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Abstract
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The increasing interest of the pharmaceutical industry in deep eutectic solvents (DESs) has heightened the de
mand for predicting their bulk properties and advancing the development of these eco-friendly solvents.
Meanwhile, caprylic acid-based DESs have gained significant attention due to their unique physicochemical
properties and potential applications in various fields. However, the influence of finite particle size on the
structural properties and bulk property predictions of these DESs remains largely unexplored. In addition, the
investigation focuses on the influence of nanoscale confinement on the organization and interactions of DES
components. In this respect, MD simulations were used to systematically investigate the influence of finite-size
effects on essential properties, including hydrogen bonding networks, diffusivity and distribution of species
around each other in the binary mixtures. Our findings reveal that system size markedly affects the local
structuring and dynamic behavior of DES components, leading to deviations from the prediction of the bulk
properties. Velocity autocorrelation functions (VACFs), vector reorientation dynamics (VRD) of DES species, and
other results provide valuable insights into the limitations and potential pitfalls of using finite-size systems for
the prediction of the properties of DESs. The results indicate that systems with 1000 particles provide satisfactory
predictions of thermophysical properties compared to other system sizes. This is because the self-diffusion co
efficient from molecular dynamics simulations (DMD) values approach the self-diffusion coefficient values
observed in the thermodynamic limit. Notably, the density profile results reveal that confinement within
nanotubes significantly influences the structural properties of eutectic solvents. Therefore, this study provides a
fundamental understanding of the confined behavior of DESs, which is crucial for their application in emerging
nanotechnologies.
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