Investigating magnetically aligned phospholipid bilayers with EPR spectroscopy at 94 GHz

In this paper, we report our initial results on studying magnetically aligned phospholipid bilayers (bicelles) at high magnetic fields (approximately 3.4 T) with electron paramagnetic resonance (EPR) spectroscopy at 95 GHz (W-band). In order to characterize this system for W-band EPR studies, we have utilized the nitroxide spin probe 3beta-doxyl-5alpha-cholestane to demonstrate the effects of macroscopic bilayer alignment. At W-band due to the increase in magnetic field strength (when compared to X-band studies at 9.5 GHz) (S. M. Garber et al., J. Am. Chem. Soc. 121, 3240-3241 (1999)), we were able to examine magnetically aligned phospholipid bilayers at two orientations with the bilayer normal oriented either perpendicular or parallel (upon addition of YbCl3) with respect to the direction of the static magnetic field. Additionally, at a magnetic field of 3.4 T (g=2 resonance at W-band), we were able to study the parallel alignment with a lower concentration of Yb3+, thereby eliminating the possible unwanted effects associated with lanthanide-protein interactions and paramagnetic shifts and/or line broadening induced by the lanthanide ions. The development of this new spin label alignment technique will open up a whole new area of investigation for phospholipid bilayer systems and membrane protein EPR studies at high magnetic fields.     

Resolving domains of interdigitated phospholipid membranes with 95 GHz spin labeling EPR

High-field W-band (95 GHz) electron paramagnetic resonance (EPR) study of partitioning of a small nitroxide TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) in multilamellar liposomes composed from 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) is described. The high-resolution spectra with a high signal-to-noise ratio were combined with automated least-squares simulation analysis to derive accurate partitioning coefficients of TEMPO in the membrane lipid phase and to follow the membrane phase transitions. The isotropic magnetic parameters, g_iso and A_iso were used to characterize the average polarity the spin label is experiencing in the membrane. We also report an empirical correlation between g_iso and A_iso for a set of protic and aprotic solvents and use this correlation to assign domains formed by interdigitation of DPPC bilayer under a high ethanol concentration of 1.2 M.     

Sensitivity enhancement in structural measurements by solid state NMR through pulsed spin locking

Free induction decay (FID) signals in solid state NMR measurements performed with magic angle spinning can often be extended in time by factors on the order of 10 by a simple pulsed spin locking technique. The sensitivity of a structural measurement in which the structural information is contained in the dependence of the integrated FID amplitude on a preceding evolution period can therefore be enhanced substantially by pulsed spin locking in the signal detection period. We demonstrate sensitivity enhancements in a variety of solid state NMR techniques that are applicable to selectively isotopically labeled samples, including 13C-15N rotational echo double resonance (REDOR), 13C-13C dipolar recoupling measurements using the constant-time finite-pulse radio-frequency-driven recoupling (fpRFDR-CT) and constant-time double-quantum-filtered dipolar recoupling (CTDQFD) techniques, and torsion angle measurements using the double quantum chemical shift anisotropy (DQCSA) technique. Further, we demonstrate that the structural information in the solid state NMR data is not distorted by pulsed spin locking in the detection period.     

Electron spin resonance shift in spin ladder compounds

We analyze the effects of different coupling anisotropies in a spin-1/2 ladder on the electron spin resonance (ESR) shift. Combining a perturbative expression in the anisotropies with density matrix renormalization group computation of the short range correlations at finite temperature, we provide the full temperature and magnetic field evolution of the ESR paramagnetic shift. We show that for well chosen parameters the ESR shift can be in principle used to extract quantitatively the anisotropies and, as an example, discuss the material BPCB.     

High-field/high-frequency EPR spectrometer operating in pulsed and continuous-wave mode at 180 GHz

A novel electron paramagnetic resonance (EPR) spectrometer is reported, which has been developed to allow pulsed EPR experiments with high sensitivity and time resolution at a microwave (MW) frequency of 180 GHz (G-band) and wavelengths of approximately 1.6 mm. This corresponds to a magnetic field of about 6.4 T forg ≈ 2 signals. The “hybrid” system architecture combines components of quasioptical as well as conventional MW techniques, making it possible to achieve excellent spectrometer performance with respect to sensitivity and time resolution. Quasioptical MW components have been used to design an MW circulator allowing high sensitivity and low bias operation in the reflection mode. A miniaturized, closed-type cylindrical cavity provides a high sample filling factor and an adequate MW field strength (B₁) enhancement and thus permits reasonably short MW pulses (60 ns for a π/2 pulse) even with a moderate MW input power (15 mW at the cavity). Commercial quartz capillaries (up to 0.5 mm internal diameter) can be used as sample holders for a broad range of applications.     

A continuous-wave and pulsed electron spin resonance spectrometer operating at 275 GHz

An electron paramagnetic resonance (EPR) spectrometer is described which allows for continuous-wave and pulsed EPR experiments at 275 GHz (wavelength 1.1 mm). The related magnetic field of 9.9 T for g approximately 2 is supplied by a superconducting solenoid. The microwave bridge employs quasi-optical as well as conventional waveguide components. A cylindrical, single-mode cavity provides a high filling factor and a high sensitivity for EPR detection. Even with the available microwave power of 1 mW incident at the cavity a high microwave magnetic field B1 is obtained of about 0.1 mT which permits pi/2-pulses as short as 100 ns. The performance of the spectrometer is illustrated with the help of spectra taken with several samples.     

Membrane fluidity profiles as deduced by saturation-recovery EPR measurements of spin-lattice relaxation times of spin labels

There are no easily obtainable EPR spectral parameters for lipid spin labels that describe profiles of membrane fluidity. The order parameter, which is most often used as a measure of membrane fluidity, describes the amplitude of wobbling motion of alkyl chains relative to the membrane normal and does not contain explicitly time or velocity. Thus, this parameter can be considered as nondynamic. The spin-lattice relaxation rate () obtained from saturation-recovery EPR measurements of lipid spin labels in deoxygenated samples depends primarily on the rotational correlation time of the nitroxide moiety within the lipid bilayer. Thus, can be used as a convenient quantitative measure of membrane fluidity that reflects local membrane dynamics. profiles obtained for 1-palmitoyl-2-(n-doxylstearoyl)phosphatidylcholine (n-PC) spin labels in dimyristoylphosphatidylcholine (DMPC) membranes with and without 50 mol% cholesterol are presented in parallel with profiles of the rotational diffusion coefficient, R_⊥, obtained from simulation of EPR spectra using Freed’s model. These profiles are compared with profiles of the order parameter obtained directly from EPR spectra and with profiles of the order parameter obtained from simulation of EPR spectra. It is shown that and R_⊥ profiles reveal changes in membrane fluidity that depend on the motional properties of the lipid alkyl chain. We find that cholesterol has a rigidifying effect only to the depth occupied by the rigid steroid ring structure and a fluidizing effect at deeper locations. These effects cannot be differentiated by profiles of the order parameter. All profiles in this study were obtained at X-band (9.5 GHz).     

Electron spin relaxation times and internal motions of radicals in the solid state investigated by ENDOR and pulsed EPR

The angular dependent ENDOR spectra of the radical formed by ψ-irradiated single crystal of 4-methyl-2,6-di-t-butylphenol have been studied and the full hyperfine tensors of all the t-butyl and the ring protons have been obtained atT=190 K. We found six different tensors for the t-butyl protons. This result shows that the t-butyl groups are slowly rotating on the ENDOR time scale, whereas each methyl group rotates fastly. The dynamical parameters of the motions have been determined by pulsed EPR experiments. The longitudinal relaxation and the phase memory times have been measured in the temperature range 130–290 K. Three different kinds of motions have been detected and the resulting values of the dynamical parameters have been compared with those obtained for the undamaged molecule by previous NMR studies.     

Reflectivity of some materials at 94 GHz

In order to better understand the characteristics of discrete natural land clutter at millimeter wavelengths, an experimental investigation of the relative reflectivity of various materials at 94 GHz was performed using a substitution technique. The data show that nonconducting materials have a relative reflectivity on the order of 2–3%, and that absorbed water can increase the relative reflectivity significantly.     

Phase diagram of an asymmetric spin ladder

We investigate an asymmetric zigzag spin ladder with different exchange integrals on both legs using bosonization and renormalization group approaches. When the leg exchange integrals and frustration both are sufficiently small, renormalization group analysis shows that the Heisenberg critical point flows to an intermediate-coupling fixed point with gapless excitations and a vanishing spin velocity. When they are large, a spin gap opens and a dimer liquid is realized. Here, we find a continuous manifold of Hamiltonians with dimer product ground states, interpolating between the Majumdar-Ghosh and sawtooth spin-chain model.     

Observation of high-temperature Heisenberg ferromagnet spin relaxation by EPR

The exponential behaviour of the wings of an exchange-narrowed EPR line is explained as the observation of high-temperature Heisenberg ferromagnet spin-relaxation.     

A generalized spin ladder in a magnetic field

We study the phase diagram of coupled spin-1/2 chains with bilinear and (chiral) three-spin exchange interactions in a magnetic field. The model is soluble on a one-parametric line in the space of coupling constants connecting the limiting cases of a single and two decoupled Heisenberg chains with nearest neighbour exchange only. We give a complete classification of the low-energy properties of the integrable system and introduce a numerical method which allows to study the possible phases of spin ladder systems away from the soluble line in a magnetic field. Received 17 November 1998 and Received in final form 22 January 1999     

Motion of bound domain walls in a spin ladder

The elementary excitation spectrum of the spin- \frac12\frac{1}{2} antiferromagnetic (AFM) Heisenberg chain is described in terms of a pair of freely propagating spinons. In the case of the Ising-like Heisenberg Hamiltonian spinons can be interpreted as domain walls (DWs) separating degenerate ground states. In dimension d > 1, the issue of spinons as elementary excitations is still unsettled. In this paper, we study two spin- \frac12\frac{1}{2} AFM ladder models in which the individual chains are described by the Ising-like Heisenberg Hamiltonian. The rung exchange interactions are assumed to be pure Ising-type in one case and Ising-like Heisenberg in the other. Using the low-energy effective Hamiltonian approach in a perturbative formulation, we show that the spinons are coupled in bound pairs. In the first model, the bound pairs are delocalized due to a four-spin ring exchange term in the effective Hamiltonian. The appropriate dynamic structure factor is calculated and the associated lineshape is found to be almost symmetric in contrast to the 1d case. In the case of the second model, the bound pair of spinons lowers its kinetic energy by propagating between chains. The results obtained are consistent with recent theoretical studies and experimental observations on ladder-like materials.     

94GHz基波复合腔回旋管数值模拟

通过对94 GHz基波复合腔回旋管中谐振腔结构、电子注参数以及注-波互作用过程的模拟计算研究,分析了复合腔回旋管的高频结构特性和工作参数优化问题.给出了基波H61 -H62模式对复合腔回旋管的模拟设计结果.数值模拟结果表明:在电子注电压40 kV、电流5A、电子横纵速度比1.3、工作磁场3.6T时,回旋管可获得78 k...     

Thermodynamic properties of a spin half ladder system

A complete dimerized state exists for one kind of two-leg spin half ladders, which has local antiferromagnetic ordering and frustration effect at the same time. The system’s low-lying excitations can be obtained exactly which enables us to calculate thermodynamic quantities such as specific heat and magnetic susceptibility at low temperatures. Our results also show that the subset energy spectrum is a good approximation to the whole spectrum even for the usual two-leg spin half ladder without frustration.     

Frustration and intermediate dimerized phase in spin ladder system

This paper studies a spin ladder model which possesses frustrating interactions.By using both the bosonization and the density matrix renormalization group techniques,it shows that the intermediate columnar dimerized phase,which exists in a narrow parameter region of the so-called J 1 J 2 model,vanishes if the interchain frustration is weak and anisotropic.Therefore,it concludes that the frustrating interaction indeed plays an important role in producing such a phase.As a complementary to our previous investigation,it reaches a more complete picture of the quantum phase transition in the frustrated spin ladder systems.     

Thermodynamic properties of a spin half ladder system

A complete dimerized state exists for one kind of two-leg spin half ladders, which has local antiferromagnetic ordering and frustration effect at the same time. The system’s low-lying excitations can be obtained exactly which enables us to calculate thermodynamic quantities such as specific heat and magnetic susceptibility at low temperatures. Our results also show that the subset energy spectrum is a good approximation to the whole spectrum even for the usual two-leg spin half ladder without frustration.     

Generation of spin motive force in a soliton lattice

The generation of a spin motive force in a chiral helimagnet due to the action of two crossed magnetic fields is considered. The cases of pulsed and periodic magnetic fields directed along the helical axis under a perpendicular dc field are analyzed. It is shown that, in the case of a pulsed field, the spin motive force is related to dissipation, whereas in a periodic field, there is a reactive component that is not related to damping processes.     

NRD leaky-wave antenna for narrow beams in 94GHz

Theoretical analyses and numerical results of NRD leaky-wave antenna are presented. The results show that the characteristics of frequency scanning and very narrow beam can be implemented by NRD leaky-wave antenna. At the freguency of 94GHz, the half-power beamwidth of 0.14° of the antenna canbe obtained when the length of the antenna is 1.5m. From 90 to 98GHz, frequency scanning is about ±7° relating to the beam angle at 94GHz. The theoretical results are compared with the experimental data.     

Li-defect interactions in electron-irradiated n-type silicon by EPR measurements

Single crystal silicon, both with and without oxygen, has been diffused with lithium to concentrations ～10¹⁷/cm², irradiated with 1 to 1.5 MeV electrons, and the ensuing defects studies by EPR measurements. The presence of oxygen strongly affects the properties of these defects. Measurements have indicated the presence of two new defects which involve Li-one in O-containing material and one in O-free material. The defects are observed in their electron-filled state, and indicate a net electron spinof ½. The defect spectra disappear (with time) at room temperature, and can be explained by the formation of other Li-involved defects which lie deeper in the energy bandgap and are not visible by EPR. Electron irradiation at 40 °K followed by annealing at higher temperatures show that both EPR defects described above begin to form at about 200 °K and begin to decrease at about 275 °K-just as does the 250 °K reverse annealing observed generally for n-type Si. Based on these data, and the work of others, it is suggested that both defects form as a result of the motion of Si interstitials which produce a (Li-O-interstitial) complex in O-containing Si, and a (Li-interstitial) complex in O-free Si.