Andrew L. LaFrate

Design of Functionalized Room-Temperature Ionic Liquid-Based Materials for CO2 Separations and Selective Blocking of Hazardous Chemical Vapors

The design and synthesis of several new types of functionalized room-temperature ionic liquids (RTILs), ionic polymers based on RTILs (i.e., poly(RTIL)s), poly(RTIL)-RTIL solid-liquid composites, and gelled RTIL systems for gas separations and reactive vapor transport applications are presented. The design concepts behind these new RTIL materials are discussed in the context of first, CO2 removal from CH4 and N2 for natural gas purification and greenhouse gas reduction, respectively; and second selective blocking or sorption of chemical warfare agent simulant and toxic industrial compound vapors from water vapor for protection applications. The role of the RTIL components and their unique properties in these two separations areas will be highlighted.

Ionic liquid crosslinkers for chiral imprinted nanoGUMBOS.

Molecularly imprinted polymers (MIPs) are an important class of selective materials for molecular specific sensors and separations. Molecular imprinting using non-covalent interactions in aqueous conditions still remains a difficult challenge due to interruption of hydrogen-bonding or electrostatic interactions water. Newly developed crosslinking ionic liquids are demonstrated herein to overcome problems of synthesizing aqueous MIPs, adding to previous examples of ionic liquids used as monomers in non-aqueous conditions or used as MIP solvents. Vinylimidazole ionic liquid crosslinkers were synthesized and subsequently explored as matrix supports for fabrication of molecularly imprinted polymeric nanoGUMBOS (nanoparticles derived from a group of uniform materials based on organic salts). Each of the four crosslinkers incorporated a unique functional spacer between the vinylimidazole groups, and the performance of the corresponding molecularly imprinted polymers was evaluated using chiral recognition as the diagnostic. High uptake values for l-tryptophan were found in the 13-87μmol/g range; and chiral recognition was determined via binding ratios of l-tryptophan over d-tryptophan that ranged from 5:1 to 13:1 for polymers made using different crosslinkers. Not only are these materials good for chiral recognition, but the results highlight the utility of these materials for imprinting aqueous templates such as biological targets for theranostic agents.