DOCSLIB.ORG

Resorcinarene-Based Cavitands: from Structural Design and Synthesis to Separations Applications

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Resorcinarene-Based Cavitands: from Structural Design and Synthesis to Separations Applications Brigham Young University BYU ScholarsArchive Theses and Dissertations 2013-03-18 Resorcinarene-Based Cavitands: From Structural Design and Synthesis to Separations Applications Na Li Brigham Young University - Provo Follow this and additional works at: https://scholarsarchive.byu.edu/etd Part of the Biochemistry Commons, and the Chemistry Commons BYU ScholarsArchive Citation Li, Na, "Resorcinarene-Based Cavitands: From Structural Design and Synthesis to Separations Applications" (2013). Theses and Dissertations. 3520. https://scholarsarchive.byu.edu/etd/3520 This Dissertation is brought to you for free and open access by BYU ScholarsArchive. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of BYU ScholarsArchive. For more information, please contact [email protected], [email protected]. Resorcinarene-Based Cavitands: From Structural Design and Synthesis to Separations Applications Na Li A dissertation submitted to the faculty of Brigham Young University in partial fulfillment of the requirements for the degree of Doctor of Philosophy John D. Lamb, Chair Roger G. Harrison Matthew R. Linford David V. Dearden Richard K. Watt Department of Chemistry and Biochemistry Brigham Young University March 2013 Copyright © 2013 Na Li All Rights Reserved ABSTRACT Resorcinarene-Based Cavitands: From Structural Design and Synthesis to Separations Applications Na Li Department of Chemistry and Biochemistry, BYU Doctor of Philosophy Resorcinarenes are cyclic tetramers that are synthesized by the condensation of resorcinol and various aldehydes. The upper and lower rims can be modified with substituents that provide specific selectivity and other chemical features. In this work, resorcinarene-based macrocyclic ligands with specific selectivities have been designed, synthesized and applied to chiral amine discrimination and transition metal ion separations. These resorcinarenes fall into two categories. In the first type, the upper rims of resorcinarenes were modified with amino acid groups, including chiral alanine groups. The lower rims were modified with –CH3, or –C11H23 groups. The structures were studied by nuclear magnetic resonance (NMR), mass spectrometry (MS), dynamic light scattering (DLS), and sustained off-resonance irradiation collision induced dissociation (SORI-CID) techniques in Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The binding strength between the resorcinarenes with amines was studied by 1H NMR titration. Among these new resorcinarenes, the chiral alanine undecyl resorcinarenes acid (AUA) showed chiral discrimination among chiral secondary amines. The AUA ligands were adsorbed onto 55% cross-linked styrene-divinylbenzene resin and used as cation-exchangers in ion chromatography (IC) for transition metal ion separations. The AUA IC column showed selectivity for Cu2+ when no chelating eluent was used in the eluent, a selectivity which was not observed with a commercial column containing standard cation-exchangers. Six metal ions (Cu2+, Mn2+, Co2+, Ni2+, Cd2+, and Zn2+) were separated on the AUA column within a reasonable time with a simple oxalic acid gradient eluent. The second type of resorcinarene-based ligand, cyclenbowl, contains four cyclen units on the upper rim and four –C11H23 chains on the lower rim. The column packed with cyclenbowl adsorbed onto polystyrene showed selectivity for Cu2+ over five other transition metal ions including Mn2+, Co2+, Ni2+, Cd2+, and Zn2+ ions. The preconcentration of Cu2+ at the parts per billion level from a high concentration matrix of Mn2+, Co2+, Ni2+, Cd2+, and Zn2+ ions 2+ was achieved using HNO3 eluent. Recovery of Cu was greater than 98%. Furthermore, the other five transition metal ions were well separated on the cyclenbowl column with an oxalic acid eluent gradient. Keywords: resorcinarene, chiral recognition, ion chromatography, selectivity, transition metal ions, preconcentration, macrocyclic ligands, separations ACKNOWLEDGEMENTS I have been supported and inspired by my family, friends, supervisor Dr. John D. Lamb, and my committee members during my Ph. D. study. When looking back the way that I have passed, I have enormous appreciation for those individuals and Brigham Young University. The great educational opportunity that BYU offered me not only taught me knowledge, but also taught me love and faith. The study and research experience in a different culture not only increased my professional knowledge, but also opened my eyes, inspired my thoughts and made me reflect on the values that I believed before. This unique experience at BYU will benefit my whole life. While working with Dr. Lamb, I have appreciated his mentorship and the research opportunity that he provided me. His keen insights always enlightened me. Every experimental result and every paper that I have published were finished under his zealous help and instruction. I would like to thank Dr. Roger Harrison for the valuable discussions in my synthesis and NMR work. He was always patient to me and willing to give me suggestions both in work and life. I also would like to express my gratitude to my Ph.D. committee members, Dr. David V. Dearden, Dr. Richard K. Watt, and Dr. Matthew R. Linford for their good advice and guidance through my research. Their advice in my yearly progress report always gave me inspiration in my research. Finally, I would like to give my special thanks to my dear sister Qing who accompanied me through all the ups and downs in my life. I dedicate this book to my mother Aiqin Gao and father Senlin Li for their support, sacrifice, understanding, and love throughout my life. TABLE OF CONTENTS ABSTRACT .................................................................................................................................... ii ACKNOWLEDGEMENTS ........................................................................................................... iii TABLE OF CONTENTS ............................................................................................................... iv Chapter 1 Ion Chromatography and Membrane Separations Using Macrocyclic Ligands ............ 1 1. Introduction ............................................................................................................................. 2 2. Selective binding by macrocyclic ligands ............................................................................... 3 2.1 Structures of macrocycles used in ion chromatography and membrane separations ......... 4 2.2 Macrocyclic ligand characteristics which influence selectivity ......................................... 6 2.2.1 Size-fit and conformational changes ........................................................................... 6 2.2.2 Donor type, number, and position ............................................................................. 11 2.2.3 Substitution effects on complexation selectivity ....................................................... 14 2.3 Ion effect on macrocycle selectivity ................................................................................ 15 2.4 Solvent ............................................................................................................................. 16 3. Ion chromatography (IC) ....................................................................................................... 19 3.1 Principles of suppressed IC .............................................................................................. 19 3.2 New perspectives of IC .................................................................................................... 23 4. Application of macrocycles to ion chromatography ............................................................. 25 iv 4.1 Macrocyclic ligands in the stationary phase .................................................................... 26 4.1.1 Crown ethers .............................................................................................................. 26 4.1.2 Crown ethers in the mobile phase ............................................................................. 32 4.1.3 Crown ethers in detection systems ............................................................................ 36 4.2 Cryptands in ion chromatography .................................................................................... 36 4.3 Calixarenes in ion chromatography ................................................................................. 43 4.4 Cyclodextrins ................................................................................................................... 45 5. Liquid membranes ................................................................................................................. 49 5.1 Facilitated transport mechanism and membrane types .................................................... 49 5.2 Macrocyclic carriers in liquid membranes ....................................................................... 52 6. Conclusions ........................................................................................................................... 64 Chapter 2 Application of Resorcinarene Derivatives in Chemical Separations ........................... 77 1. Introduction ........................................................................................................................... 77 2. High Performance Liquid Chromatography (HPLC) ............................................................ 82 3. Gas Chromatography
Load more

Recommended publications
  • Final Drafttetrahedron 2014 70 1111.Pdf
    This is an electronic reprint of the original article. This reprint may differ from the original in pagination and typographic detail. Author(s): Tero, Tiia-Riikka; Nissinen, Maija Title: A perspective to resorcinarene crowns Year: 2014 Version: Please cite the original version: Tero, T.-R., & Nissinen, M. (2014). A perspective to resorcinarene crowns. Tetrahedron, 70(6), 1111-1123. https://doi.org/10.1016/j.tet.2013.12.057 All material supplied via JYX is protected by copyright and other intellectual property rights, and duplication or sale of all or part of any of the repository collections is not permitted, except that material may be duplicated by you for your research use or educational purposes in electronic or print form. You must obtain permission for any other use. Electronic or print copies may not be offered, whether for sale or otherwise to anyone who is not an authorised user. 1 A Perspective to Resorcinarene Crowns Tiia-Riikka Teroa and Maija Nissinena* a Nanoscience Center, Department of Chemistry, University of Jyväskylä, P.O. Box 35, FIN-40014 JYU, Finland * Corresponding author. Tel.: +358 50 4280804; e-mail: [email protected] Abstract In this report, we have summarized different synthesis methods of the resorcinarene crowns, discussed their structural and complexation properties together with the possible application aspects. Keywords Resorcinarene, Resorcinarene crown, Calix crown, Complexation, Receptor 1. Introduction In supramolecular chemistry crown ethers are one of the oldest and most explored but still today a very intriguing class of compounds. They have a remarkable ability to act as receptors or ionophores for a variety of guest species depending on their chemical and structural properties, which can be modified just by changing the number of oxygen donors, i.e.
    [Show full text]
  • Molecular Encapsulation in Kinetically Trapped, Hydrogen-Bonded Pyrogallolarene Hexamers
    University of Denver Digital Commons @ DU Electronic Theses and Dissertations Graduate Studies 6-1-2014 Molecular Encapsulation in Kinetically Trapped, Hydrogen-Bonded Pyrogallolarene Hexamers Jennifer Christine Chapin Lake University of Denver Follow this and additional works at: https://digitalcommons.du.edu/etd Part of the Organic Chemistry Commons Recommended Citation Chapin Lake, Jennifer Christine, "Molecular Encapsulation in Kinetically Trapped, Hydrogen-Bonded Pyrogallolarene Hexamers" (2014). Electronic Theses and Dissertations. 120. https://digitalcommons.du.edu/etd/120 This Dissertation is brought to you for free and open access by the Graduate Studies at Digital Commons @ DU. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Digital Commons @ DU. For more information, please contact [email protected],[email protected]. MOLECULAR ENCAPSULATION IN KINETICALLY TRAPPED, HYDROGEN-BONDED PYROGALLOLARENE HEXAMERS __________ A Dissertation Presented to the Faculty of Natural Sciences and Mathematics University of Denver __________ In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy __________ by Jennifer Christine Chapin Lake June 2014 Advisor: Byron W. Purse ©Copyright by Jennifer Christine Chapin Lake 2014 All Rights Reserved Author: Jennifer Christine Chapin Lake Title: MOLECULAR ENCAPSULATION IN KINETICALLY TRAPPED, HYDROGEN-BONDED PYROGALLOLARENE HEXAMERS Advisor: Byron W. Purse Degree Date: June 2014 Abstract Pyrogallolarene and resorcinarene hexamers are hydrogen-bonded capsules that self-assemble in the solid state and can be studied in gaseous and solution phases. Guest loading within pyrogallolarene hexamers in solution has primarily been comprised of solvent molecules with some tertiary amines. A novel solvent-free method for loading guests into the interior of the hexamer has been shown to be effective for encapsulation of a variety of molecules.
    [Show full text]
  • Novel Hydrogen-Bonded Supramolecular Assemblies From
    Novel Hydrogen-bonded Supramolecular Assemblies from Resorcinarene-derived Macrocycles & Elucidation of the Prerequisites for Terpene Cyclizations inside the Resorcinarene Capsule Inauguraldissertation zur Erlangung der Würde eines Doktors der Philosophie vorgelegt der Philosophisch-Naturwissenschaftlichen Fakultät der Universität Basel von Severin Merget 2021 Originaldokument gespeichert auf dem Dokumentenserver der Universität Basel edoc.unibas.ch Genehmigt von der Philosophisch-Naturwissenschaftlichen Fakultät auf Antrag von Prof. Dr. Konrad Tiefenbacher, Prof. Dr. Marcel Mayor und Prof. Dr. Alessandro Scarso. Basel, den 30. 03. 2021 Prof. Dr. Marcel Mayor (Dekan) ii Die vorliegende Arbeit wurde von Mai 2017 bis April 2021 an der Universität Basel unter Leitung von Prof. Dr. Konrad Tiefenbacher angefertigt. Teile dieser Arbeit wurden veröffentlicht: (1) Merget, S., Catti, L., Piccini, G.M., Tiefenbacher, K. Requirements for Terpene Cyclizations inside the Supramolecular Resorcinarene Capsule: Bound Water and its Protonation Determine the Catalytic Activity, J. Am. Chem. Soc. 2020, 142, 4400−4410 (2) Merget, S., Catti, L., Zev, S., Major, D. T., Trapp, N., Tiefenbacher, K., Concentration- dependent Self-assembly of an Unusually Large Hexameric Hydrogen-bonded Molecular Cage, Chem. Eur. J. 2021, 27, 4447−4453. iii Acknowledgements First and foremost, I would like to thank my supervisor Prof. Dr. Konrad Tiefenbacher for giving me the opportunity to work in his group on a very interesting subject. I am truly thankful for his unwavering support, his assistance and motivation also during the more difficult times of the project. For extremely valuable discussions and always worthwhile scientific input I am also deeply grateful to my second supervisor Prof. Dr. Marcel Mayor. I am happy to acknowledge my colleagues from the Tiefenbacher research group for a pleasant working atmosphere and never a dull moment in the lab.
    [Show full text]
  • Understanding the Self-Assembly Process and Behavior of Metal- Seamed Pyrogallol[4]Arene Nanocapsules
    UNDERSTANDING THE SELF-ASSEMBLY PROCESS AND BEHAVIOR OF METAL-SEAMED PYROGALLOL[4]ARENE NANOCAPSULES A Dissertation Presented to The Faculty of the Graduate School University of Missouri-Columbia In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy By ANDREW V. MOSSINE Dr. Jerry L. Atwood, Dissertation Supervisor MAY 2014 The undersigned, appointed by the dean of the Graduate School, have examined the dissertation entitled UNDERSTANDING THE SELF-ASSEMBLY PROCESS AND BEHAVIOR OF METAL-SEAMED PYROGALLOL[4]ARENE NANOCAPSULES Presented by Andrew V. Mossine A candidate for the degree of doctor of philosophy of Chemistry, And hereby certify that, in their opinion, it is worthy of acceptance Professor Jerry L. Atwood (CHAIR) Professor Stephen Lombardo (OUTSIDE MEMBER) Professor Carol A. Deakyne (MEMBER) Professor Silvia Jurisson (MEMBER) Professor Timothy Glass (MEMBER) ACKNOWLEDGMENTS First of all, I would like to thank Dr. Jerry Atwood for giving me the opportunity to be a part of his group, not only as a graduate student, but also as a fresh and untested undergraduate more than five years ago. This early research experience certainly solidified my resolve to attend graduate school, but it also showed me what a joy research can be. Dr. Atwood’s valuable advice, faith in my abilities, and his encouragement to think independently has allowed me to not only grow as a researcher but also as a person. I am also extremely grateful to Dr. Silvia Jurisson, both for the opportunity to collaborate with her group, but also for giving me the chance to take part in the NIBIB training grant program, which allowed me to broaden my research experience by traveling to Washington D.C.
    [Show full text]
  • Synthetic and Structural Studies of Calix[4]Pyrogallolarenes Towards
    Synthetic and Structural Studies of Calix[4]pyrogallolarenes Towards Biological Applications Neil Bowley A thesis submitted in partial fulfilment of the Requirements of Nottingham Trent University For the degree of Doctor of Philosophy September 2008 Acknowledgements Firstly I wish to thank my supervisor Dr. Gareth Cave for the help and advice he has provided during the three years of my Ph.D. Thanks are due to the people who I have shared a lab with over the three years of my Ph.D. The numerous project students and fellow researchers that have passed through the synthetic chemistry lab ensured my time in the lab has been interesting and sometimes entertaining! Thank you to Erasmus student Alex Massard for investigations into the solvent free preparation of calixarenes and acetals, and to M.Chem. project student Carl Rogers for synthesising bulk quantities of terpyridines. Thanks to M.Sc. students Winston Vetharoy and Kirsten Bostock under the supervision of Dr. Stéphanie. McArdle for performing cellular toxicity studies on the calixarenes. Thank you to Dr. Patrick Huddlestone, for invaluable practical advice on a variety of organic chemistry problems. Thank you to Prof. John Wallis for proofreading this thesis and many valuable contributions to my project throughout my time as a postgraduate student. Thanks to Andrew Brooks whose friendship has been a constant support throughout my time at NTU. I couldn’t have done it without you! Thank you is simply not enough to Hannah and my Parents whose unswerving support has enabled me to achieve what I could only dream of. 2 Contents Acknowledgements ...............................................................................................................................
    [Show full text]
  • Calix[4]Resorcinarenes-DMSO Inclusion Complexes
    Jordan Journal of Chemistry Vol. 9 No.3, 2014, pp. 170-186 JJC Green Synthesis, Crystal Structure and Bioactivity of C-(p- substituted phenyl)calix[4]resorcinarenes-DMSO Inclusion Complexes Solhe F. Alshahateeta, Salah A. Al-Trawneha, Wael A. Al-Zereinib, Saad S. Al-Sarhana aDepartment of Chemistry, Mutah University, P.O. BOX 7, Mutah 61710, Alkarak, Jordan bDepartment of Biological Sciences, Mutah University, P.O. BOX 7, Mutah 61710, Alkarak, Jordan Received on April 24, 2014 Accepted on Jun. 26, 2014 Abstract Green synthesis of calix[4]resorcinarene hosts with p-substituted phenyl group at their methine carbons was achieved. Fluorine, chlorine and bromine atoms, as well as methoxy group, were selected as substituents at the para position of the benzaldehyde which was condensed with resorcinol in presence of solid p-toluenesulfonic acid. The solid state structures of the newly prepared C-(p-fluorophenyl)calix[4]resorcinarene-DMSO and C-(p-chlorophenyl)- calix[4]resorcinarene-DMSO inclusion complexes were determined by single-crystal X-ray diffraction and found to form different structural conformations; chair (C2h) and boat (C2v), respectively. In addition, both crystal structures adopted several intermolecular noncovalent supramolecular interactions which were carefully investigated and presented in terms of crystal engineering and supramolecular chemistry. The synthesized C-(p-substitutedphenyl)calix[4]- resorcinarene hosts inhibited the growth of Gram-positive bacteria with the C-(p-bromophenyl)- calix[4]resorcinarene derivative being the most potent agent (MIC=15.6-125 μg/ml). Keywords: C-(p-substituted phenyl)calix[4]resorcinarenes-DMSO inclusion complex; Boat conformation; Chair conformation; Crystal structure; Bioactivity; Non-covalent interactions.
    [Show full text]
  • Investigation of Resorcin[4]Arenes Upper Rim Functionalization
    Investigation of Resorcin[4]arenes Upper Rim Functionalization by Cristina - Adriana Macarov A Doctoral Thesis Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy at The University of East Anglia May 2018 "This copy of the thesis has been supplied on condition that anyone who consults it is understood to recognise that its copyright rests with the author and that use of any information derived there from must be in accordance with current UK Copyright Law. In addition, any quotation or extract must include full attribution.” © Cristina A. Macarov (2018) Pentru familia mea extraordinara. Va iubesc din tot sufletul. [For my extraordinary family. I love you with all my soul.] i Preface The research in this thesis is, to the best of my knowledge, original and my own work except where due reference has been made. Neither the thesis nor the original work contained therein has been submitted to this or any other institution for a degree. Cristina-Adriana Macarov May 2018 ii Acknowledgements I am happy, grateful and lucky because I am always supported by my amazing family, so a huge thank you. I thank my supervisor Prof. Phil Page for the incredible opportunity, for funding and for always being there to guide me. Without your support I wouldn’t be here. I am grateful to have met Pat, Phil’s wife, I wish you much health and love, you’ve been a ray of light and you are my favourite person to hug alongside Fran and the cats. Dr. Yohan, thank you for the kicks in my rear and always saving the day, and the NMR machine… {Bat Chan}, and of course, thank you for the best pancakes that I’ve ever eaten.
    [Show full text]
  • Supramolecular Chemistry Supramolecular Chemistry
    Supramolecular Chemistry Sources: -e-source - K.Ariga, T.Kunitake - Supramolecular Chemistry - Fundamentals and Applications - Advanced Textbook -Research papers 1 The Nobel Prize awarded to Jean-Marie Lehn, Donald J Cram, and Charles J Pedersen in 1987, for ‘development and use of molecules with structure-specific interactions of high selectivity’ and established supramolecular chemistry / as a discipline which is now being explored in various areas such as drug development sensors catalysis nanoscience molecular devices etc. 2 Supramolecular chemistry as defined by Lehn ‘chemistry beyond the molecule’…focuses on the development of functional complex architectures through non-covalent interactions. The year 2017, marked the fiftieth anniversary of the serendipitous discovery of crown ethers. Since then, the field is growing, and due to the efforts of various researchers now it is possible to have some control over the arrangement of things on a small scale. 3 4 5 Supramolecular chemistry has been defined by phrases such as ‘chemistry beyond the molecule’, ‘chemistry of molecular assemblies and of the intermolecular bond’, and ‘non-molecular chemistry’. The main objective of supramolecular chemistry is to design and develop novel functional systems by joining multiple chemical components through non-covalent interactions 6 7 Supramolecular chemistry focuses on two partly cover areas, ‘supramolecules’ and ‘molecular assemblies’. 8 …A supramolecule is a well-defined distinct system generated through interactions between a molecule (receptor or host) having convergent binding sites such as donor atoms, sites for formation of hydrogen bonds and sizable cavity, and another molecule (analyte or guest) having divergent binding sites such as hydrogen bond acceptor atoms. 9 The receptor can be a macromolecule or aggregates and the analyte may be ions (cations and anions) or molecules.
    [Show full text]
  • Preparation and Properties of Self-Assembled Resorcinarene Monolayers
    Department of Chemistry Preparation and Properties of Self-Assembled Resorcinarene Monolayers Jade Kristin Pettersen This thesis is presented for the Degree of Doctor of Philosophy of Curtin University of Technology January 2010 Declaration To the best of my knowledge and belief this thesis contains no material previously published by any other person except where due acknowledgment has been made. This thesis contains no material which has been accepted for the award of any other degree or diploma in any university. Signature: …………………………………………. Date: ………………………... i Acknowledgments I would like to acknowledge the following people for their generous contributions to this project: Professor Mark Ogden and Associate Professor Mauro Mocerino; for their endless optimism, patience, and advice over the course of this project. It would not have been completed without their encouragement, for which I am extremely grateful. Dr Matthew McIldowie, who regularly dispensed immensely helpful advice, and for always being willing to act as a sounding board. Dr Thomas Becker for his invaluable support in obtaining and interpreting my AFM and STM data, especially as he generously sacrificed his leave to help me submit on time. Dr Andrew Ross, and Dr Peter Eadington, along with their group at CSIRO. Peter Chapman, Joyce Wong, Robert Herman, and Allan Oliveira for their assistance, advice, and humour that went far beyond their job descriptions. I would also like to thank Dr David Brown, Professor Bill van Bronswijk, Dr Franca Jones and Dr Matt Myers for their contributions. Finally I would like to acknowledge the financial contributions to this project from the Commonwealth Scientific and Industrial Research Organisation (CSIRO) Wealth from Oceans Flagship, Western Australian Energy Research Alliance (WA:ERA), and Curtin University of Technology.
    [Show full text]
  • Glutamic Acid Resorcinarene-Based Molecules and Their Application in Developing New Stationary Phases in Ion Chromatography Tayyebeh Panahi Brigham Young University
    Brigham Young University BYU ScholarsArchive All Theses and Dissertations 2016-06-01 Glutamic Acid Resorcinarene-based Molecules and Their Application in Developing New Stationary Phases in Ion Chromatography Tayyebeh Panahi Brigham Young University Follow this and additional works at: https://scholarsarchive.byu.edu/etd Part of the Chemistry Commons BYU ScholarsArchive Citation Panahi, Tayyebeh, "Glutamic Acid Resorcinarene-based Molecules and Their Application in Developing New Stationary Phases in Ion Chromatography" (2016). All Theses and Dissertations. 6436. https://scholarsarchive.byu.edu/etd/6436 This Dissertation is brought to you for free and open access by BYU ScholarsArchive. It has been accepted for inclusion in All Theses and Dissertations by an authorized administrator of BYU ScholarsArchive. For more information, please contact [email protected], [email protected]. Glutamic Acid Resorcinarene-Based Molecules and Their Application in Developing New Stationary Phases in Ion Chromatography Tayyebeh Panahi A dissertation submitted to the faculty of Brigham Young University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Roger G. Harrison, Chair John D. Lamb David V. Dearden Richard K. Watt Matt A. Peterson Department of Chemistry and Biochemistry Brigham Young University June 2016 Copyright © 2016 Tayyebeh Panahi All Rights Reserved ABSTRACT Glutamic Acid Resorcinarene-Based Molecules and Their Application in Developing New Stationary Phases in Ion Chromatography Tayyebeh Panahi Department of Chemistry and Biochemistry, BYU Doctor of Philosophy Resorcinarenes can be functionalized at their upper and lower rims. In this work, the upper rim of a resorcinarene was functionalized with glutamic acids and the lower rim was functionalized with either methyl or undecyl alkyl groups.
    [Show full text]
  • The Synthesis and Structure of C4 Symmetric Resorcinarenes
    Department of Applied Chemistry The Synthesis and Structure of C4 Symmetric Resorcinarenes Matthew J McIldowie This thesis is presented for the Degree of Doctor of Philosophy of Curtin University of Technology October 2007 Declaration To the best of my knowledge and belief this thesis contains no material previously published by any other person except where due acknowledgment has been made. This thesis contains no material which has been accepted for the award of any other degree or diploma in any university. Signature: …………………………………………. Date: ………………………... Contents Abstract iii Acknowledgements iv Preface v 1.0 A brief review of Cn Symmetric calixarenes and resorcinarenes. 1 1.1 The C1 dissymmetric 7 1.1.1 Calixarene based 7 1.1.2 Resorcinarene based 13 1.2 The C2 dissymmetric 14 1.2.1 Calixarene based 14 1.2.2 Resorcinarene based 19 1.3 The C4 dissymmetric 20 1.3.1 Calixarene based 20 1.3.2 Resorcinarene based 22 1.4 Outlook 33 2.0 Synthesis and characterisation of C4 dissymmetric resorcinarenes 34 2.1 Mechanism of resorcinarene formation 39 2.2 Alkylation of the octahydroxy resorcinarenes 48 2.3 Physical and spectroscopic properties of the C4 resorcinarenes 49 2.4 Chirality of the resorcinarenes 51 2.5 Structure of the resorcinarenes 52 2.6 Functionalisation of the resorcinarene phenols 55 2.6.1 Formation and structure of the resorcinarene esters 56 2.6.2 Alkylation of the C4 dissymmetric resorcinarenes 58 2.7 Synthesis of C4 dissymmetric resorcinarenes using other aromatics 62 2.8 Experimental 65 i 3.0 Resolution of C4 dissymmetric resorcinarenes by formation of their diastereomeric camphorsulfonates 82 3.1 Synthesis of the camphorsulfonyl derivatives 87 3.2 Resolution of the tetracamphorsulfonate diastereomers 87 3.3 Physical and spectroscopic properties of the tetra- camphorsulfonates 88 3.3.1 Crystallinity and solubility 88 3.3.2 N.m.r.
    [Show full text]
  • Simple Calix[N]Arene and Calix[4]Resorcinarene As Drug
    Journal of Nanomedicine Research Simple Calix[n]arenes and Calix[4]resorcinarenes as Drug Solubilizing Agents Abstract Review Article Many drug molecules have low solubility in aqueous media and, hence, poor Volume 2 Issue 3 - 2015 bioavailability. The formation of a host-guest complex with some other compound which has a good solubility profile can facilitate solubilization of hydrophobic drugs. Complex formation relies upon the formation of non-covalent interactions Clare Hoskins and Anthony DM Curtis* between the host molecule and the drug guest. The use of calix[n]arenes, a well- Institute of Science and Technology in Medicine, Keele characterized class of cyclic oligomers, has been investigated for their ability University, UK to form complexes with a variety of ionic and molecular species. This review highlights those studies which have demonstrated the potential of calix[n]arenes *Corresponding author: Anthony D.M. Curtis, Institute of Science and Technology in Medicine, Keele University, as host molecules in novel drug delivery systems. Keele, Staffordshire, UK, Tel: +441782 733040; Email: Keywords: Calix[n]arene; Calix[4]resorcinarene; Drug solubilization Received: March 28, 2015 | Published: April 20, 2015 Introduction which the phenolic residues are bridged by sulfur atoms and calix[4]pyrroles, for example, have also been studied but not to The administration of drug molecules to the body requires them the same extent as the parent compounds. This review will focus to be formulated into a suitable dosage form that may be dictated on the use of calix[n]arenes and calix[4]resorcinarenes bearing by the fundamental properties of the drug or the site of the drug functionalities on the upper and lower rims in facilitating the target and disease being treated.
    [Show full text]