Date of Award

Fall 2014

Document Type


Degree Name

Doctor of Philosophy (PhD)



First Advisor

Tran, Chieu D.

Second Advisor

Fiedler, Adam T.

Third Advisor

Timerghazin, Qadir


Macrocycles, such as crown ethers (CRs) and resorcinarenes (RESs), exhibit selective complexation of heavy metal ions and organic pollutants respectively. Consequently, they have been investigated for their suitability in adsorbing these aqueous pollutants. However, they are difficult to handle and recycle for reuse because, by themselves, they can only be fabricated in powder form. To alleviate this challenge, we developed a method to encapsulate these macrocycles into film-forming polysaccharides--cellulose (CEL) and chitosan (CS). This was achieved by using a green and recyclable solvent, an ionic liquid, to dissolve both macrocycles and polysaccharides and regenerate corresponding composites in water. Resultant composites were characterized by FTIR, UV-Visible, X-ray powder diffraction and scanning electron microscopy. These polysaccharides are attractive because they are naturally abundant, biodegradable and biocompatible. The composites retained desirable properties of their individual constituents, namely superior mechanical strength (from CEL), excellent adsorption capability for cadmium and zinc ions (from CRs and CS) and organic solutes (from RESs and CS). Specifically, increasing the concentration of CEL from 50% to 90% in [CEL+CR] resulted in almost 2X increase in tensile strength. Adding 40% benzo 15-crown-5 ether (B15C5) to CS led to a 4X enhancement in the amount of cadmium ions adsorbed by [CS+B15C5]. Interestingly, RES-based composites exhibited selectivity amongst dinitrobenzene (DNB) isomers. For example, one g of [CEL+RES] adsorbed more 1,2-DNB (5.37±0.05 mol L-1) than 1,3-DNB (4.52±0.03 mol L-1) and 1,4-DNB (2.74±0.04 mol L-1). These results help to extend the potential applications of supramolecular composites in water remediation. We also successfully synthesized hydroxyapatite (HAp) in situ by alternately soaking [CEL+CS] composite films in calcium and phosphate salt solutions. These composites will be expected to be osteoconductive (due to HAp), thereby necessitating their use in bone tissue engineering. In another related study, we developed a simple, one step process to encapsulate an antibiotic, ciprofloxacin (CPX) in composites containing various proportional concentrations of CEL, CS, and keratin (KER). KER was found to slow down the release of CPX from the composites. These results clearly indicate that the release of CPX can be controlled by judicious adjustment of the concentrations of KER in the composites.