Sulfation of Diethylaminoethyl-Cellulose: QTAIM Topological Analysis and Experimental and DFT Studies of the Properties

[Image: see text] Sulfated cellulose derivatives are biologically active substances with anticoagulant properties. In this study, a new sulfated diethylaminoethyl (DEAE)-cellulose derivative has been obtained. The effect of a solvent on the sulfation process has been investigated. It is shown that 1,4-dioxane is the most effective solvent, which ensures the highest sulfur content in DEAE-cellulose sulfate under sulfamic acid sulfation. The processes of sulfamic acid sulfation in the presence of urea in 1,4-dioxane and in a deep eutectic solvent representing a mixture of sulfamic acid and urea have been compared. It is demonstrated that the use of 1,4-dioxane yields the sulfated product with a higher sulfur content. The obtained sulfated DEAE-cellulose derivatives have been analyzed by Fourier transform infrared spectroscopy, X-ray diffractometry, and scanning electron and atomic force microscopy, and the degree of their polymerization has been determined. The introduction of a sulfate group has been confirmed by the Fourier transform infrared spectroscopy data; the absorption bands corresponding to sulfate groups have been observed in the ranges of 1247–1256 and 809–816 cm(–1). It is shown that the use of a deep eutectic solvent leads to the side carbamation reactions. Amorphization of DEAE-cellulose during sulfation has been demonstrated using X-ray diffractometry. The geometric structure of a molecule in the ground state has been calculated using the density functional theory with the B3LYP/6-31G(d, p) basis set. The reactive areas of DEAE-cellulose and its sulfated derivatives have been analyzed using molecular electrostatic potential maps. The thermodynamic parameters (heat capacity, entropy, and enthalpy) of the target sulfation products have been determined. The HOMO–LUMO energy gap, Mulliken atomic charges, and electron density topology of the title compound have been calculated within the atoms in molecule theory.