characterization of (a) the dynamic magnetic properties of microscale magnetic devices, and (b) the spatial dependence of ferromagnetic resonance within a sample. Both are impossible with conventional ferromagnetic resonance techniques.

Ferromagnetically coupled systems, however, pose unique challenges for force detection. In this thesis the attainable spatial resolution - and the underlying physical mechanisms that determine it - are established. We analyze the dependence of the magnetostatic modes upon sample dimensions using a series of microscale yttrium iron garnet (YIG) samples. Mapping of mode amplitudes within these sample is attained with an unprecedented spatial resolution of 15μm. The modes, never before analyzed on this scale, fit simple models developed in this thesis for samples of micron dimensions. The application of stronger gradient fields induces localized perturbation of the ferromagnetic resonance modes. The first demonstrations of this effect are presented in this study, and a simple theoretical model is developed to explain our observations. The results indicate that the characteristics of the locally-detected ferromagnetic modes are still largely determined by the external fields and dimensions of the entire sample, rather than by the localized interaction volume (i.e., the locale most strongly affected by the local gradient field). Establishing this is a crucial first step toward understanding FMRFM in the high gradient field limit where the dispersion relations become locally determined. In this high gradient field regime, FMRFM imaging becomes analogous with that of EPR MRFM.

FMRFM has also been employed to characterize magnetic multilayers, similar to those utilized in giant magnetoresistance (GMR) devices, on a lateral scale 40 x 40μm. This is orders of magnitude smaller than possible via conventional methods. Anisotropy energies, thickness, and interface qualities of individual layers have been resolved.

This initial work clearly demonstrates the immense and unique potential that FMRFM offers for characterizing advanced magnetic nanostructures and magnetic devices.

Magnetic susceptibility and electron magnetic resonance study of monovalent potassium doped manganites Pr0.6Sr0.4-xK xMnO3

The monovalent potassium doped manganites Pr0.6Sr 0.4-xKxMnO3 (x = 0.05-0.2) are characterized using the complementary magnetic susceptibility and electron resonance methods. In paramagnetic phase the temperature variations of the inverse magnetic susceptibility and the inverse intensity of resonance signal obey the Curie-Weiss law. A similarity in temperature variation of resonance signal width and the adiabatic polaron conductivity points to the polaron mechanism controlling the resonance linewidth. The low temperature limit of the pure paramagnetic phase is determined from the electron resonance spectra revealing the mixed phase spread down to the Curie temperature. © 2013 Elsevier B.V. All rights reserved.

Experimental measurement of microwave-induced electron spin-flip time

The electron spin resonance (ESR) is optically detected by monitoring the microwave-induced changes in the circular polarization of the neutral exciton (X) and the negatively charged exciton (X-) emission in CdTe quantum wells with low density of excess electrons. We find that the circular polarization of the X and X- emission is a mapping of the spin polarization of excess electrons. By analyzing the ESR-induced decrease in the circular polarization degree of the X emission, we deduce the microwave-induced electron spin-flip time >0.1 mus, which is much longer than the recombination time of X and X-. This demonstrates that the optically detected ESR in type I quantum wells with low density of excess electrons does not obey the prerequisite for the conventional optically detected magnetic resonance. (C) 2001 American Institute of Physics.

Preparation and electrical-magnetic properties of polyaniline doped with ionic ferrocenesulfonic acid

Conducting polyamline with electrical conductivity of 2.34 x 10(-1) S cm(-1) was obtained using ferrocenesulfonic acid as dopant. After the ferrocenesulfonic acid was oxidized with FeCl3, though the electrical conductivity of the doped polyaniline decreased by 1-2 orders of magnitude, the magnetic susceptibility (chi) increased with the increase of the oxidation degree of ferrocenesulfonic acid. EPR spectra showed not only a signal with a g value of around 2, but also a so-called half-field signal with a g value of about 4 even at room temperature. Coexistence of ferromagnetic intrachain interactions and antiferromagnetic interchain interactions in the materials has been suggested.

Formation of the V center on H-type zeolites with thermal treatment

The effect of thermal treatment on H-MCM-22 and H-ZSM-5 zeolites was investigated using the electron spin resonance technique. A six-line signal (denoted as A, g = 2.048, A = 22. 15 G) was detected on H-MCM-22 after He purging at high temperatures, whose intensities increased with the treating temperature. The same signal was also found on H-ZSM-5 zeolites with different crystal sizes. The paramagnetic center was identified as a V center, namely, a hole of an electron trapped on an oxygen atom bonding to a nearby aluminum atom. These signals appeared only on a dealuminated sample or a sample concomitantly with dealumination. The formation of the hole might involve an electron transferring from the lattice oxygen to a nonframework aluminum species, and the hyperfine splitting is caused by the interaction between the electron hole locating on the p orbit of oxygen and the framework aluminum bonding with the oxygen. The signal disappeared after the sample was exposed to air or oxygen at room temperature. However, the process was reversible. A new set of signals (denoted as B, g(1) = 2.008, g(2) = 2.003, g(3) = 1.9985) was observed after oxygen adsorption on the H-MCM-22 pretreated with He at 973 K or He purging at 973 K on the H-MCM-22 pretreated with oxygen at 813 K, which was attributed to the O- species.

Characterization of iron atoms in the framework of MFI-type zeolites by UV resonance Raman spectroscopy

Silicalite-I, ZSM-5, and Fe-ZSM-5 zeolites prepared from two different silicon sources are characterized by UV resonance Raman (UVRR) spectroscopy, X-ray diffraction (XRD), electron spin resonance (ESR), and UV/visible diffuse reflectance spectroscopy (UV/Vis DRS). A new technique for investigating zeolitic structure, UV resonance Raman spectroscopy selectively enhances the Raman bands associated with framework iron atoms incorporated into MFI-type zeolites, and it is very sensitive in identifying the iron atoms in the framework of zeolites, while other techniques such as XRD, ESR, and UV/Vis DRS have failed in uncovering trace amounts of iron atoms in the framework of zeolites. (C) 2000 Academic Press.

Spin-orbit effects in GaAs quantum wells: Interplay between Rashba, Dresselhaus, and Zeeman interactions

The interplay between Rashba, Dresselhaus, and Zeeman interactions in a quantum well submitted to an external magnetic field is studied by means of an accurate analytical solution of the Hamiltonian, including electron-electron interactions in a sum-rule approach. This solution allows us to discuss the influence of the spin-orbit coupling on some relevant quantities that have been measured in inelastic light scattering and electron-spin resonance experiments on quantum wells. In particular, we have evaluated the spin-orbit contribution to the spin splitting of the Landau levels and to the splitting of charge- and spin-density excitations. We also discuss how the spin-orbit effects change if the applied magnetic field is tilted with respect to the direction perpendicular to the quantum well.

Spin-orbit effects in GaAs quantum wells: Interplay between Rashba, Dresselhaus, and Zeeman interactions

The interplay between Rashba, Dresselhaus, and Zeeman interactions in a quantum well submitted to an external magnetic field is studied by means of an accurate analytical solution of the Hamiltonian, including electron-electron interactions in a sum-rule approach. This solution allows us to discuss the influence of the spin-orbit coupling on some relevant quantities that have been measured in inelastic light scattering and electron-spin resonance experiments on quantum wells. In particular, we have evaluated the spin-orbit contribution to the spin splitting of the Landau levels and to the splitting of charge- and spin-density excitations. We also discuss how the spin-orbit effects change if the applied magnetic field is tilted with respect to the direction perpendicular to the quantum well.

New age estimates for the Palaeolithic assemblages and Pleistocene succession of Casablanca, Morocco

Marine and aeolian Quaternary sediments from Casablanca, Morocco were dated using the optically stimulated luminescence (OSL) signal of quartz grains. These sediments form part of an extensive succession spanning the Pleistocene, and contain a rich faunal and archaeological record, including an Acheulian lithic assemblage from before the Brunhes–Matayama boundary, and a Homo erectus jaw from younger cave deposits. Sediment samples from the sites of Reddad Ben Ali, Oulad J’mel, Sidi Abderhamane and Thomas Quarries have been dated, in order to assess the upper limits of OSL. The revision of previously measured mammalian tooth enamel electron spin resonance (ESR) dates from the Grotte des Rhinocéros, Oulad Hamida Quarry 1, incorporating updated environmental dose rate measurements and attenuation calculations, also provide chronological constraint for the archaeological material preserved at Thomas Quarries. Several OSL age estimates extend back to around 500,000 years, with a single sample providing an OSL age close to 1 Ma in magnetically reversed sediments. These luminescence dates are some of the oldest determined, and their reliability is assessed using both internal criteria based on stratigraphic consistency, and external lithostratigraphic, morphostratigraphic and independent chronological constraints. For most samples, good internal agreement is observed using single aliquot regenerative-dose OSL measurements, while multiple aliquot additive-dose measurements generally have poorer resolution and consistency. Novel slow-component and component-resolved OSL approaches applied to four samples provide significantly enhanced dating precision, and an examination of the degree of signal zeroing at deposition. A comparison of the OSL age estimates with the updated ESR dates and one U-series date demonstrate that this method has great potential for providing reliable age estimates for sediments of this antiquity. We consider the cause of some slight age inversion observed at Thomas Quarries, and provide recommendations for further luminescence dating within this succession.

DNA alters the bilayer structure of cationic lipid diC14-amidine: A spin label study

Cationic lipids-DNA complexes (lipoplexes) have been used for delivery of nucleic acids into cells in vitro and in vivo. Despite the fact that, over the last decade, significant progress in the understanding of the cellular pathways and mechanisms involved in lipoplexes-mediated gene transfection have been achieved, a convincing relationship between the structure of lipoplexes and their in vivo and in vitro transfection activity is still missing. How does DNA affect the lipid packing and what are the consequences for transfection efficiency is the point we want to address here. We investigated the bilayer organization in cationic liposomes by electron spin resonance (ESR). Phospholipids spin labeled at the 5th and 16th carbon atoms were incorporated into the DNA/diC14-amidine complex. Our data demonstrate that electrostatic interactions involved in the formation of DNA-cationic lipid complex modify the packing of the cationic lipid membrane. DNA rigidifies the amidine fluid bilayer and fluidizes the amidine rigid bilayer just below the gel-fluid transition temperature. These effects were not observed with single nucleotides and are clearly related to the repetitive charged motif present in the DNA chain and not to a charge-charge interaction. These modifications of the initial lipid packing of the cationic lipid may reorient its cellular pathway towards different routes. A better knowledge of the cationic lipid packing before and after interaction with DNA may therefore contribute to the design of lipoplexes capable to reach specific cellular targets. (c) 2009 Elsevier B.V. All rights reserved.

On the interaction of the anthraquinone barbaloin with negatively charged DMPG bilayers

Barbaloin is a bioactive glycosilated 1,8-dihydroxyanthraquinone present in several exudates from plants, Such as Aloe vera, which are used for cosmetic or food purposes. It has been shown that barbaloin interacts with DMPG (dimyristoylphosphatidylglycerol) model membranes, altering the bilayer structure (Alves, D. S.; Perez-Fons, L.; Estepa, A.; Micol, V. Biochem. Pharm. 2004, 68, 549). Considering that ESR (electron spin resonance) of spin labels is one of the best techniques to monitor structural properties at the molecular level, the alterations caused by the anthraquinone barbaloin on phospholipid bilayers will be discussed here via the ESR signal of phospholipid spin probes intercalated into the membranes. In DMPG at high ionic strength (10 mM Hepes pH 7.4 + 100 mM NaCl), a system that presents a gel-fluid transition around 23 degrees C, 20 mol % barbaloin turns the gel phase more rigid, does not alter much the fluid phase packing, but makes the lipid thermal transition less sharp. However, in a low-salt DMPG dispersion (10 mM Hepes pH 7.4 + 2 mM NaCl), which presents a rather complex gel-fluid thermal transition (Lamy-Freund, M. T.; Riske, K. A. Chem. Phys. Lipids 2003, 122, 19), barbaloin strongly affects bilayer structural properties, both in the gel and fluid phases, extending the transition region to much higher temperature values. The position of barbaloin in DMPG bilayers will be discussed on the basis of ESR results, in parallel with data from sample viscosity, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering).

Observation of two-magnon bound states in the spin-1 anisotropic Heisenberg antiferromagnetic chain system NiCl2-4SC(NH2)(2)

Results of systematic tunable-frequency ESR studies of the spin dynamics in NiCl2-4SC(NH2)(2) (known as DTN), a gapped S = 1 chain system with easy-plane anisotropy dominating over the exchange coupling (large-D chain), are presented. We have obtained direct evidence for two-magnon bound states, predicted for S = 1 large-D spin chains in the fully spin-polarized (FSP) phase. The frequency-field dependence of the corresponding excitations was calculated using the set of parameters obtained earlier [S.A. Zvyagin, et al., Phys. Rev. Lett. 98 (2007) 047205]. Very good agreement between the calculations and the experiment was obtained. It is argued that the observation of transitions from the ground to two-magnon bound states might indicate a more complex picture of magnetic interactions in DTN, involving a finite in-plane anisotropy. (C) 2007 Elsevier B.V. All rights reserved.