In vivo lactate editing in single voxel proton spectroscopy and proton spectroscopic imaging by homonuclear polarisation transfer

Volume-selective lactate editing has been performed successfully in vitro and in vivo in the brain on a clinical scanner using a PRESS-based single voxel ¹H spectroscopy and a ¹H spectroscopic imaging sequence. The PRESS sequence was made sensitive to homonuclear polarisation by replacing the standard 180° refocusing pulses with 90° pulses. Two acquisitions were made at a total echo time around 2/J (J is the coupling constant for CH and CH₃ spins in lactate ≈7 Hz) whose individual echo times differed by 5.5 ms. Subtraction of one signal from the other yielded the lactate resonance alone. The technique is an effective method of separating the overlapping signals of lactate and lipids. Furthermore this editing method can be performed without state of the art MRI scanner hardware.     

A new strategy for in vivo spectral editing. Application to GABA editing using selective homonuclear polarization transfer spectroscopy

A novel single-shot in vivo spectral editing method is proposed in which the signal to be detected, is regenerated anew from the thermal equilibrium magnetization of a source to which it is J-coupled. The thermal equilibrium magnetization of the signal to be detected together with those of overlapping signals are suppressed by single-shot gradient dephasing prior to the signal regeneration process. Application of this new strategy to in vivo GABA editing using selective homonuclear polarization transfer allows complete suppression of overlapping creatine and glutathione while detecting the GABA-4 methylene resonance at 3.02 ppm with an editing yield similar to that of conventional editing methods. The NAA methyl group at 2.02 ppm was simultaneously detected and can be used as an internal navigator echo for correcting the zero order phase and frequency shifts and as an internal reference for concentration. This new method has been demonstrated for robust in vivo GABA editing in the rat brain and for study of GABA synthesis after acute vigabatrin administration.     

Efficient spin-spin scalar coupling mediated C-13 homonuclear polarization transfer in biological solids without proton decoupling

We demonstrate that an efficient C′↔C polarization transfer based on J-coupling can be realized under fast magic-angle spinning (MAS) condition without ¹H decoupling. Experimental results are presented for model crystalline compounds as well as a non-crystalline 17-residue polypeptide MB(i+4)EK. Measurements on MB(i+4)EK demonstrate that 53% of the initial C′ polarization was transferred to the cross peaks at 7.05 T under 25 kHz MAS spinning.     

A phase-insensitive single-scan method for volume-selective editing of NMR signals using cyclic polarization transfer. In vivo determination of lactate

A phase-insensitive pulse sequence serving the volume-selective editing of resonances in biomedical NMR spectroscopy is described. The editing principle is the temporary transfer of polarization of the spins to be detected to other species coupled to them. The technique is of particular interest for the localized detection of the lactate methyl proton line while spoiling coherences of uncoupled as well as coupled lipid nuclei otherwise overlapping the lactate resonance. The whole line-editing and coherence-spoiling procedure takes place completely in each scan of any accumulation or phase-cycling series. Phantom studies were carried out with an experimental 4.7 T system. The technique was also tested with volunteers in whole-body tomographs operating at 2 and 3 T. Comparative spectra are presented. It is concluded that editing is crucial for the reliable determination of lactate in muscle and in brain.     

Relativistic DWBA calculations for polarization transfer in proton inelastic scattering

The matrix element for inelastic scattering of protons leading to the excitation of collective states in even-even nuclei is calculated in the framework of Dirac phenomenology using a DWBA approach. The deformed parts of the Lorentz scalar and four-vector optical potentials serve as the transition operators. The results are compared with the recently measured polarization transfer coefficients on ⁴⁰Ca and ²⁰⁸Pb at 500 MeV. The agreement with experiment is good.     

Simultaneous spectral editing for gamma-aminobutyric acid and taurine using double quantum coherence transfer

Conventional double quantum (DQ) editing techniques recover resonances of one metabolite at a time and are thus inefficient for monitoring metabolic changes involving several metabolites. A DQ coherence transfer double editing sequence using a dual-band DQ coherence read pulse is described here. The sequence permits simultaneous spectral editing for two metabolites with similar J coupling constants in a single scan. Simultaneous editing for taurine and gamma-aminobutyric acid (GABA) is demonstrated using solution phantoms and rat brain tissue. Selectivity of the double editing sequence for the target metabolites is as good as that achieved using conventional DQ editing which selects each metabolite individually. With experimental parameters of the double editing sequence chosen to optimize GABA editing, the sensitivity for GABA detection is the same as that with GABA editing only, while the sensitivity for taurine detection is decreased slightly compared to that with taurine editing only.     

Echo-time independent signal modulations using PRESS sequences: a new approach to spectral editing of strongly coupled AB spin systems

In clinical MR spectroscopy, double spin-echo point resolved spectroscopy (PRESS) sequences are routinely used for volume selection. For strongly coupled AB spin systems under PRESS excitation, the dependence of the signal on the echo time TE has been thoroughly investigated, whereas less attention has been paid to the signal modulation which occurs at constant TE with varying interpulse delays. A substantial TE-independent J modulation is here predicted from analytical solutions of the Liouville equation and density matrix simulations, and verified with experiments on citrate at 1.5 and 3T. It is also shown that this modulation effect could be exploited for editing of strongly coupled AB resonances or for removal of singlets in spectra-by means of difference spectroscopy-just using a standard PRESS sequence. The applicability in vivo of this new spectral editing approach is also demonstrated, with selective detection of citrate resonances in the human prostate. This novel approach has the advantages of being simple, and directly applicable on standard clinical MR scanners, provided that the exact behavior of the resonance is known.     

Off-resonance effects of the radiofrequency pulses used in spectral editing with double-quantum coherence transfer

Spectral editing using gradient selected double-quantum (DQ) coherence transfer is often used for the selective observation of metabolites in vivo. In attempting to optimize the detection sensitivity of a conventional DQ spectral editing sequence, the effects of using radiofrequency (RF) pulses that are not at the resonance frequency of the observed peaks were investigated both theoretically and experimentally. The results show that spectral editing using pulses at the frequency of the observed resonance does not necessarily give the optimal detection sensitivity. At 7 T, the detection sensitivity of lactate observed using a DQ editing method can be increased by up to 30% by setting the RF pulses off resonance at the proper frequency. The results also suggest that slice selective RF pulses used in DQ spectral editing combined with PRESS localization may have slice profiles different from those when the same pulses are used for standard PRESS spatial localization.     

The effects of slice-selective excitation/refocusing in localized spectral editing with gradient-selected double-quantum coherence transfer

Spectral editing using gradient-selected double-quantum filtering (DQF) with PRESS localization has been used for selective observation of metabolites in vivo. In previous studies using localized DQF sequences, it is generally assumed that the slice-selective pulses used in the sequence have no roles in coherence transfer, and do not interfere with DQF. To validate this assumption, the effects of slice-selective excitation/refocusing on DQF were investigated in DQF lactate editing sequences combined with PRESS localization. Contrary to the previous assumption, the results show that, due to chemical shift displacement artifact and J coupling, slice selection in DQF does interfere with coherence transfer, affecting both the accuracy of spatial localization and the detection sensitivity adversely. In the case of lactate editing, the effects of this interference can be accounted for simply by adjusting the strength of the slice-selection gradients and by using narrowband slice-selective refocusing pulses.     

C CPMAS studies of plant cell wall materials and model systems using proton relaxation-induced spectral editing techniques

The solid state ¹³C CPMAS NMR spectra of plant cell walls are often complex owing to superposition of resonances from different polysaccharides and the heterogeneity of the cell wall assembly. In this paper, we describe the application of a set of proton relaxation-induced spectral editing (PRISE) experiments which combine ¹H relaxation properties (T₁, T_1ρ, T₂) with ¹³C high resolution spectroscopy (CPMAS) to relate the dynamics of the plant cell walls and model systems to their domain structural details. With PRISE it has been found that in plant cell wall materials, cellulose is always associated with the long components of spin–lattice relaxation in both the laboratory and rotating frames whereas non-cellulose polysaccharides (pectin and hemicellulose) are associated with the short ones. For the proton T₂ relaxation, cellulose is only associated with the short component (below 20 μs), pectin contributes to both the short component and the long one.     

13C CPMAS studies of plant cell wall materials and model systems using proton relaxation-induced spectral editing techniques

The solid state 13C CPMAS NMR spectra of plant cell walls are often complex owing to superposition of resonances from different polysaccharides and the heterogeneity of the cell wall assembly. In this paper, we describe the application of a set of proton relaxation-induced spectral editing (PRISE) experiments which combine 1H relaxation properties (T1, T1rho, T2) with 13C high resolution spectroscopy (CPMAS) to relate the dynamics of the plant cell walls and model systems to their domain structural details. With PRISE it has been found that in plant cell wall materials, cellulose is always associated with the long components of spin-lattice relaxation in both the laboratory and rotating frames whereas non-cellulose polysaccharides (pectin and hemicellulose) are associated with the short ones. For the proton T2 relaxation, cellulose is only associated with the short component (below 20 micros), pectin contributes to both the short component and the long one.     

Elimination of spectral distortion in polarization transfer experiments. Improvements and comparison of techniques

Three modified polarization transfer techniques, INEPT⁺, DEPT⁺, and DEPT⁺⁺, are introduced for the elimination of distortions in proton-coupled spectra of low-gyromagnetic-ratio spins. The existing polarization transfer techniques are analyzed in view of their susceptibility to intensity, multiplet, and phase anomalies.     

Coulomb effects in polarization transfer in elastic antiproton and proton electron scattering at low energies

The influence of Coulomb distortion on the polarization transfer in elastic proton and antiproton electron scattering at low energies is calculated in a distorted-wave Born approximation. For antiproton electron scattering Coulomb effects reduce substantially the polarization transfer cross-section compared to the plane-wave Born approximation, whereas for proton electron scattering they lead to a dramatic increase for kinetic proton lab energies below about 20keV.     

Insights into homonuclear decoupling from efficient numerical simulation: techniques and examples

A combination of techniques, including rational number synchronisation and pre-diagonalisation of the time-dependent periodic Hamiltonian, are described which allow the efficient simulation of NMR experiments involving both magic-angle spinning (MAS) and RF irradiation, particularly in the important special case of phase-modulated decoupling sequences. Chebyshev and conventional diagonalisation approaches to calculating propagators under MAS are also compared, with Chebyshev methods offering significant advantages in cases where the Hamiltonian is large and time-dependent but not block-diagonal (as is the case for problems involving combined MAS and RF). The ability to simulate extended coupled spin systems efficiently allows 1H spectra under homonuclear decoupling to be calculated directly and compared to experimental results. Reasonable agreement is found for the conditions under which homonuclear decoupling is typically applied for rigid solids (although the increasing deviation of experimental results from the predictions of theory and simulation at higher RF powers is still unexplained). Numerical simulations are used to explore three features of these experiments: the interaction between the magic-angle spinning and RF decoupling, the effects of tilt pulses in acquisition windows and the effects of "phase propagation delays" on tilted axis precession. In each case, the results reveal features that are not readily anticipated by previous analytical studies and shed light on previous empirical observations.     

2-D homonuclear correlation and separated local field experiments for solids with strong homonuclear dipolar couplings

An experiment for acquiring two-dimensional homonuclear correlation spectra of nuclei in solids in the presence of strong homonuclear dipolar couplings is described. The experiment utilizes a multiple-pulse homonuclear decoupling sequence with an effective precession axis parallel to the rotating frame z-axis during the evolution and detection periods. A multiple-pulse sequence that suppresses chemical shift and heteronuclear dipolar coupling evolution and scales the static homonuclear dipolar coupling is proposed for the mixing period. The evolution during the mixing period is analogous to the dynamics of the mixing period in solution-state TOCSY experiments, and can be interpreted as the oscillatory exchange of longitudinal magnetization between coupled spins. For nuclides with large gyromagnetic ratios, the static homonuclear dipolar interaction will be substantially larger than the mechanisms used to develop internuclear correlations in solution state 2-D experiments, which should make it possible to establish correlations over much longer distances and with significantly shorter mixing times. Extensions to separated local field experiments are discussed.     

How to reconcile the Rosenbluth and the polarization transfer methods in the measurement of the proton form factors

The apparent discrepancy between the Rosenbluth and the polarization transfer methods for the ratio of the electric to magnetic proton form factors can be explained by a two-photon exchange correction which does not destroy the linearity of the Rosenbluth plot. Though intrinsically small, of the order of a few percent of the cross section, this correction is accidentally amplified in the case of the Rosenbluth method.