Structural Studies of Supramolecular Host-Guest Systems
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STRUCTURAL STUDIES OF SUPRAMOLECULAR HOST-GUEST SYSTEMS A Thesis Submitted to the College of Graduate Studies and Research In Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy In the Department of Chemistry University of Saskatchewan Saskatoon By ABDALLA H. KAROYO Copyright Abdalla Hamisi Karoyo, August 2014. All rights reserved. Permission To Use In presenting this thesis in partial fulfillment of the requirements for a Postgraduate degree from the University of Saskatchewan, I agree that the Libraries of this University may make it freely available for inspection. I further agree that permission for copying of this thesis in any manner, in whole or in part, for scholarly purposes may be granted by Professors L. D. Wilson and P. Hazendonk who supervised my thesis work or, in their absence, by the Head of the Department or the Dean of the College in which my thesis work was done. It is understood that any copying or publication or use of this thesis or part thereof for financial gain shall not be allowed without my written permission. It is also understood that due recognition shall be given to me and to the University of Saskatchewan in any scholarly use which may be made of any material in my thesis. Requests for permission to copy or to make other use of material in this thesis in whole or part should be addressed to: Head of the Department of Chemistry University Of Saskatchewan 110 Science Place Saskatoon, Saskatchewan S7N 5C9 Canada i Acknowledgements ﻬ In The Name of Allah The Most Beneficent The Most Merciful ﻬ I would like to express my sincere thanks to my supervisors Drs. Lee D. Wilson and Paul Hazendonk, to whom am deeply indebted by the support and guidance they accorded me throughout the course of my PhD program. My heartfelt thanks to the Department of Chemistry for the opportunity to do research and further my scientific career. I wish to thank the University of Lethbridge (U of L) for the opportunity to train and work on the solid-state NMR spectrometer; the University of Saskatchewan for the Graduate Teaching Fellowship; and the Natural Sciences and Engineering Research Council (NSERC) for the financial support. I am grateful to members of my PhD advisory committee, Drs. Richard Bowles, Steve Reid, and Oleg Dmitriev for their expert guidance. I wish to thank Drs. Sammynaiken and K. Brown, J. Maley, and K. Thoms (Saskatchewan Structural Sciences Center (SSSC)) for their technical support; Dr. P. Sidhu, Alex Borisov, and T. Montina (U of L) for their support in Solids NMR; Drs. Wajdi Zoghaib (Sultan Qaboos, Oman) and Hashim Ali (Arkansas State, USA) for their words of encouragement. To my colleagues in the Lab; Drs. Mohamed, Rui Guo and Jae Kwon, Dawn Pratt, Louis Poon, Chen Xue, Shagufta Younis, Leila Dehabadi, and Inimfon for their help in the Lab. I wish to thank Mohamed and Regeye, Denis and Catherine for making me feel at home away from home, especially during the early days of my stay in Canada. Lastly, my special thanks go to the most important person in this journey; my wife, Mwanajuma. I never realized how strong a woman she was until I embarked on this journey; her patience, love and encouragement allowed me to finish this journey. ii Dedications This thesis is dedicated to my wife and my sons Hamisi, Faisal, and Fadhil. To my parents; my mam Mwanasha Mwacharo, and my dad Hamisi Karoyo. To my sisters Mwanamisi, Bibi (twin), Mwanaulu, and Mwanasiti; and brothers Baya, Kassim, Dinar, and Juma. Thank you for your love and support. iii Abstract This research work details a systematic study of the structure and function of supramolecular host-guest systems. Host-guest inclusion complexes were formed between β- Cyclodextrin (β-CD) and its copolymers (as hosts), with several types of guest molecules both in aqueous solution and the solid state. The research is divided into two themes; (1) structural characterization and dynamic properties of the inclusion compounds of -CD with various guest systems in aqueous solution and the solid phase, and (2) heterogeneous adsorption and structural studies of β-CD based copolymers with various guest systems in aqueous solutions. The guest systems include alkyl and perfluoroalkyl carboxylates, perfluoroalkyl sulfonate, and p- nitrophenol (PNP) at variable experimental conditions. In the first theme (chapters 2–5), perfluorinated compounds (PFCs), namely; perfluorooctanoic acid (PFOA), perfluorobutyric acid (PFBA), and sodium perfluorooctanoate (SPFO) represent the guest molecules. The host-guest complexes in the solid state were prepared using dissolution and slow cool methods at variable host/guest mole ratios (i.e., 1:1 and 2:1). The complexes were further characterized using 19F/13C DP/MAS and CP/MAS solid-state NMR spectroscopy. The solution state complexes were prepared in D2O for structural characterization using 1H/19F NMR spectroscopy. The NMR studies were complemented using FT-IR, thermal analyses (DSC, and TGA), and powder X-ray diffraction (PXRD). Evidence for the formation of host-guest inclusion compounds (ICs) was provided using CP/MAS solids NMR spectroscopy and complexation-induced chemical shift (CIS) values of 1H/19F nuclei in aqueous solution. The β-CD/PFC ICs displayed variable guest geometry and hydration states as determined by the host- guest stoichiometry and the conformation of the guest. PFOA and SPFO form 1:1 and 2:1 ICs with β-CD, wherein the guest adopts a range of gauche and trans conformations, respectively. iv 1:1 host-guest complexes were concluded for short perfluorocarbon chains (i.e., PFBA) where the gauche conformation of the PFC guest in the bound state was favoured. The phase purity of the β-CD/PFC ICs was assessed using DSC and 19F DP/MAS NMR spectroscopy at ambient and variable temperature (VT) conditions. The complexes prepared by the slow cool method were found to be of relatively high phase purity when compared to complexes prepared by the dissolution method. However, a simple modified dissolution method was developed to afford complexes with greater phase purity. The phase purity of the complexes was further assessed using deconvolution analyses of the 19F DP/MAS NMR resonance line 1 13 19 shapes. H/ C/ F NMR relaxation (T1/T2/T1ρ) data of the phase pure β-CD/PFC ICs in the solid state revealed variable host and guest dynamics that were governed by dipolar coupling, H- bonding, and combinations of host-guest motional dynamics that involve peripheral and hydrate water within the cavity of β-CD. Coupling constants of the simulated 19F spectra and deconvolution analyses of selected 19F nuclei were used to supplement the 19F NMR relaxation results. In general, two types of motional dynamics of the guest were concluded; (i) 120° rotational jumps of the fluoromethyl (CF3) group at the termini of the PFC chain, and (ii) axial (libration) motion of the entire PFC chain. The rotational and axial dynamics of the guest in the complexes differ in their distribution and magnitude, in accordance with the host-guest stoichiometry and the geometry of the guest within the host. In the second theme (chapters 6–8), β-CD based copolymers were used as host materials. The structural characterization of a soluble poly-CD material (known as HDI-1) revealed that the solution behaviour of such polymeric hosts are sensitive to the presence of guest compounds such as p-nitrophenol (PNP) (i.e. chemo-responsive), as well as temperature variations (i.e. thermo-responsive). The host-guest chemistry of the soluble poly-CD material, as studied by 2-D v solution NMR and induced circular dichroism (ICD) spectroscopy, indicates that PNP was bound within the cavity sites of β-CD and the interstitial domains of the copolymer (cf. Scheme 1.6 and chapter 6). The observed responsive nature of such polymeric host materials to temperature variation and chemical potential resembles behaviour characteristic of ‘smart materials’. Herein, ‘smart materials’ refer to systems which are responsive to external stimuli (e.g. temperature and chemical). The adsorption properties of the soluble (HDI-1) and insoluble (HDI-3 and -6) poly-CD adsorbents with octyl and perfluorooctyl carboxylate and sulfonate anions were estimated using the Sips and BET models. The hydrocarbon (HC) and fluorocarbon (FC) anions form monolayer and multilayer structures at the surface of the polymeric adsorbents, respectively. The formation of layered structures was controlled by the relative hydrophobicity of the alkyl/perfluoroalkyl chains and their mutual miscibility with the adsorbent surface. Other factors include the inductive effects of the alkyl/perfluoroalkyl head groups and their interactions with aqueous solvent or dipolar domains of the adsorbent surface. The adsorbed species at the liquid-solid interface were characterized using FT-IR spectroscopy, thermal analyses, and contact angle. vi TABLE OF CONTENTS Permission To Use …..…..………………….…………………………………….i Acknowledgements …..……………………………………………………………ii Dedications ……………………………………………………………….iii Abstract …..………………………………………………………...iv-vi Table of Contents .…....……………….….…………………………………....vii Table of Contents ………………………………………….………………viii-xvi Appendices ………………...……………………………………...xvii-xviii List of Tables …..…..…………..…….………………………...………xix-xx List of Schemes …...…………..………..………………………………xxi-xxiv List of Figures ….……………..……………………………………xxv-xxxiii List of Abbreviations …...…………..……..……………………….……..xxxiv-xxxv vii Chapter 1…………………………………………………………………………………………... 1 1. Introduction………………………………………………………………………………... 1 1.1. Introduction