Assessing signal enhancement in distant dipolar field-based sequences

The possibility of improving the signal-to-noise efficiency of NMR signal refocused by long-range dipolar interactions has been discussed recently [R.T. Branca, G. Galiana, W.S. Warren, Signal enhancement in CRAZED experiments, J. Magn. Reson. 187 (2007) 38-43]. For systems where T(1)>T(2), by including an extra radio-frequency pulse in a standard CRAZED sequence, it is possible to increase the available signal by exploiting its sensitivity to T(1) relaxation. Here, we use analytical calculations to investigate the source of this improved signal and determine the maximum enhancement provided by the method.     

Diffraction-like phenomena in a periodic magnetization distribution at 1.5 T using the distant dipolar field (DDF)

In the CRAZED experiment (COSY revamped by asymmetric Z-gradient echo detection, Warren et al.), a spatially anisotropic magnetization distribution is created by application of a magnetic field gradient (strength G, duration tau) which in turn generates a response called the distant dipolar field (DDF). The DDF is a source of intermolecular multiple-quantum coherences (iMQC) which contain information on the distance d=pi/(gammaGtau) between pairs of dipolar-coupled spins. Diffraction-like phenomena may result for periodically structured samples. In this study, we report the observation of diffraction owing to the DDF at 1.5 T using a clinical whole-body tomograph. Based on the semi-classical treatment of the problem by Robyr and Bowtell, diffraction conditions were obtained for a CRAZED-type pulse sequence that selects iMQC of order N. The predicted distinct difference in N=2 and N not equal2 coherences, i.e., a dominant continuous course as a function of tau (N=2) and prominent diffraction peaks otherwise, could be verified in CRAZED experiments in a periodically structured sample selecting coherence orders N=2 and N=3. The diffractive signal component contains information on the geometric structure of the sample. Applications of this technique may permit the detection of changes in composition and geometry of periodic structures.     

Minor magnetization loops in two-dimensional dipolar Ising model

The two-dimensional dipolar Ising model is investigated for the relaxation and dynamics of minor magnetization loops. Monte Carlo simulations show that in a stripe phase an exponential decrease can be found for the magnetization maxima of the loops, M∼exp(−αN_l) where N_l is the number of loops. We discuss the limits of this behavior and its relation to the equilibrium phase diagram of the model.     

Compound radiofrequency-driven recoupling pulse sequences for efficient magnetization transfer by homonuclear dipolar interaction under magic-angle spinning conditions

The maximum of the transferred magnetization in rotating powdered solids under the radiofrequency-driven recoupling (RFDR) pulse sequence is enhanced by reducing the orientation dependence of the effective recoupled homonuclear dipolar interaction. The compound RFDR (CRFDR) pulse sequence for this enhancement consists of RFDR pulse units (tau(i)-pi-tau(R)-pi-1171;tau(i)) with different tau(i), where tau(R) is the sample rotation period, tau(i) and 1171;tau(i) (=tau(R) - tau(i)) are delays, and pi is a 180 degrees pulse. The delay tau(i) modifies the zero-quantum spin operators and the sample rotation-angle dependence of the recoupled dipolar Hamiltonian. The CRFDR pulse sequences were optimized for mixing by varying tau(i). Numerical simulation for the two-spin system only with a dipolar interaction and isotropic chemical shifts indicates that the transfer efficiency of CRFDR averaged over the powder is about 70%, which is 30% higher than the efficiency of the RFDR pulse over a broad range of about 1/tau(R) in resonance frequency difference. The CRFDR sequences need about 60% longer mixing times to maximize the transferred magnetizaion in comparison with the original RFDR sequence. Chemical shift anisotropy, the other dipolar interactions, and relaxation generally reduce the enhancement by CRFDR. Experiments for fully (13)C-labeled alanine, however, show that the maximum of the magnetization transferred with CRFDR from the carboxyl to alpha carbon is about 15% greater than that with RFDR. Copyright 2000 Academic Press.     

Spatially nonuniform distribution of magnetization in laser-irradiated ferromagentic materials

Ferromagnetic austenite–martensite steels are laser-irradiated to obtain spatially nonuniform distribution of magnetization. An original setup that employs the Faraday effect in epitaxial ferrite-garnet films is used to visualize and measure the spatial distribution of magnetization in steels that are processed with the aid of a fiber laser at different scanning rates. It is demonstrated that rapid laser heating of samples causes modification of the microstructure from the martensite state to the austenite state that provides paramagnetic properties.     

Solid state NMR analysis of the dipolar couplings within and between distant CF3-groups in a membrane-bound peptide

Dipolar couplings contain information on internuclear distances as well as orientational constraints. To characterize the structure of the antimicrobial peptide gramicidin S when bound to model membranes, two rigid 4-CF3-phenylglycine labels were attached to the cyclic backbone such that they reflect the behavior of the entire peptide. By solid state 19F NMR we measured the homonuclear dipolar couplings of the two trifluoromethyl-groups in oriented membrane samples. Using the CPMG experiment, both the strong couplings within each CF3-group as well as the weak coupling between the two CF3-groups could be detected. An intra-CF3-group dipolar coupling of 86 Hz and a weak inter-group coupling of 20 Hz were obtained by lineshape simulation of the complex dipolar spectrum. It is thus possible to explore the large distance range provided by 19F-labels and to resolve weak dipolar couplings even in the presence of strong intra-CF3 couplings. We applied this approach to distinguish and assign two epimers of the labeled gramicidin S peptide on the basis of their distinct 19F dipolar coupling patterns.     

Effect of dipolar interaction on the magnetization state of chains of rectangular particles located either head-to-tail or side-by-side

Magnetostatic coupling in arrays of closely spaced magnetic elements is becoming an important issue in the path to the fabrication of spintronic devices. Dense chains of rounded-corners rectangular particles (dots) of lateral size 1025 × 450 nm², with interdot spacing variable in the range between 55 and 700 nm, have been patterned by deep UV lithography, followed by the lift-off of two permalloy films of thickness 20 and 40 nm. Magneto-optical Kerr effect (MOKE) and magnetic force microscopy (MFM) experiments, together with micromagnetic simulations, were performed to study the dependence of the magnetization configuration on the dipolar coupling. Both MOKE measurements and MFM images clearly show that, at remanence, the magnetic state of isolated particles of thickness 20 nm takes the form of a distorted single domain (C-state or S-State configurations). Instead, when the particle thickness is double (40 nm), closure states characterized by one, two or three vortices occur at remanence. However, when the 40 nm thick dots are placed in chains along the easy axis (head to tail), as the separation is progressively reduced, the single domain state is stabilized at remanence. On the other hand, when the 40 nm thick particles are placed side by side in chains the effect of dipolar interactions is to favour the nucleation of vortex states. For small inter-element separation, there is only one vortex per particle and it has the same chirality in adjacent particles, due to the dipolar interaction. Different from this, for the 20 nm thick samples and sub-100 nm separation, adjacent particles are single-domain but with antiparallel magnetization in neighbour elements, like in an artificial antiferromagnet.     

1H NMR imaging of residual dipolar couplings in cross-linked elastomers: dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum filters.

Contrastfilters for NMR imaging of residual 1H dipolar couplings of elastomers are introduced based on dipolar-encoded longitudinal magnetization, as well as double- and triple-quantum coherences. The spin response is discussed in the initial excitation time regime for methylene, methyl, and methine protons applicable to poly(isoprene) and other elastomers, taking into account the hierarchy of dipolar couplings and the associated editing features of multiple-quantum experiments. The efficiency of these filters is investigated for a series of cross-linked poly(isoprene) samples. Spatially resolved dipolar-encoded longitudinal magnetization decays and double-quantum and triple-quantum buildup curves are presented for a phantom made of poly(isoprene) with different cross-link densities. Two-dimensional images representing residual dipolar couplings are presented using dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum contrast filters. Images from dipolar-encoded longitudinal magnetization and triple-quantum coherences show the highest resolution and contrast, respectively.     

Spatially varying interactions induced in ultra-cold atoms by optical Feshbach resonance

Optical Feshbach resonance can induce spatially varying interactions in ultra-cold atoms. Its applications to pancake-shaped clouds of bosons and fermions enable one to study several fresh phenomena. We examine possibilities of unexplored structures such as a bosonic superfluid enclave inside a Mott insulator and a normal-gas core enclosed by a fermionic superfluid shell. We discuss feasible experimental setups and signatures of those interesting structures. While a superfluid enclave in a Mott insulator may be useful for atomic devices in atomtronics, the superconducting islands observed in scanning-tunneling microscopy of heavily underdoped high-temperature superconductors may be simulated by ultra-cold fermions.     

Low temperature MQ NMR dynamics in dipolar ordered state

We investigate analytically and numerically the Multiple Quantum (MQ) NMR dynamics in dipolar ordered spin systems of nuclear spins 1/2 at low temperatures. We consider two different methods of MQ NMR. One of them is based on the measurement of the dipolar energy. The other method uses an additional resonance (π/4)_y-pulse after the preparation period of the standard MQ NMR experiment in solids and allows one to measure the Zeeman energy. Both considered methods are sensitive to the contribution of remote spins in the interaction and to the spin system structure. The QS method is sensitive to the spin number in the molecule while the PS method gives very similar time dependencies of the intensities of MQ coherences for different spin numbers. It is shown that the use of the dipolar ordered initial state has the advantage of exciting the highest order MQ coherences in clusters of 4m identical spins, where m=1,2,3,…, that is impossible to do with the standard MQ method. MQ NMR methods based on the dipolar ordered initial states at low temperatures complement the standard NMR spectroscopy for better studying structures and dynamic processes in solids.     

Small fluctuations in a steady non-equilibrium state

An expression for the probability of fluctuations in a given probability distribution deduced in an earlier paper is used to derive a relation between autocorrelations of velocities and the dynamics of small fluctuations in a stable steady state. The steady state may lie in the region of nonlinear thermodynamics. The considerations are restricted to systems with a distinctly separated behaviour on short and long time scale and the corresponding use of Mori distributions.     

Sideband patterns from rotor-encoded longitudinal magnetization in MAS recoupling experiments

Recent multiple-quantum MAS NMR experiments have shown that a change in the rotor phase (and, hence, in the Hamiltonian) between the excitation and reconversion periods can lead to informative spinning-sideband patterns. However, such "rotor encoding" is not limited to multiple-quantum experiments. Here it is shown that longitudinal magnetization can also be rotor-encoded. Both homonuclear and heteronuclear rotor encoding of longitudinal magnetization (RELM) experiments are performed on dipolar-coupled spin-1/2 systems, and the corresponding sideband patterns in the indirect dimension are analyzed. In both cases, only even-order sidebands are produced, and their intensity distribution depends on the durations of the recoupling periods. In heteronuclear experiments using REDOR-type recoupling, purely dipolar sideband patterns that are entirely free of effects due to the chemical-shielding anisotropy can be generated. Advantages and disadvantages of the heteronuclear RELM experiment are discussed in the context of other methods used to measure heteronuclear dipolar couplings.     

Efficient heteronuclear dipolar decoupling in solid-state NMR using frequency-swept SPINAL sequences

Aiming to improve heteronuclear spin decoupling efficiency in NMR spectroscopy of solids and liquid crystals, we have modified the original Small Phase Incremental ALteration (SPINAL) sequence by incorporating a frequency sweep into it. For the resulting sequence, termed SW_f-SPINAL, the decoupling performance of a large number of sweep variants was explored by both numerical simulations and NMR experiments. It is found that introducing a frequency sweep generally increases both the ‘on-resonance’ decoupling performance and the robustness towards parameter offsets compared to the original SPINAL sequence. This validates the concept of extending the range of efficient decoupling by introducing frequency sweeps, which was recently suggested in the context of the frequency-swept SW_f-TPPM method. The sequence found to be best performing among the SW_f-SPINAL variants consists of fully swept 16 pulse pairs and is designated (32)-SPINAL-32. Its good decoupling performance for rigid spin systems is confirmed by numerical simulations and also experimentally, by evaluating the CH₂ resonance of a powder sample of l-tyrosine under MAS. For moderate MAS frequencies, the new sequence matches the decoupling achieved with SW_f-TPPM, and outperforms all other tested sequences, including TPPM and SPINAL-64. (32)-SPINAL-32 also shows excellent decoupling characteristics for liquid crystalline systems, as exemplified by experiments on the 5CB liquid crystal.     

Equilibrium state and non-equilibrium steady state in an isolated human system

The principle of increasing entropy （PIE） is commonly considered as a universal physical law tbr natural systems. It also means that a non-equilibrium steady state （NESS） must not appear in any isolated natural systems. Here we experimentally investigate an isolated human social system with a clustering effect. We report that the PIE cannot always hold, and that NESSs can come to appear. Our study highlights the role of human adaptability in the PIE, and makes it possible to study human social systems by using some laws originating from traditional physics.     

Imaging the long-range dipolar field in structured liquid state samples

We describe imaging experiments in which the pattern of the dipolar field generated by spatially modulated nuclear magnetization is directly visualized in simply structured phantoms. Two types of experiment have been carried out at 11.7 T using (1)H NMR signals. In the first, the field from a single spin species is imaged via its own NMR signal. In the second, the NMR signal from one spin species is used to image the field generated by a second species. The field patterns measured in these experiments correspond well with those calculated using simple theoretical expressions for the dipolar field. The results also directly demonstrate the spatial sensitivity of the signal generated using dipolar field effects, indicating that the range of the field depends upon the inverse of the spatial frequency with which the magnetization is modulated.     

Apparent diffusion behaviors of spins in the presence of distant dipolar field in two-component solution NMR

The diffusion behaviors of spins in the presence of distant dipolar field in two-component spin systems during the second evolution period of a modified CRAZED sequence before acquisition were investigated. Theoretical formulas were deduced based on the distant dipolar field model. The simulation results and experimental observations are consistent with the theoretical predictions. This study shows that the relative intensities of signals from intermolecular zero-quantum coherences (iZQCs) and intermolecular double-quantum coherences (iDQCs) have the same diffusion attenuation characteristic under the combined effect of diffusion weighting gradients and distant dipolar field during the second evolution period. This diffusion attenuation may be different from that of conventional single-quantum coherence signal, depending on the relative orientation of the diffusion weighting gradients to the coherence selection gradients. The results presented herein are helpful for understanding the effect of distant dipolar field from a spin system on the diffusion behavior of other spin system and the signal properties in the iZQC or iDQC magnetic resonance imaging.     

Heteronuclear dipolar recoupling in liquid crystals and solids by PISEMA-type pulse sequences

A pulse sequence is described for the recoupling of heteronuclear dipolar interactions under MAS. The method is similar to the PISEMA experiment, but employs a well-defined amplitude modulation of one of the two radio-frequency fields. The technique is used for measurements of 1H-13C dipolar couplings in unoriented solid and liquid-crystalline samples.     

Spatially varying effective mass effects on energy level populations in semiconductor quantum devices

For the analysis and design of semiconductor intersubband devices, accurate values for the Fermi energy and the subband electron population are needed. The effect of the position-dependent electron effective massm ^*  (z) is commonly neglected in the determination of these two intersubband device parameters. This approach is nearly valid for single-well devices in the GaAs/Al _xGa_1 − x As material system. However, in multiple-coupled-well devices, the variable nature of the effective mass must be taken into account. In material systems other than the ones based on GaAs, failure to include the position-dependence of the electron mass may give rise to significant errors in the values of the Fermi energy and other device parameters such as the intersubband absorption coefficient. In this paper, the effects ofm ^*  (z) on the Fermi level and the intersubband charge distribution are explored and quantified.Theoretical formulation for the intersubband Fermi energy and the subband electron distribution, with the inclusion of position-dependent electron mass, is presented. The eigenenergies of the intersubband structures are obtained by solving the single-band effective-mass Schroedinger equation using the argument principle method. The electron distribution and the Fermi energy are calculated using both the approximate method ( m₀ ^* ) and the rigorous formulation [ m ^* (z)], and the relative differences in the corresponding values are presented. It is demonstrated that these differences are small in the GaAs/Al _xGa_1 − x As material system, but can become very significant in other materials. In addition, the variable nature of carrier effective mass plays an important role in other types of devices such as interband quantum well photodetectors and lasers that employ optical transitions between the valence and the conduction bands. Electronic devices such as the resonant tunneling diode are also affected by the position-dependence of carrier mass and thus the results are applicable to both optoelectronic and electronic quantum devices.