Evidence of superdiffusive nanoscale motion in anionic polymeric hydrogels: Analysis of PGSE- NMR data and comparison with drug release properties

Polymeric hydrogels are promising candidates for drug delivery applications, thanks to their ability to encapsulate, transport and release a wide range of chemicals. The successful application of these materials requires a deep understanding of the mechanisms governing solute transport at the nanoscale and its impact on release kinetics. In this work, we investigate the translational diffusion of ibuprofen loaded in anionic agarose-carbomer (AC) hydrogels by 1H high resolution magic angle spinning (HR-MAS) NMR spectroscopy, and compare it to its macroscopic release kinetics. The analysis of the experimental NMR data provides the first evidence of superdiffusion for ibuprofen in AC hydrogels. Superdiffusive transport is observed in the majority of our samples, especially those with the smallest mesh size (7 nm) and highest ibuprofen concentrations (90-120 mg/mL). This outcome is rationalized in terms of heavy-tailed distributions of spatial displacements (Lèvy flights) and of waiting times, which depend on the nanoscopic structural heterogeneity of the gels and the strong but reversible association between ibuprofen and the agarose matrix.