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

Omar Azougagh, Issam Jilal, Loubna Jabir, Hayat El-Hammi, Soumya Essayeh, Nor Mohammed, Nafea Achalhi, Ridouan El Yousfi, Abderrahmane El Idrissi, Youssef El Ouardi, Katri Laatikainen, Mohamed Abou-Salama, Soufian El Barkany

2023Physical Chemistry Chemical Physics23 citationsDOIOpen Access PDF

Abstract

) 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.

Topics & Concepts

CelluloseDensity functional theoryDissolutionMolecular dynamicsDeep eutectic solventCrystallinityChemistryPolymerComputational chemistryPhysical chemistryMaterials scienceChemical physicsChemical engineeringEutectic systemCrystallographyOrganic chemistryEngineeringMicrostructureAdvanced Cellulose Research StudiesIonic liquids properties and applicationsLignin and Wood Chemistry
Dissolution mechanism of cellulose in a benzyltriethylammonium/urea deep eutectic solvent (DES): DFT-quantum modeling, molecular dynamics and experimental investigation | Litcius