The structural α-relaxation times of prilocaine confined in 1 nm pores of molecular sieves: quantitative explanation by the coupling model

Abstract

The molecular glass-former and pharmaceutical, prilocaine, distinguishes itself by exhibiting seven general and fundamental dynamic and thermodynamic properties [Z. Wojnarowska, et al., J. Phys. Chem. B, 2015, 39, 12699.], all of which have been explained using the coupling model. What has not been studied before are the changes in properties of the structural α-relaxation of prilocaine when subjected to extreme nano-confinement in spaces with a size of about 1 nm. Recently, Ruis et al. [G. N. Ruiz, et al., Phys. Chem. Chem. Phys., 2019, 21, 15576.] measured the α-relaxation times, τ_α,conf(T), of prilocaine confined in 1 nm pores of molecular sieves. They found that τ_α,conf(T) are significantly reduced from those of bulk prilocaine, τ_α,bulk(T), and assume a weaker temperature dependence. The data in toto pose a challenge for any theory of glass transition to explain quantitatively. The coupling model (CM) was applied to this problem to predict the α-relaxation times of prilocaine when cooperativity is removed, which is expected because only a few prilocaine molecules can fit into the 1 nm pores. The results from the CM are in quantitative agreement with the experimental values of τ_α,conf(T) and the temperature dependence. The success is nontrivial because no other extant theory can do the same to the best of our knowledge.