How hydrogen bond donor acceptor ratio and water content impact heterogeneity in microstructure and dynamics of N,N-diisooctylacetamide and decanol based hydrophobic deep eutectic solvent

Recently hydrophobic deep eutectic solvents (HDESs) have emerged as a potential green alternative media for the extraction of compounds from aqueous environment, and their increased importance as water immiscible solvent has attracted researchers to gain more insights into this domain. The present study employs atomistic molecular dynamics simulations to elucidate the microscopic structural organization, dynamics, and crucial interactions in N,N-diisooctylacetamide (DOA) plus decanol (DEO) based HDES at different mole ratios of the hydrogen bond donor (HBD) and acceptor (HBA). The analysis of simulated X-ray and neutron scattering structure functions reveals a nanoscale heterogeneous structural organization in the HDES at all compositions. The genesis for this heterogeneity can be derived from the polarity alternation peaks of partial structure functions in the low-q region. Polarity ordering in DOA:DEO (1:2) HDES is observed at longer length-scales in comparison to that in DOA:DEO (1:1) and DOA:DEO (2:1) HDESs. Moreover, the liquid morphologies are portrayed by nano-polar domains ingrained into the apolar environment depicting polar and apolar self-segregation. The analysis of angle-resolved radial distribution functions suggests that the microstructures of these HDESs are dominated by a strong DEO-DEO and DEO-DOA hydrogen bonding interactions. Slower decay of the hydrogen bond autocorrelation function corresponding to DOA-DEO suggests stronger hydrogen bonding in DOA-DEO than DEO-DEO. The translational mobility of both the components decreases as the DOA concentration increases. The DEO molecules exhibit faster diffusion in bulk HDES than the DOA molecules. A small water content in the HDES leads to slightly enhanced segregation of polar and apolar environments in the HDESs. We observe that water molecules interfere with the hydrogen bonding network of DOA and DEO by establishing hydrogen bond with them, thereby reducing the strength of DEO-DEO and DOA-DEO hydrogen bond interactions. The hydration also causes slightly faster hydrogen bond relaxation dynamics, indicating the weakening of hydrogen bond interactions between the constituent species of the HDESs.