Daso Rachel E, Mitchell Saige M, Lebedenko Charlotta G, Heise Ryan M, Banerjee Ipsita A
Department of Chemistry, Fordham University, 441 East Fordham Road, Bronx, New York 10458, United States.
ACS Omega. 2021 Nov 19;6(48):32460-32474. doi: 10.1021/acsomega.1c03864. eCollection 2021 Dec 7.
Bio-organic amphiphiles have been shown to effectively impart unique physicochemical properties to ionic liquids resulting in the formation of versatile hybrid composites. In this work, we utilized computational methods to probe the formation and properties of hybrids prepared by mixing three newly designed bio-organic amphiphiles with 14 ionic liquids containing cholinium or glycine betaine cations and a variety of anions. The three amphiphiles were designed such that they contain unique biological moieties found in nature by conjugating (a) malic acid with the amino acid glutamine, (b) thiomalic acid with the antiviral, antibacterial pyrazole compound [3-(3,5-dimethyl-1-pyrazol-1-yl)benzyl]amine, and (c) Fmoc-protected valine with diphenyl amine. Conductor-like screening model for real solvents (COSMO-RS) was used to obtain sigma profiles of the hybrid mixtures and to predict viscosities and mixing enthalpies of each composite. These results were used to determine optimal ionic liquid-bio-organic amphiphile mixtures. Molecular dynamics simulations of three optimal hybrids were then performed, and the interactions involved in the formation of the hybrids were analyzed. Our results indicated that cholinium-based ILs interacted most favorably with the amphiphiles through a variety of inter- and intramolecular interactions. This work serves to illustrate important factors that influence the interactions between bio-organic amphiphiles and bio-ILs and aids in the development of novel ionic liquid-based composites for a wide variety of potential biological applications.
生物有机两亲物已被证明能有效地赋予离子液体独特的物理化学性质，从而形成多功能杂化复合材料。在这项工作中，我们利用计算方法探究了由三种新设计的生物有机两亲物与14种含有胆碱或甘氨酸甜菜碱阳离子以及各种阴离子的离子液体混合制备的杂化物的形成和性质。设计这三种两亲物时，使其通过将（a）苹果酸与氨基酸谷氨酰胺共轭、（b）硫代苹果酸与抗病毒、抗菌的吡唑化合物[3-(3,5-二甲基-1-吡唑-1-基)苄基]胺以及（c）芴甲氧羰基保护的缬氨酸与二苯胺共轭，从而含有自然界中发现的独特生物部分。使用导体类真实溶剂筛选模型（COSMO-RS）来获得杂化混合物的σ轮廓，并预测每种复合材料的粘度和混合焓。这些结果用于确定最佳的离子液体-生物有机两亲物混合物。然后对三种最佳杂化物进行了分子动力学模拟，并分析了杂化物形成过程中涉及的相互作用。我们的结果表明，基于胆碱的离子液体通过多种分子间和分子内相互作用与两亲物的相互作用最为有利。这项工作有助于阐明影响生物有机两亲物与生物离子液体之间相互作用的重要因素，并有助于开发用于各种潜在生物应用的新型离子液体基复合材料。
