Theses and Dissertations from UMD
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Item ACYCLIC CUCURBIT[N]URIL MOLECULAR RECEPTORS: SEQUESTRANTS FOR DRUGS, MICROPOLLUTANTS, AND IODINE(2024) Perera, Wahalathanthreege Sathma Suvenika; Isaacs, Lyle; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Molecular containers are extensively utilized for their exceptional molecular recognition capabilities, making them suitable for use as sensors and sequestration agents. Cucurbit[n]urils, in particular, are recognized for their strong binding affinities, especially towards cationic guest molecules. These applications can be further enhanced by adjusting the size and shape of the host and incorporating functional groups.In Chapter 1, the concept of supramolecular chemistry is introduced, with a specific focus on cucurbit[n]urils. The chapter provides an overview of the development of cucurbit[n]urils and their potential applications. It also addresses the challenge of poor water solubility of cucurbit[n]urils, and discusses the enhancement of water solubility through the development of acyclic CB[n]s. Furthermore, the potential application of these containers as sequestration agents is explored. Chapter 2 describes the synthesis of a novel sulfated acyclic CB[n] receptor (Me4TetM0) and its recognition properties towards a panel of drugs of abuse. The obtained results were compared with two other sulfated acyclic CB[n]s (TetM0 and TriM0). Furthermore, in vivo studies were conducted with TetM0 to assess its efficacy as a sequestration agent for methamphetamine. Chapter 3 presents the synthesis of a series of water insoluble acyclic CB[n]-type receptors and studies their function as solid state sequestrants for organic micropollutants. The results are compared with CB[6] and CB[8]. The time course experiments performed with H4 show a rapid sequestration ability of the five micropollutants studied. Furthermore, under identical conditions, the micropollutant removal efficiency is higher than activated charcoal. Chapter 4 investigates the use of water-insoluble acyclic CB[n]-type receptors for the reversible capture of iodine from the vapor phase. H2 exhibits an iodine capture of 2.2 g g-1, equivalent to 12 iodine atoms per H2 molecule. Following iodine uptake, H2 undergoes partial oxidation, and the uptake of I3- and I5- was confirmed through Raman spectroscopy. Chapter 5 details the synthesis of glycoluril dimer bis(cyclic) ether-based hosts with diverse aromatic side walls. The chapter presents a comparative analysis of dye removal from a solid state and delves into the influence of distinct aromatic walls and various attached substituents.Item High Affinity Host-Guest Pairs Enable In Vitro and In Vivo Sequestration of Drugs of Abuse(2020) Murkli Jr., Steven Louis; Isaacs, Lyle L.I.; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Molecular containers of diverse structure and binding preferences has led to their incorporation in numerous applications such as drug solubilization, drug delivery, and drug sequestration. A detailed understanding of the binding properties of novel molecular containers can both guide future structural refinement and open up new potential applications.Chapter 1 introduces molecular containers and the associated benefits of their use in the pharmacokinetic approach to drug sequestration. Among these containers, CB[n] show the highest promise due to their high affinity and selectivity for their intended drug target while displaying high levels of biocompatibility. Accordingly, innovations to the CB[n] scaffold has led to the development of acyclic CB[n]-type receptors capable of achieving drug reversal in vivo, although further design can yield sequestration agents with higher potency. Chapter 2 provides a thorough investigation of the binding preferences of CB[8] towards a set of biologically relevant drugs. These findings serve as both a blinded experimental dataset for computational chemists to validate their predictive capability on host-guest interactions and to establish a working knowledge of CB[8] binding preferences for future applications. Chapter 3 puts the aforementioned binding preferences of CB[8] to the test versus a panel of drugs of abuse in a continuation of the efforts outlined in Chapter 1. This study is then translated to the successful in vivo sequestration and prevention of phencyclidine (PCP)-induced hyperlocomotion by a water-soluble CB[8] derivative previously studied in the Isaacs group. Chapter 4 presents a new member of the acyclic CB[n]-type receptor class bearing anthracene terminated walls, M3, that by design is capable of increased binding affinity across a large guest library. This increased binding affinity is elucidated versus a comparator host bearing naphthalene walls, M2, that has been previously used as a sequestration agent for Neuromuscular Blocking Agents, (NMBA’s) and is currently the highest potency acyclic CB[n]-type receptor available. Finally, the fluorescent responsiveness of M3 is investigated to create a sensing array capable of distinguishing 22 guests providing basis for future sensing experiments.