The Effects of Cross-Link Density and Chemical Exchange on Magnetization Transfer in Polyacrylamide Gels

The effects of polymer structure and water–macromolecule interactions on proton relaxation in an aqueous model polymer have been investigated using quantitative measurements of magnetization transfer. Polyacrylamide gels composed of 95% water, 5% comonomers acrylamide andN,N′-methylene-bis-acrylamide were studied. The structure and rigidity were varied by changing the cross-linking density of the polymer. The polymer showed a biphasic change in transverse relaxation with increasing cross-linking density which was accompanied by a sudden increase in magnetization transfer above 40% cross linking. This change may be attributed to the formation of rigid domains in the polymer which exhibit solid-like behavior with a shortT2(11 μs) and a Gaussian lineshape. Water–macromolecule interactions were controlled by varying the pH of the gel. At high pH (>8), there was an increase in magnetization transfer and transverse relaxivity consistent with a chemical-exchange-mediated interaction between water protons and the polymer. By analyzing the system as two proton reservoirs coupled by magnetization exchange, the proton populations, intrinsic relaxation rates, and exchange rates were estimated, for different degrees of cross linking and pH. This model affords useful insights into the relevance of both supramolecular structure and chemical exchange on relaxation in tissues.