A single-shot measurement of time-dependent diffusion over sub-millisecond timescales using static field gradient NMR

Abstract

Time-dependent diffusion behavior is probed over sub-millisecond timescales in a single shot using a nuclear magnetic resonance static gradient time-incremented echo train acquisition (SG-TIETA) framework. The method extends the Carr-Purcell-Meiboom-Gill cycle under a static field gradient by discretely incrementing the π-pulse spacings to simultaneously avoid off-resonance effects and probe a range of timescales (50-500 µs). Pulse spacings are optimized based on a derived ruleset. The remaining effects of pulse inaccuracy are examined and found to be consistent across pure liquids of different diffusivities: water, decane, and octanol-1. A pulse accuracy correction is developed. Instantaneous diffusivity, Dinst(t), curves (i.e., half of the time derivative of the mean-squared displacement in the gradient direction) are recovered from pulse accuracy-corrected SG-TIETA decays using a model-free log-linear least squares inversion method validated by Monte Carlo simulations. A signal-averaged 1-min experiment is described. A flat Dinst(t) is measured on pure dodecamethylcyclohexasiloxane, whereas decreasing Dinst(t) is measured on yeast suspensions, consistent with the expected short-time Dinst(t) behavior for confining microstructural barriers on the order of micrometers.