Dissolution mechanism of cellulose in a benzyltriethylammonium/urea deep eutectic solvent (DES): DFT-quantum modeling, molecular dynamics and experimental investigation.

In this paper, a benzyltriethylammonium/urea DES was investigated as a new green and eco-friendly medium for the progress of organic chemical reactions, particularly the dissolution and the functionalization of cellulose. In this regard, the viscosity-average molecular weight of cellulose (M̄w) during the dissolution/regeneration process was investigated, showing no significant degradation of the polymer chains. Moreover, X-ray diffraction patterns indicated that the cellulose dissolution process in the BTEAB/urea DES decreased the crystallinity index from 87% to 75%, and there was no effect on type I cellulose polymorphism. However, a drastic impact of the cosolvents (water and DMSO) on the melting point of the DES was observed. Besides, to understand the evolution of cellulose-DES interactions, the formation mechanism of the system was studied in terms of H-bond density and radial distribution function (RDF) using molecular dynamics modeling. Furthermore, density functional theory (DFT) was used to evaluate the topological characteristics of the polymeric system such as potential energy density (PED), laplacian electron density (LED), energy density, and kinetic energy density (KED) at bond critical points (BCPs) between the cellulose and the DES. The quantum theory of atoms in molecules (AIM), Bader's quantum theory (BQT), and reduced density gradient (RDG) scatter plots have been exploited to estimate and locate non-covalent interactions (NCIs). The results revealed that the dissolution process is attributed to the physical interactions, mainly the strong H-bond interactions.

New benzyltriethylammonium/urea deep eutectic solvent: Quantum calculation and application to hyrdoxylethylcellulose modification.

In this paper, a new deep eutectic solvent (DES) has been successfully synthesized that is based on benzyltriethylammonium bromide as a hydrogen bond acceptor (HBA) and urea as a hydrogen bond donor (HBD). However, its usability in modifying cellulose derivatives, especially acylating hydroxyethylcellulose (HEC) was investigated. The chemical modification (acetylation) of HEC was carried out in BTEAB/urea DES system without any additional conventional solvent or catalyst. However, the proposed structure of acetylated HEC (HECA) was confirmed according to the structural spectra analyses FTIR-ATR, 1H, 13C, and APT-NMR. The crystalline behavior of acetylated and unmodified HEC in the DES system has been evaluated using XRD patterns, where the thermal stability was evaluated basing on the TD-TGA thermograms. Hence, SEM images and EDX spectra were recorded to prove the changes that are expected at the morphological level and elemental profile. Yet, the nanometric sheets aspect was observed. The Functional Density Theory (DFT) was investigated as a useful computational tool to understand mechanism and donor-acceptor interactions. The topological parameters (electron density Laplacian, kinetic energy density, potential energy density, and energy density) at the bond critical points (BCP), between TBEAB and urea, are deducted according to Quantum Bader's theory, and Atoms-in-molecules (AIM). The non-covalent interactions and steric effect in the DES system were studied using the reduced density gradient isosurface (RDG). Theoretical and computational calculations revealed that the H-bonds and the electrostatic coexist, as predominant interactions in the BTEAB-based DES resulting chemical structure, and mechanism formation. The physical interactions between the component entities of DES lead to a new equilibrium that is more stable than that of HBA and HBD in their separate states.