Bena-Marie Lue

Predictions of flavonoid solubility in ionic liquids by COSMO-RS: experimental verification, structural elucidation, and solvation characterization

Predictions of the solubility of flavonoids in a large variety of ionic liquids (ILs) with over 1800 available structures were examined based on COSMO-RS computation. The results show that the solubilities of flavonoids are strongly anion-dependent. Experimental measurement of the solubilities of esculin and rutin in 12 ILs with varying anions and cations show that predicted and experimental results generally have a good agreement. Based on the sound physical basis of COSMO-RS, the solubility changes of flavonoids were quantitatively associated with solvation interactions and structural characteristics of ILs. COSMO-RS derived parameters, i.e. misfit, H-bonding and van der Waals interaction energy, are shown to be capable of characterizing the complicated multiple interactions in the IL system effectively. H-bonding interaction is the most dominant interaction for ILs (followed by misfit and van der Waals interactions) to determine the solubility of flavonoids, and the anionic part has greater effect on the overall H-bonding capability of the IL. Based on basicity of anions, ILs were categorized into 3 groups, corresponding to the classification of the solubility of flavonoid. COSMO sigma-moment descriptors, which roughly denote the characteristic properties of the ILs, might be of general value to have a fast estimation for the solubilities of flavonoids as well as those compounds with massive moieties as H-bonding donors. The results obtained in this work may be important for achieving an improved understanding of IL solvations and the tailoring of the desired structures of ILs used as the media for efficient enzymatic esterification of flavonoids.

Enzymatic synthesis of esculin ester in ionic liquids buffered with organic solvents.

The enzymatic esterification of esculin catalyzed by Candida antarctica lipase B (Novozym 435) was carried out in ionic liquid (IL)-organic solvent mixed systems in comparison with individual systems. The reaction behaviors in IL-organic solvents were systemically evaluated using acetone as a model solvent. With organic solvents as media, the esterification rates of esculin depended mainly on its solubility in solvents; for the reactions in ILs, the reaction rates were generally low, and the anion part of the IL played a critical role in enzyme activity. Therefore, the esterification of esculin in IL-acetone mixtures made it possible to improve the solubility of esculin while the effects of ILs on lipase activity were minimized. Following the benignity of ILs to lipase activity, the anions of ILs were ranked in the order as [Tf(2)N](-) > [PF(6)](-) > [BF(4)](-) > [CF(3)SO(3)](-) > [C(4)F(9)SO(3)](-) > [TAF](-) > [MDEGSO(4)](-) > [OctSO(4)](-) > [ES](-) = [DMP](-) = [OTs](- )= Cl(-). The reaction behaviors differed in different systems and largely depended on the properties of the ILs and organic solvents. In general, improvements were observed in terms of both solubility and reaction efficiency. The knowledge acquired in this work gives a better understanding of multiple interactions in IL-organic solvent systems, which provide guidance for system design and optimization.

Preparation of CLA ascorbyl ester with improved volumetric productivity by an ionic liquid-based reaction system

A new approach to the enzymatic production of conjugated linoleic acid (CLA) ascorbyl ester with a remarkably high volumetric productivity (120-200 g L(-1)) has been developed, in which strong solvation by tOMA.TFA (methyltrioctylammonium trifluoroacetate) enables a high concentration of ascorbic acid to be applied, and in which t-butanol enhances conversion by changing the equilibrium constant of the activity coefficients. This work has experimentally demonstrated the practicability of achieving efficient reactions of polar compounds at high concentrations in ionic liquids without significant loss of enzyme activity.

High-performance liquid chromatography analysis methods developed for quantifying enzymatic esterification of flavonoids in ionic liquids

Methods using reversed-phase high-performance liquid chromatography (RP-HPLC) with ELSD were investigated to quantify enzymatic reactions of flavonoids with fatty acids in the presence of diverse room temperature ionic liquids (RTILs). A buffered salt (preferably triethylamine-acetate) was found essential for separation of flavonoids from strongly polar RTILs, whereby RTILs were generally visible as two major peaks identified based on an ion-pairing/exchanging hypothesis. C8 and C12 stationary phases were optimal while mobile phase pH (3-7) had only a minor influence on separation. The method developed was successfully applied for primary screening of RTILs (>20), with in depth evaluation of substrates in 10 RTILs, for their evaluation as reaction media.

SURFACE ACTIVE LIPIDS AS ENCAPSULATION AGENTS AND DELIVERY VEHICLES

Surface active lipids, such as partial acylglycerols, phospholipids, and glycolipids, are amphiphilic molecules that lower either the surface tension of the medium in which they are dissolved or the interfacial tension between phases at which they are adsorbed. Due to their amphiphilicity, surface active lipids are able to self-assemble into various unique supramolecular structures ranging from micro- to nanoscales. These unique supramolecular structures are found to have enhanced physical properties ranging from increased gelation capability, guest molecules loading capacity, and in-vivo stability to targeted delivery and molecular recognition. Thus, surface active lipids have garnered huge interest as encapsulation agents and delivery vehicles in various industries including food, pharmaceutical, and cosmetics. Work has also been directed toward synthesis of novel compounds and structural modification of existing surface active lipids. This chapter presents a review on current state-of-the art design, synthesis, and purification of surface active lipids—partial acylglycerols, phospholipids, glycolipids, aminolipids and lipopeptides, phytosterol surfactant, and antioxidant esters and elucidates physical properties of such lipids, including self-assembling and formation of various supramolecular structures. It also discusses some potential applications of the surface active lipids.