Repetitive cross-polarization contacts via equilibration-re-equilibration of the proton bath: Sensitivity enhancement for NMR of membrane proteins reconstituted in magnetically aligned bicelles

Thermodynamic limit of magnetization corresponding to the intact proton bath usually cannot be transferred in a single cross-polarization contact. This is mainly due to the finite ratio between the number densities of the high- and low-gamma nuclei, quantum-mechanical bounds on spin dynamics, and Hartmann-Hahn mismatches due to rf field inhomogeneity. Moreover, for fully hydrated membrane proteins refolded in magnetically oriented bicelles, short spin-lock relaxation times (T1ρ) and rf heating can further decrease cross polarization efficiency. Here we show that multiple equilibrations-re-equilibrations of the high- and low-spin reservoirs during the preparation period yield an over twofold gain in the magnetization transfer as compared to a single-contact cross polarization (CP), and up to 45% enhancement as compared to the mismatch-optimized CP-MOIST scheme for bicelle-reconstituted membrane proteins. This enhancement is achieved by employing the differences between the spin-lattice relaxation times for the high- and low-gamma spins. The new technique is applicable to systems with short T1ρ's, and speeds up acquisition of the multidimensional solid-state NMR spectra of oriented membrane proteins for their subsequent structural and dynamic studies.     

Detection of current-induced spins by ferromagnetic contacts

Detection of current-induced spin accumulation via ferromagnetic contacts is discussed. Onsager's relations forbid that in a two-probe configuration, spins excited by currents in time-reversal symmetric systems can be detected by switching the magnetization of a ferromangetic detector contact. Nevertheless, current-induced spins can be transferred as a torque to a contact magnetization and can affect the charge currents in many-terminal configurations. We demonstrate the general concepts by solving the microscopic transport equations for the diffuse Rashba system with magnetic contacts.     

A Curie-Weiss Model with Dissipation

We consider stochastic dynamics for a spin system with mean field interaction, in which the interaction potential is subject to noisy and dissipative stochastic evolution. We show that, in the thermodynamic limit and at sufficiently low temperature, the magnetization of the system has a time periodic behavior, despite of the fact that no periodic force is applied.     

J-ONLY-TOCSY: efficient suppression of RDC-induced transfer in homonuclear TOCSY experiments using JESTER-1-derived multiple pulse sequences

The main purpose of homonuclear Hartmann-Hahn or TOCSY experiments is the assignment of spin systems based on efficient coherence transfer via scalar couplings. In partially aligned samples, however, magnetization is also transferred via residual dipolar couplings (RDCs) and therefore through space correlations can be observed in COSY and TOCSY experiments that make the unambiguous assignment of covalently bound spins impossible. In this article, we show that the JESTER-1 multiple pulse sequence, originally designed for broadband heteronuclear isotropic Hartmann-Hahn transfer, efficiently suppresses the homonuclear dipolar coupling Hamiltonian. This suppression can be enhanced even further by variation of the supercycling scheme. The application of the resulting element in homonuclear TOCSY periods results in coherence transfer via J-couplings only. As a consequence, the assignment of scalar coupled spin systems is also possible in partially aligned samples. The bandwidth of coherence transfer for the JESTER-1-derived sequences is comparable to existing TOCSY multiple pulse sequences. Results are demonstrated in theory and experiment.     

Conditional Gaussian Fluctuations and Refined Asymptotics of the Spin in the Phase-Coexistence Region

We present four results on the fluctuations of the spin per site around the thermodynamic magnetization in the mean-field Blume-Capel model. Our first two results refine the main theorem in a previous paper (Ellis et al. in Ann. Appl. Probab. 20:2118?C2161, 2010), in which the first rigorous confirmation of the statistical mechanical theory of finite-size scaling for a mean-field model is given. Our first main result studies the asymptotics of the centered, finite-size magnetization, giving its precise rate of convergence to 0 along parameter sequences lying in the phase-coexistence region and converging sufficiently slowly to either a second-order point or the tricritical point of the model. A simple inequality yields our second main result, which generalizes the main theorem in Ellis et al. (Ann. Appl. Probab. 20:2118?C2161, 2010) by giving an upper bound on the rate of convergence to 0 of the absolute value of the difference between the finite-size magnetization and the thermodynamic magnetization. These first two results have direct relevance to the theory of finite-size scaling. They are consequences of our third main result. This is a new conditional limit theorem for the spin per site, where the conditioning allows us to focus on a neighborhood of the pure states having positive thermodynamic magnetization. Our fourth main result is a conditional central limit theorem showing that the fluctuations of the spin per site are Gaussian in a neighborhood of the pure states having positive thermodynamic magnetization.     

Finite-Volume Excitations of the¶111 Interface in the Quantum XXZ Model

We show that the ground states of the three-dimensional XXZ Heisenberg ferromagnet with a 111 interface have excitations localized in a subvolume of linear size R with energies bounded by O(1/R²). As part of the proof we show the equivalence of ensembles for the 111 interface states in the following sense: In the thermodynamic limit the states with fixed magnetization yield the same expectation values for gauge invariant local observables as a suitable grand canonical state with fluctuating magnetization. Here, gauge invariant means commuting with the total third component of the spin, which is a conserved quantity of the Hamiltonian. As a corollary of equivalence of ensembles we also prove the convergence of the thermodynamic limit of sequences of canonical states (i.e., with fixed magnetization).     

Solid-state NMR spectroscopy using the lost I spin magnetization in polarization transfer experiments

A variation of the cross polarization (CP) experiment is discussed. The method requires two scans where the difference signal is equivalent to the I spin magnetization that is transferred to the S spins. The acquired signal is equivalent to F1 sum projection of a two-dimensional (2D) heteronuclear correlation experiment and is obtained by just two scans without the need to increment the indirect time domain t(1). Any polarization transfer method and any kind of spin manipulations during the t(1) incrementation period of a 2D NMR experiment can be applied. The method allows fast measurements of the CP transfer, particularly if various S spins signal overlap and is good for spectral editing of I spin signals with contact to S spins. Various examples for biomaterials are presented. Most importantly, this novel approach is ideal for detailed investigations of organic-mineral interfaces in bone, here demonstrated for O-phospho-l-serine as simple model compound.     

Transverse magnetization transfer under planar mixing conditions in spin systems consisting of three coupled spins 1/2

Polarization transfer under planar mixing conditions is a widely used tool in modern NMR-experiments. In the case of two coupled spins 1/2 or a chain of three or more spins 1/2 with only nearest neighbor couplings, it is only possible to transfer a single magnetization component (longitudinal magnetization in the principle axis system of the planar coupling tensors). However, if all couplings in a three-spin system are non-zero, it turns out that all magnetization components can be efficiently transferred even under strictly planar mixing conditions. In this article a detailed theoretical analysis is presented based on analytical transverse coherence transfer functions and on the underlying commutator algebra. In addition, transverse magnetization transfer is demonstrated experimentally. The results show that in highly coupled spin systems, as for example in the case of partially aligned samples with many residual dipolar couplings, special care has to be taken to avoid phase distortions if planar mixing steps are used.     

Spin-polarized ground state for interacting electrons in two dimensions

We study numerically the ground state magnetization for clusters of interacting electrons in two dimensions in the regime where the single particle wave functions are localized by disorder. It is found that the Coulomb interaction leads to a spontaneous ground state magnetization. For a constant electronic density, the total spin increases linearly with the number of particles, suggesting a ferromagnetic ground state in the thermodynamic limit. The magnetization is suppressed when the single particle states become delocalized.     

Biased quasiballistic spin torque magnetization reversal

We explore the ultrafast limit of spin torque magnetization reversal time. Spin torque precession during a spin torque current pulse and free magnetization ringing after the pulse is detected by time-resolved magnetotransport. Adapting the duration of the pulse to the precession period allows coherent control of the final orientation of the magnetization. In the presence of a hard axis bias field, we find optimum quasiballistic spin torque magnetization reversal by a single precessional turn directly from the initial to the reversed equilibrium state.     

Core-halo distribution in the Hamiltonian mean-field model

We study a paradigmatic system with long-range interactions: the Hamiltonian mean-field (HMF) model. It is shown that in the thermodynamic limit this model does not relax to the usual equilibrium Maxwell-Boltzmann distribution. Instead, the final stationary state has a peculiar core-halo structure. In the thermodynamic limit, HMF is neither ergodic nor mixing. Nevertheless, we find that using dynamical properties of Hamiltonian systems it is possible to quantitatively predict both the spin distribution and the velocity distribution functions in the final stationary state, without any adjustable parameters. We also show that HMF undergoes a nonequilibrium first-order phase transition between paramagnetic and ferromagnetic states.     

Macroscopic magnetization jumps due to independent magnons in frustrated quantum spin lattices

For a class of frustrated spin lattices including the Kagomé lattice we construct exact eigenstates consisting of several independent, localized one-magnon states and argue that they are ground states for high magnetic fields. If the maximal number of local magnons scales with the number of spins in the system, which is the case for the Kagomé lattice, the effect persists in the thermodynamic limit and gives rise to a macroscopic jump in the zero-temperature magnetization curve just below the saturation field. The effect decreases with increasing spin quantum number and vanishes in the classical limit. Thus it is a true macroscopic quantum effect.     

Sensitivity enhanced recoupling experiments in solid-state NMR by gamma preparation

In this paper, we introduce a class of dipolar recoupling experiments under magic angle spinning (MAS), which use gamma dependent antiphase polarization during the t1 evolution period. We show that this helps us to design dipolar recoupling experiments that transfer both components of the transverse magnetization of spin S to a coupled spin I in the mixing step of a 2D NMR experiment. We show that it is possible to design such transfer schemes and make them insensitive to the orientation dependency of the couplings in powders. This helps us to develop sensitivity enhanced 2D NMR experiments of powder samples under MAS.     

Magnetic determination of H(c2) under accurate alignment in (TMTSF)2ClO4

Cantilever magnetometry has been used to measure the upper critical magnetic field H(c2) of the quasi-one-dimensional molecular organic superconductor (TMTSF)2ClO4. From simultaneous resistivity and torque magnetization experiments conducted under precise field alignment, H(c2) at low temperature is shown to reach 5 T, nearly twice the Pauli paramagnetic limit imposed on spin singlet superconductors. These results constitute the first thermodynamic evidence for a large H(c2) in this system and provide support for spin triplet pairing in this unconventional superconductor.     

Current driven magnetization dynamics in helical spin density waves

A mechanism is proposed for manipulating the magnetic state of a helical spin density wave using a current. It is shown that a current through a bulk metal with a helical spin density wave induces a spin transfer torque, which gives rise to a rotation of the order parameter. The use of spin transfer torque to manipulate the magnetization in bulk systems does not suffer from the obstacles seen for magnetization reversal using interface spin transfer torque in multilayered systems. The effect is demonstrated by a quantitative calculation of the current induced magnetization dynamics of a rare earth metal, Er. Finally, we propose a setup for experimental verification.     

On evaluation of transverse spin fluctuations in quantum magnets

A numerical method is described for evaluating transverse spin correlations in the random phase approximation. Quantum spin-fluctuation corrections to sublattice magnetization are evaluated for the antiferromagnetic ground state of the half-filled Hubbard model in two and three dimensions in the whole U/t range. Extension to the case of defects in the AF is also discussed for spin vacancies and low-U impurities. In the limit, the vacancy-induced enhancement in the spin fluctuation correction is obtained for the spin-vacancy problem in two dimensions, for vacancy concentration up to the percolation threshold. For low-U impurities, the overall spin fluctuation correction is found to be strongly suppressed, although surprisingly spin fluctuations are locally enhanced at the low-U sites. Received 27 April 1998 and Received in final form 13 August 1998     

Selective Injection of Magnetization by Slow Chemical Exchange in NMR

In a system in slow dynamic equilibrium two NMR methods are shown to be suitable for injecting magnetization from one resonance to another by means of slow chemical exchange. The combined outputs of the methods may be employed to measure the value of the off-rate constant kappa(off) in the complex. The methods are implemented experimentally using the complex of molecules composed of the enzyme Escherichia coli dihydrofolate reductase (DHFR) and the ligand folate. In an equilibrium solution with DHFR, folate is known to undergo chemical exchange between a free state and a bound state. The modified synchronous nutation method is applied to a spin of the folate molecule in the free and bound states; magnetization transfer occurs between the two sites due to the underlying exchange process. As a preliminary step for the application of the synchronous nutation method, a new one-dimensional 1H NMR technique is proposed which facilitates the assignment of the resonance of a spin in the bound state, provided the resonance of its exchange partner in the free state is known. This experiment is also used to obtain quantitative estimates of the transverse relaxation rate constant of the bound resonance. The numerical procedure necessary to analyze the experimental results of the synchronous nutation experiment is presented.     

Anatomy of field effects on magnetization dynamics and spin transfer noise

Spin transfer-related phenomena in nanomagnets have attracted extensive studies. In this paper we shall focus on analysis of individual and combined effects of the external, anisotropy, and demagnetization fields on magnetization dynamics and spin transfer noise. It is found that individual roles of the external, anisotropy, and demagnetization fields, as well as the combined roles of external plus anisotropy fields and anisotropy plus demagnetization fields, do not change the behavior of current induced magnetization switching. Such magnetization reversal procedures are of low noise. Our dynamics and power spectral density calculations show that it is the demagnetization field that plays a major role in inducing spin transfer noise: the demagnetization field itself or in combination with the anisotropy field will result in wave-like switching; moreover, the demagnetization field, together with the external field (not too small), will lead to precession and hence the system would be in noisy states. Our modeling work for an elliptical Py alloy is qualitatively consistent with Cornell's experiment and simulation [Science 307 (2005) 228].     

Dynamics of paramagnetic agents by off-resonance rotating frame technique in the presence of magnetization transfer effect

The simple method for measuring the rotational correlation time of paramagnetic ion chelates via off-resonance rotating frame technique is challenged in vivo by the magnetization transfer effect. A theoretical model for the spin relaxation of water protons in the presence of paramagnetic ion chelates and magnetization transfer effect is described. This model considers the competitive relaxations of water protons by the paramagnetic relaxation pathway and the magnetization transfer pathway. The influence of magnetization transfer on the total residual z-magnetization has been quantitatively evaluated in the context of the magnetization map and various difference magnetization profiles for the macromolecule conjugated Gd-DTPA in cross-linked protein gels. The numerical simulations and experimental validations confirm that the rotational correlation time for the paramagnetic ion chelates can be measured even in the presence of strong magnetization transfer. This spin relaxation model also provides novel approaches to enhance the detection sensitivity for paramagnetic labeling by suppressing the spin relaxations caused by the magnetization transfer. The inclusion of the magnetization transfer effect allows us to use the magnetization map as a simulation tool to design efficient paramagnetic labeling targeting at specific tissues, to design experiments running at low RF power depositions, and to optimize the sensitivity for detecting paramagnetic labeling. Thus, the presented method will be a very useful tool for the in vivo applications such as molecular imaging via paramagnetic labeling.     

Self-consistent calculation of spin transport and magnetization dynamics

A spin-polarized current transfers its spin-angular momentum to a local magnetization, exciting various types of current-induced magnetization dynamics. So far, most studies in this field have focused on the direct effect of spin transport on magnetization dynamics, but ignored the feedback from the magnetization dynamics to the spin transport and back to the magnetization dynamics. Although the feedback is usually weak, there are situations when it can play an important role in the dynamics. In such situations, simultaneous, self-consistent calculations of the magnetization dynamics and the spin transport can accurately describe the feedback. This review describes in detail the feedback mechanisms, and presents recent progress in self-consistent calculations of the coupled dynamics. We pay special attention to three representative examples, where the feedback generates non-local effective interactions for the magnetization after the spin accumulation has been integrated out. Possibly the most dramatic feedback example is the dynamic instability in magnetic nanopillars with a single magnetic layer. This instability does not occur without non-local feedback. We demonstrate that full self-consistent calculations generate simulation results in much better agreement with experiments than previous calculations that addressed the feedback effect approximately. The next example is for more typical spin valve nanopillars. Although the effect of feedback is less dramatic because even without feedback the current can make stationary states unstable and induce magnetization oscillation, the feedback can still have important consequences. For instance, we show that the feedback can reduce the linewidth of oscillations, in agreement with experimental observations. A key aspect of this reduction is the suppression of the excitation of short wavelength spin waves by the non-local feedback. Finally, we consider nonadiabatic electron transport in narrow domain walls. The non-local feedback in these systems leads to a significant renormalization of the effective nonadiabatic spin transfer torque. These examples show that the self-consistent treatment of spin transport and magnetization dynamics is important for understanding the physics of the coupled dynamics and for providing a bridge between the ongoing research fields of current-induced magnetization dynamics and the newly emerging fields of magnetization-dynamics-induced generation of charge and spin currents.