Localized double-spin-echo proton spectroscopy of weakly coupled homonuclear spin systems

The effect of localized double-spin-echo spectroscopy (PRESS) on a homonuclear weakly coupled AX spin system was calculated by the use of the product-operator formalism. Due to flip-angle distributions within the excited slices, different unwanted coherences are created which give rise to signal losses after the second and third RF pulse. The amount of signal loss is dependent on the timing of the sequence; i.e., only a proper choice of the time intervals between the pulses results in a high signal strength for coupled spins. Experiments were carried out on a Siemens Magnetom 1.5 T whole-body imager to verify the theory. Signal gains of far more than 100% were obtained for the coupled spins of lactate.     

Theoretical treatment of volume localized NMR spectroscopy in weakly coupled spin systems

A pulse sequence is proposed for obtaining volume selective echoes with both chemical shift and homonuclear scalar coupling refocused. Theory, in terms of product operator formalism, is presented and the full response of the spin system is computed. The theoretical spatial dependence of the power signal given by spins localized in different planes (x=0,y=0, respectivez=0) is presented.     

On the dynamics of polymers in dense systems – Results of neutron spin echo spectroscopy

One of the basic problems in the dynamics of polymers concerns the importance of geometrical or topological interactions which are directly related to the large scale molecular structures. In the famous reptation model these constraints are pictured in terms of a tube of localization following the average chain profile and confining the chain motion to the curve‐linear tube. Recently studying the dynamic structure factor of a single labeled chain in a polymer melt by means of neutron spin echo spectroscopy (NSE) led to a direct observation of these tube constraints. Here I shall summarize these neutron spin echo experiments. I shall address the NSE technique, present results on the entropy driven segmental chain dynamics, discuss the dynamics of single chains in the melt where the chain length is increased through the transition to “reptation” dynamics and display NSE measurements on long chain systems which revealed the molecular existence of the entanglement distance. Their magnitudes agree very well with tube diameters derived from dynamical mechanical measurements on the basis of the reptation model proving thereby the basic assumption of this Nobel Price winning concept. This revised version was published online in August 2006 with corrections to the Cover Date.     

Relaxation properties of weakly coupled classical systems

The relaxation properties of a small classical system weakly coupled to a large classical system which acts as a heat bath are described using a generalized Fokker-Planck equation. The Fokker-Planck equation is derived in general using a modification of the elimination of fast variables techniques previously described. The specific example in which the small system is a harmonic oscillator linearly coupled to the heat bath is treated in detail and it is demonstrated that there is a dynamic frequency shift as well as a statistical shift of the oscillator frequency.     

Spectral editing of weakly coupled spins using variable flip angles in PRESS constant echo time difference spectroscopy: Application to GABA

A general in vivo magnetic resonance spectroscopy editing technique is presented to detect weakly coupled spin systems through subtraction, while preserving singlets through addition, and is applied to the specific brain metabolite γ-aminobutyric acid (GABA) at 4.7 T. The new method uses double spin echo localization (PRESS) and is based on a constant echo time difference spectroscopy approach employing subtraction of two asymmetric echo timings, which is normally only applicable to strongly coupled spin systems. By utilizing flip angle reduction of one of the two refocusing pulses in the PRESS sequence, we demonstrate that this difference method may be extended to weakly coupled systems, thereby providing a very simple yet effective editing process. The difference method is first illustrated analytically using a simple two spin weakly coupled spin system. The technique was then demonstrated for the 3.01 ppm resonance of GABA, which is obscured by the strong singlet peak of creatine in vivo. Full numerical simulations, as well as phantom and in vivo experiments were performed. The difference method used two asymmetric PRESS timings with a constant total echo time of 131 ms and a reduced 120° final pulse, providing 25% GABA yield upon subtraction compared to two short echo standard PRESS experiments. Phantom and in vivo results from human brain demonstrate efficacy of this method in agreement with numerical simulations.     

Loschmidt echo of a central spin coupled to an XY spin chain: Role of three-site interaction

Effects of two types of three-site interaction, i.e., XZX+YZY and XZY−YZX, on Loschmidt Echo (LE) of a central spin coupled to an XY spin chain are studied. The dynamical evolution behaviors of the LE are investigated analytically and numerically. The XZX+YZY type of three-site interaction (α₁) can shift the critical points of the magnetic field λ. At the critical points |λ−α₁|=1, the decay of the LE is enhanced. The role of the XZY−YZX type of three-site interaction (α₂) depends on its strength. In some specific intervals, α₂ can remarkably delay the decay of the LE.     

Exploring the limits of polarization transfer efficiency in homonuclear three spin systems

The limits of polarization transfer efficiency are explored for systems consisting of three isotropically coupled spins 1/2 in the absence of relaxation. An idealized free evolution and control Hamiltonian is studied, which provides an upper limit of transfer efficiency (in terms of transfer amplitude and transfer time) for realistic homonuclear spin systems with arbitrary Heisenberg-type coupling constants J12, J13, and J23. It is shown that optimal control based pulse sequences have significantly improved transfer efficiencies compared to conventional transfer schemes. An experimental demonstration of optimal polarization transfer is given for the case of the carbon spin system of fully 13C labelled alanine at 62.5 MHz Larmor frequency.     

Time displacement rotational echo double resonance: heteronuclear dipolar recoupling with suppression of homonuclear interaction under fast magic-angle spinning

We have developed a novel variant of REDOR which is applicable to multiple-spin systems without proton decoupling. The pulse sequence is constructed based on a systematic time displacement of the pi pulses of the conventional REDOR sequence. This so-called time displacement REDOR (td-REDOR) is insensitive to the effect of homonuclear dipole-dipole interaction when the higher order effects are negligible. The validity of td-REDOR has been verified experimentally by the P-31{C-13} measurements on glyphosate at a spinning frequency of 25 kHz. The experimental dephasing curve is in favorable agreement with the simulation data without considering the homonuclear dipole-dipole interactions.     

Nonresonant echo spectroscopy of inhomogeneously broadened two-level systems

Effects which arise in inhomogeneously broadened systems upon nonresonant excitation are examined theoretically. The effect of such excitation on the signals representing a decaying free polarization and a two-pulse echo is discussed. The onset of echo signals generated in two-pulse retarded nutation during the application of a field is studied. The response can acquire a multicomponent structure. This structure is manifested in the appearance of a single-pulse echo, eight satellites in the two-pulse echo, and four nutation echo signals in the retarded two-pulse nutation. An experimental study of these effects is reported. The possibility of using them to determine relaxation times is analyzed.Institute of Solid-State and Semiconductor Physics, Academy of Sciences of Belarus. Scientific-Research Institute of Problems of Semiconductor Physics, Belarus State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 59–71, July, 1993.     

Creation and destruction of a spin gap in weakly coupled quarter-filled ladders

We investigate weakly coupled quarter-filled ladders with model parameters relevant for NaV(2)O(5) using density-matrix renormalization group calculations on an extended Hubbard model coupled to the lattice. NaV(2)O(5) exhibits super-antiferroelectric charge order with a zigzag pattern on each ladder. We show that this order causes a spin dimerization along the ladder and is accompanied by a spin gap of the same magnitude as that observed experimentally. The spin gap is destroyed again at large charge order due to a restructuring of the spins. An analysis of an effective spin model predicts a recreation of the gap by interladder singlets when the charge order increases further.     

The roles of homonuclear line narrowing and the1H amide chemical shift tensor in structure determination of proteins by solid-state NMR spectroscopy

The seminal contributions of Ulrich Haeberlen to homonuclear line narrowing and the determination of¹H chemical shift tensors are crucial for protein structure determination by solid-state nuclear magnetic resonance spectroscopy. The¹H chemical shift is particularly important in spectra obtained on oriented samples of membrane proteins as a mechanism for providing dispersion among resonances that are not resolved with the¹H-¹⁵N dipolar coupling and¹⁵N chemical shift frequencies. This is demonstrated with three-dimensional experiments on uniformly¹⁵N-labeled samples of Magainin antibiotic peptide and the protein Vpu from HIV-1 in oriented lipid bilayers. These experiments enable resonances in two-dimensional¹H-¹⁵N dipolar coupling/¹⁵N chemical shift planes separated by¹H chemical shift frequencies to be resolved and analyzed. These three-dimensional spectra are compared to one-dimensional spectra of full-length Vpu, the cytoplasmic domain of Vpu, and Magainin, as well as to two-dimensional spectra of fd coat protein and Colicin El polypeptide. The¹H amide chemical shift tensor provides valuable structural information, and this is demonstrated with its contributions to orientational restrictions to one of the in-plane helical residues of Magainin.     

Detection of homonuclear decoupled in vivo proton NMR spectra using constant time chemical shift encoding: CT-PRESS

A new pulse sequence, termed CT-PRESS, is presented, which allows the detection of in vivo ¹H NMR spectra with effective homonuclear decoupling. A PRESS sequence with a short echo-time TE, used for spatial localization, is supplemented by an additional 180° pulse. The temporal position of this 180° pulse is shifted within a series of experiments, while the time interval between signal excitation and detection is kept constant. CT-PRESS is a two-dimensional (2D) spectroscopic experiment as far as data acquisition and processing are concerned, although only diagonal signals are generated in the 2D spectrum. However, since the principle of constant time chemical shift encoding is used in the t₁ domain, effective homonuclear decoupling is obtained by projecting the 2D spectrum onto the corresponding f₁ axis. Thus, good spectral resolution and high signal-to-noise ratio are obtained. The main advantage, as compared to localized 2D J-resolved MRS, is that optimized experiments can be performed for coupled resonances of interest by choosing the sequence parameters dependent on the type of multiplets, the J-coupling constants and T₂. Major fields of application will be parametric studies on coupled resonances, (e.g., T₁, diffusion behavior or magnetization transfer) and/or the detection of spatial and temporal changes of metabolites with coupled spin systes.     

Optimization of INEPT and DEPT experiments for spin systems with hetero- and homonuclear couplings

The application of INEPT and DEPT pulse sequences to weakly coupled spin-$\text{1}\text{2}$ systems with different hetero- and homonuclear coupling constants has been investigated. For the simulation of the spectra arising from these multiple-pulse experiments, general computer programs have been written based on the density matrix approach. Numerical results calculated in this way allow the investigation of the polarization transfer in detail. Analytical expressions which describe the attainable sensitivity enhancement are presented. Their use in the experimental optimization of these pulse sequences is demonstrated for ¹³C and ¹⁵N NMR spectra.     

A comparison of selective saturation and selective echo chemical shift imaging techniques

We report on a comparative study of two methods of chemical shift imaging which can be used to selectively image fat and water in vivo. Both methods require a B0 field sufficiently homogenous to resolve the methylene and water spectral lines. One method, called CHESS, uses a chemically selective pulse to saturate the unwanted spectral line. The other method, called SECSI, achieves chemical selectivity by using a soft 180 degree RF pulse in forming a spin echo image. Both methods require that the strength of the B1 RF field be accurately calibrated and homogenous. We show by theoretical analysis that the suppression of unwanted spectral lines is sensitive to the first power of B1 errors in the CHESS method but to the second power of B1 errors in the SECSI method. Experiments with phantoms confirmed the expected non linearity of the SECSI method, and showed superior water suppression factors in phantoms with it. Experiments with a large phantom and a living rabbit showed superior results using the SECSI method, and the best results were obtained using a combination of the two techniques.     

Energy gap in tunneling spectroscopy: Effect of the chemical potential shift

We study the effect of a shift of the chemical potential level on the tunneling conductance spectra. In the systems with gapped energy spectra, significant chemical-potential dependent distortions of the differential tunneling conductance curves, dI/dV, arise in the gap region. An expression is derived for the correction of dI/dV, which in a number of cases is found to be large. The sign of the correction depends on the chemical potential level position with respect to the gap. The correction of associated with the dI/dV chemical potential shift has a nearly linear dependence on the tip-sample separation z and vanishes at z → 0.     

Proper definition of spin current in spin-orbit coupled systems

The conventional definition of spin current is incomplete and unphysical in describing spin transport in systems with spin-orbit coupling. A proper and measurable spin current is established in this study, which fits well into the standard framework of near-equilibrium transport theory and has the desirable property to vanish in insulators with localized orbitals. Experimental implications of our theory are discussed.     

自旋-轨道耦合系统中的自旋流定义

通常的自旋流定义在描述自旋-轨道耦合系统中的自旋输运是不完整的与非物理的.文章作者提出在这类系统中自旋流的恰当定义.新定义的自旋流克服了通常定义下的本质缺点,可通过实验直接观测.