Document Type

Dissertation - Open Access

Award Date

2019

Degree Name

Doctor of Philosophy (PhD)

Department / School

Chemistry and Biochemistry

First Advisor

Douglas Raynie

Keywords

Deep eutectic solvents, Density Functional Theory, Extraction, Hydrophobic deep eutectic solvents, Principal component analysis, olvatochromism

Abstract

Deep eutectic solvents are a new generation of ionic liquid-like solvents formed by combining hydrogen bond acceptor with hydrogen bond donor which result in the depression of the melting point of the solvent. Like ionic liquids, anions play a critical role in tuning the polarity, physicochemical properties, and thermodynamic behavior of deep eutectic solvent (DES). Choline chloride is the most widely used quaternary ammonium salt (QAS) in the literature and has remarkable advantages from reduced cost to low toxicity and volatility. Choline bromide and choline iodide are other QAS that have not been used often for DES synthesis and applications, probably with the opinion that chlorides form stronger hydrogen bonds. Developing new DES from these anions will broaden the scope of green solvents selection for diverse applications. The first objective of this dissertation looked into the synthesis and characterization of DES from choline chloride, choline bromide, and choline iodide with malic acid, malonic acid, and urea. Also, we studied the thermodynamic behavior of the solvents by measuring their vapor pressure, density, and infinite activity coefficient in polar and nonpolar solvents. The results show that choline bromide can sometimes be used to replace choline chloride because both QAS share comparable physicochemical behavior. In most cases, choline iodide forms weaker hydrogen bonding with the donors leading to the formation of a solid at room temperature. Nevertheless, all the solvents have melting temperature below 100℃. In summary, DES can be synthesized from the choline cation bonded with the halides, with the melting point and nature of the solvent dependent on the hydrogen bond donor (HBD). Secondly, despite the rapid rise in publications and applications since their inception in 2001, most of the DES synthesized are generally hydrophilic. The low cost, low toxicity, and bioavailability of DES make the solvent green and sustainable for diverse applications. Conversely, the hydrophilicity of DES practically limits their application to only polar compounds, which is a major drawback of the solvent. For the past three years, hydrophobic deep eutectic solvents (HDES) have emerged as alternative extractive media capable of extracting nonpolar molecules from aqueous environments. In chapter three of this dissertation, the general objective was to design a cost-effective hydrophobic DES from choline chloride and fatty acids. Varying the alkyl chain of the fatty acid broadened our understanding about the role of HBD in DES and also helped in the tunability of the HDES polarity. Due to the infancy of HDES, for the first time, this dissertation expands on the design, synthesis, and physicochemical characterization of HDES developed from choline chloride and fatty acids. To understand the hydrogen-bonding pattern of HDES, a multivariate unsupervised principal component analysis was used to cluster HDES by using known DES as a control. The HDES was able to extract about 70% of piperine, a bioactive compound from Piper nigrum. In the future, it is believed that HDES could replace the majority of toxic organic solvents used for analytical purposes. Lastly, the electronic and molecular properties of the HDES synthesized were studied by using a solvatochromic molecular probes and a hybrid density functional theory at 6-31G (d) basis set. The empirical polarity assay and quantum theoretical calculations showed that decreasing the alkyl chain length of the hydrogen bond donor increases viscosity of the DES. Optimization of the DES molecular geometry indicates a reduced bond angle between the C15-O16-H17 atoms in choline chloride, signifying a change in electronegativity of the central atom (O16) during DES formation. From our results, we predict a possible molecular reorientation between the donor and the acceptor molecules during DES formation. The combined theoretical calculations and experimental approaches are useful to establish clear correlations between electronic parameters and physiochemical parameters like polarity, viscosity, and stability of carboxylic acid-DES and can be extended to other conventional solvents.

Library of Congress Subject Headings

Solvents.
Anions.
Choline.
Green chemistry.

Format

application/pdf

Number of Pages

195

Publisher

South Dakota State University

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Rights Statement

In Copyright