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.     

Optimal echo spacing for multi-echo imaging measurements of Bi-exponential T2 relaxation

Calculations, analytical solutions, and simulations were used to investigate the trade-off of echo spacing and receiver bandwidth for the characterization of bi-exponential transverse relaxation using a multi-echo imaging pulse sequence. The Cramer–Rao lower bound of the standard deviation of the four parameters of a two-pool model was computed for a wide range of component T₂ values and echo spacing. The results demonstrate that optimal echo spacing (TE_opt) is not generally the minimal available given other pulse sequence constraints. The TE_opt increases with increasing value of the short T₂ time constant and decreases as the ratio of the long and short time constant decreases. A simple model of TE_opt as a function of the two T₂ time constants and four empirically derived scalars is presented.     

The Role of Specific Side Groups and pH in Magnetization Transfer in Polymers

The nature of water–macromolecule interactions in aqueous model polymers has been investigated using quantitative measurements of magnetization transfer. Cross-linked polymer gels composed of 94% water, 3%N,N′-methylene-bis-acrylamide, and 3% functional monomer (acrylamide, methacrylamide, acrylic acid, methacrylic acid, 2-hydroxyethyl-acrylate, or 2-hydroxyethyl-methacrylate) were studied. Water–macromolecule interactions were modified by varying the pH and specific functional group on the monomer. The magnitudes of the interactions were quantified by measuring the rate of proton nuclear spin magnetization exchange between the polymer matrix and the water. This rate was highly sensitive to the presence of carboxyl side groups on the macromolecule. However, the dependence of the rate on pH was not consistent with simple acid/base-catalyzed chemical exchange, and instead, the data suggest that multiequilibria proton exchange, a wide distribution in surface group pKvalues, and/or a macromolecular structural dependence on pH may play a significant role in magnetization transfer in polymer systems. These model polymer gels afford useful insights into the relevance of chemical composition and chemical dynamics on relaxation in tissues.     

The relationship of problems in biomedical MRI to the study of porous media.

The NMR methods that are used to characterize inanimate porous media measure relaxation times and related phenomena and material transport, fluid displacement and flow. Biological tissues are comprised of multiple small, fluid-filled compartments, such as cells, that restrict the movement of the bulk solvent water and whose constituents influence water proton relaxation times via numerous interactions with macromolecular surfaces. Several of the methods and concepts that have been developed in one field of application are also of great value in the other, and it may be expected that technical developments that have been spurred by biomedical applications of MR imaging will be used in the continuing study of porous media. Some recent specific studies from our laboratory include the development of multiple quantum coherence methods for studies of ordered water in anisotropic macromolecular assemblies, studies of the degree of restriction of water diffusion in cellular systems, multiple selective inversion imaging to depict the ratios of proton pool sizes and rates of magnetization transfer between proton populations, and diffusion tensor imaging to depict tissue anisotropies. These illustrate how approaches to obtain structural information from biological media are also relevant to porous media. For example, the recent development of oscillating gradient spin echo techniques (OGSE), an approach that extends our ability to resolve apparent diffusion changes over different time scales in tissues, has also been used to compute surface to volume measurements in assemblies of pores. Each of the new methods can be adapted to provide spatially resolved quantitative measurements of properties of interest, and these can be efficiently acquired with good accuracy using fast imaging methods such as echo planar imaging. The community of NMR scientists focused on applications to porous media should remain in close communication with those who use MRI to study problems in biomedicine, to their mutual benefits.     

Exchange-mediated contrast in CEST and spin-lock imaging

Purpose

Magnetic resonance images of biological media based on chemical exchange saturation transfer (CEST) show contrast that depends on chemical exchange between water and other protons. In addition, spin–lattice relaxation rates in the rotating frame (R_1ρ) are also affected by exchange, especially at high fields, and can be exploited to provide novel, exchange-dependent contrast. Here, we evaluate and compare the factors that modulate the exchange contrast for these methods using simulations and experiments on simple, biologically relevant samples.

Methods

Simulations and experimental measurements at 9.4 T of rotating frame relaxation rate dispersion and CEST contrast were performed on solutions of macromolecules containing amide and hydroxyl exchanging protons.

Results

The simulations and experimental measurements confirm that both CEST and R_1ρ measurements depend on similar exchange parameters, but they manifest themselves differently in their effects on contrast. CEST contrast may be larger in the slow and intermediate exchange regimes for protons with large resonant frequency offsets (e.g. > 2 ppm). Spin-locking techniques can produce larger contrast enhancement when resonant frequency offsets are small (< 2 ppm) and exchange is in the intermediate-to-fast regime. The image contrasts scale differently with field strength, exchange rate and concentration.

Conclusion

CEST and R_1ρ measurements provide different and somewhat complementary information about exchange in tissues. Whereas CEST can depict exchange of protons with specific chemical shifts, appropriate R_1ρ-dependent acquisitions can be employed to selectively portray protons of specific exchange rates.     

Simultaneous measurement of D and T2 using the distant dipolar field

The presence of long-range dipolar fields in liquids is known to introduce a non-linear term in the Bloch-Torrey equations which is responsible for many interesting effects in nuclear magnetic resonance as well as in magnetic resonance imaging. We show here, for the first time, that the diffusion coefficient D and the spin-spin relaxation time T2 can be obtained simultaneously from the time evolution profile of the long-range dipolar field refocused signal. In a COSY Revamped by Z-asymmetric Echo Detection sequence, the analytical first-order approximation solution of the Bloch-Torrey equations modified to include the effect of the distant dipolar field is used to demonstrate the technique in an experiment using doped water.