Prototropic Exchange Governs T-1 and T-2 Relaxivities of a Potential MRI Contrast Agent Nanozeolite Gd-LTL with a High pH Responsiveness
Aqueous suspensions of lanthanide exchsanged zeolite LTL have been investigated by 1H, 17O NMR, and EPR relaxivity studies. Both the longitudinal and the transverse relaxivity of these Gd3+ loaded materials are strongly pH dependent and therefore, they have great potential as pH responsive contrast agents. For example, LTL-nanocrystals loaded with 3.5 wt % Gd show a dramatic decrease in the longitudinal relaxivity from 32 to 7 s(-1) mM(-1) (7.5 T and 25 degrees C) when going from pH 4 to 9. 1H and O-17 NMR show that this phenomenon can be rationalized by a decrease in proton mobility between the zeolite interior and the exterior due to a change from a fast prototropic exchange to a 3 orders of magnitude slower water exchange mechanism. The same material also has a high transverse relaxivity (98 s(-1) mM(-1) at 7.5 T, 25 degrees C, and pH 5 as measured with the CPMG pulse sequence), which is governed by proton exchange too, while water diffusion plays a minor role. The high relaxivities and pH dependence render Gd-loaded LTL materials promising pH responsive contrast agents. Since the r(2)/r(1) ratio of the designed probe strongly increases with the magnetic field strength, these materials are expected to be applicable for both T-1 and T-2 weighted imaging at low and high fields, respectively.
jpcc119-5080.pdf
restricted
1.29 MB
Adobe PDF
de7182bfe5d527bd002e91642aea3397
jpcc119-5080-supp.pdf
restricted
1.65 MB
Adobe PDF
db081ac89404e65f2c60920e7b13cee0