Kazachenko Aleksandr, Akman Feride, Medimagh Mouna, Issaoui Noureddine, Vasilieva Natalya, Malyar Yuriy N, Sudakova Irina G, Karacharov Anton, Miroshnikova Angelina, Al-Dossary Omar Marzook
Institute of Chemistry and Chemical Technology, Krasnoyarsk Science Center, Siberian Branch, Russian Academy of Sciences, Akademgorodok, 50/24, Krasnoyarsk 660036, Russia.
Siberian Federal University, pr. Svobodny, 79, Krasnoyarsk 660041, Russia.
ACS Omega. 2021 Aug 25;6(35):22603-22615. doi: 10.1021/acsomega.1c02570. eCollection 2021 Sep 7.
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. 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.
硫酸化纤维素衍生物是具有抗凝特性的生物活性物质。在本研究中，获得了一种新型的硫酸化二乙氨基乙基（DEAE）-纤维素衍生物。研究了溶剂对硫酸化过程的影响。结果表明，1,4-二氧六环是最有效的溶剂，在氨基磺酸硫酸化过程中能确保硫酸化DEAE-纤维素中硫含量最高。比较了在1,4-二氧六环中以及在由氨基磺酸和尿素组成的低共熔溶剂中，在尿素存在下进行氨基磺酸硫酸化的过程。结果表明，使用1,4-二氧六环可得到硫含量更高的硫酸化产物。通过傅里叶变换红外光谱、X射线衍射、扫描电子显微镜和原子力显微镜对所得硫酸化DEAE-纤维素衍生物进行了分析，并测定了它们的聚合度。傅里叶变换红外光谱数据证实了硫酸根的引入；在1247 - 1256和809 - 816 cm范围内观察到了对应于硫酸根的吸收带。结果表明，使用低共熔溶剂会导致副氨基甲酰化反应。利用X射线衍射证明了硫酸化过程中DEAE-纤维素的非晶化。使用密度泛函理论，采用B3LYP/6 - 31G(d, p)基组计算了基态分子的几何结构。利用分子静电势图分析了DEAE-纤维素及其硫酸化衍生物的反应区域。测定了目标硫酸化产物的热力学参数（热容、熵和焓）。在分子中的原子理论范围内计算了标题化合物的HOMO - LUMO能隙、Mulliken原子电荷和电子密度拓扑结构。
