Document Type



Doctor of Philosophy (PhD)



First Advisor's Name

Dr. Konstantinos Kavallieratos

First Advisor's Committee Title

Committee chair

Second Advisor's Name

Dr. Christopher Dares

Second Advisor's Committee Title

Committee member

Third Advisor's Name

Dr. Stanislaw Wnuk

Third Advisor's Committee Title

Committee member

Fourth Advisor's Name

Dr. Raphael Raptis

Fourth Advisor's Committee Title

Committee member

Fifth Advisor's Name

Dr, Joerg Reinhold

Fifth Advisor's Committee Title

Committee member


Sulfonamide, sulfonamidophenols, lanthanides, actinides, alkaline, high-level waste, legacy waste, Savannah river site, dodecane, ligand, solvent extraction, optical sensing, fluorescence sensing

Date of Defense



The accumulated (>100 Mgal) alkaline high-level waste (HLW), which is a legacy of nuclear weapons manufacturing during the cold war era, is an issue of environmental concern that has presented reprocessing challenges, due to its complex physicochemical properties and the presence of 137Cs, 90Sr, and long-lived actinides.

This study is focused on o-sulfonamidophenol derivatives bearing electron-rich O- and N- donor sites (when deprotonated in alkaline conditions) for effective complexation, sensing, and extraction of f-elements from highly alkaline solutions. Using Ln(III) as experimental surrogates for An(III), a family of o-sulfonamidophenol ligands (L1H2 – L4H2) bearing tert-butyl and/or isopropyl groups gave high extraction for Sm(III), with recoveries as high as 96.1 (±4.4)% and 93.3 (±5.2)% at pH 13.0 and 14.0, respectively, after just one extraction/stripping contact using CH2Cl2 as a diluent (Chapter 2). Using a diluent similar to those used in the waste reprocessing industry (n‑dodecane:octanol (80:20, v/v)), extraction as high as 82.6 (±9.3)% and 53.9 (±4.0)% was achieved at pH 12.5 and 14.0 respectively as well as a binding constant range of ß2 = 3.98 (±0.01) × 1010 – 1.26 (±0.04) × 1012 M-2. DFT studies further suggested the likely formation of close ion pairs of type {Na[Sm(III)L2(H2O)x]}org as the extracted species. This work was expanded to even more lipophilic analogs (Chapter 3) that showed extraction even in n-dodecane with recoveries as high as 50.7 (±1.2)%. Sensing for Ln(III) in alkaline conditions was explored using dansyl (Chapter 4) and p‑nitro (Chapter 5) derivatives of our o-sulfonamidophenol framework. The dansyl derivative (Chapter 4) demonstrated fluorescent sensing along with Sm(III) recovered after extraction in CH2Cl2, as high as 92.2 (±13.5)% at pH 13.0. The p‑nitro derivative demonstrated µM optical sensing for Lu(III) (in CH3CN) in the presence of competing metals which are predominant in HLW - with color change from yellow to colorless observed only in the presence of Lu(III). Lu(III) complexation was further confirmed with the isolation and X-ray characterization of two unique complexes, a monomeric (Et3NH)3[Lu(LH)6] and a trimeric (Et3NH)5[Lu3(µ3-OH)2(LH)6(L)3]. These results, overall, point to the potential application of easily synthesized and affordable o‑sulfonamidophenol ligands for large-scale actinide extraction and sensing from alkaline HLW.





Rights Statement

Rights Statement

In Copyright. URI:
This Item is protected by copyright and/or related rights. You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).