Table Of ContentMacrocyclic Receptors
for Environmental and
Biosensing Applications
Satish Kumar
Department of Chemistry
St. Stephen’s College, University Enclave, Delhi, India
Priya Ranjan Sahoo
Institute of Multidisciplinary Research for Advanced Materials
Tohoku University, Sendai, Miyagi, Japan
Violet Rajeshwari Macwan
Department of Chemistry
St. Stephen’s College, University Enclave, Delhi, India
Jaspreet Kaur
Department of Chemistry
St. Stephen’s College, University Enclave, North Campus
Delhi, India
Mukesh
Department of Chemistry, Keshav Mahavidyalaya
University of Delhi, Delhi, India
Rachana Sahney
Amity Institute of Biotechnology
Amity University, AUUP, Noida, Uttar Pradesh, India
Cover credit: Priya Ranjan Sahoo
First edition published 2022
by CRC Press
6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742
and by CRC Press
4 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN
© 2022 Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, LLC
Reasonable efforts have been made to publish reliable data and information, but the author and
publisher cannot assume responsibility for the validity of all materials or the consequences of
their use. The authors and publishers have attempted to trace the copyright holders of all material
reproduced in this publication and apologize to copyright holders if permission to publish in this
form has not been obtained. If any copyright material has not been acknowledged please write and
let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted,
reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other
means, now known or hereafter invented, including photocopying, microfilming, and
recording, or in any information storage or retrieval system, without written permission
from the publishers.
For permission to photocopy or use material electronically from this work, access www.copyright.
com or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers,
MA 01923, 978-750-8400. For works that are not available on CCC please contact
[email protected]
Trademark notice: Product or corporate names may be trademarks or registered trademarks and are
used only for identification and explanation without intent to infringe.
Library of Congress Cataloging‑in‑Publication Data (applied for)
ISBN: 978-0-367-85632-8 (hbk)
ISBN: 978-1-003-01403-4 (ebk)
DOI: 10.1201/9781003014034
Typeset in Times New Roman
by Shubham Creation
Preface
Metals, anions and gases are ubiquitous and are involved in almost every biological
and environmental process. However, any increase in their concentration beyond
the permissible limits leads to detrimental effects on both human health and its
environment. Human advancements and indiscriminate industrial and farming
practices during the last century have largely contributed to environmental
pollution and also have increased the risk of diseases in humans, plants and
animals. Consequently, the design and synthesis of highly sensitive and selective
receptors for the detection and estimation of different metal ions, anions and
gases owing to their biological, analytical and environmental applications has
become of utmost importance. Based on the inspiration and learning from the
biological world, scientists and engineers have actively utilized the principles of
molecular recognition from the past few decades to augment the sensitivity as
well as selectivity of various available sensing techniques through the usage of
macrocyclic receptors. These have vast potential to differentiate between various
analytes at very low concentration due to their variable cavity dimensions. The
recent developments in supramolecular chemistry, a plethora of macrocyclic
receptors have been reported in the literature and the field has received considerable
attention in the past few decades. The development of newer macrocyclic receptors
has strengthened host-guest bonhomie in the last decade. Apart from conventional
macrocycles, tailoring of new hybridized receptors such as “multifarenes” from
multiple building blocks has led to its usage in nitroaromatics detection, metal
ion sensing. Very recently, prismarenes were added into the macrocyclic field in
the year 2020. Fortunately, new kinds of arene receptors such as saucer[n]arenes,
pagoda[n]arenes, helicarenes, etc. are being discovered constantly. The discovery
of new receptors is bringing new avenues to fine-tune their chemistry as well as
biosensing techniques.
The book also outlines recent development in macrocyclic chemistry covering
areas like self-assembly, stimuli-responsive systems, molecular motors, switches,
biosensing, and medicine. Molecular switches and motors based on macrocyclic
iv Macrocyclic Receptors for Environmental and Biosensing Applications
receptors are the focus of current scientific efforts to integrate them into larger
assemblies of molecular machines to generate macroscopic motions. The stimuli-
responsive systems, which drive the amazing concepts like molecular switches
and motors based on well-known supramolecules such as calixarenes, crown
ethers, cyclodextrins, pillar[n]arenes have been discussed in detail in the book.
Details of the design and basic mechanism behind the development of responsive
molecular switches and motors have also been discussed. Moreover, the rapidly
developing field of nanomaterials further provides strong motivation to the
development of stimuli-responsive materials based on macrocyclic chemistry due
to their directional and preorganized nature. Stimuli-responsive systems with the
macrocyclic unit at the core have also been discussed as a function of stimuli like
light, heat, pH, metal ion, solvent polarity, redox, and chemical reaction. The book
attempts to provide the theory behind the relevance of supramolecular chemistry
in biology that provides a basis for the development of macrocyclic responsive
systems with utility in areas like enzyme mimic, drug delivery, and environment.
The main purpose of this book is to give an idea about the discovery as well
as biosensing perspectives of both recent and conventional macrocyclic receptors.
We have introduced various kinds of macrocyclic receptors and their historical
development.
Authors hope that the reader will find the book valuable and stimulating
in the emerging area of macrocyclic chemistry, stimuli-responsive materials,
switches molecular motors, chemical biology, and organic chemistry. We have
also discussed the applications of different macrocycles in the recognition of
various analytes.
Satish Kumar
Priya Ranjan Sahoo
Violet Rajeshwari Macwan
Jaspreet Kaur
Mukesh
Rachana Sahney
Contents
Preface iii
Chapter 1 Macrocyclic Receptors Synthesis, History, Binding
Mechanism: An Update on Current Status 1
Introduction 1
Macrocyclic Receptors and Types 2
Crown Ethers 2
Synthesis of Crown Ether 3
Binding Mode of Crown Ether 7
Cryptands 7
Synthesis of Cryptands 8
Cyclodextrins 9
Synthesis of Cyclodextrins 10
Calixarenes 12
Synthesis of Calixarenes 12
Resorcinarenes 16
Synthesis of Resorcinarenes 16
Multifarenes 20
Calixpyrroles 20
Synthesis of Calixpyrroles 21
Synthesis of N-confused Calix[4]pyrrole 23
Helic[6]arenes 24
Synthesis of Helic[6]arenes 24
Cyanostars 25
Synthesis of Cyanostars 26
Oxatub[4]arene 27
Pillararenes 29
Synthesis of Pillararenes 29
Homo-cyclooligomerization 30
Co-cyclooligomerization 30
vi Macrocyclic Receptors for Environmental and Biosensing Applications
Prismarenes 32
Synthesis of Prismarenes 32
Cucurbiturils 33
Bambus[n]urils 33
Cyclotriveratrylenes 37
Synthesis of Cyclotriveratrylene 38
Cryptophanes 39
Synthesis of Cryptophanes 40
Rotaxanes and Catenanes 41
Synthesis of Rotaxanes and Catenanes 42
Functionalized Tetrathiafulvalenes 43
Synthesis of Tetrathiafulvalenes 44
Conclusions 45
References 45
Chapter 2 Macrocyclic Receptors for Environmentally
Sensitive Metal Ions 54
Introduction 54
Macrocyclic Receptors for Alkali Metal Ions 56
Macrocyclic Receptors for Li + Ions 56
Macrocyclic Receptors for Na+ Ions 57
Macrocyclic Receptors for K + Ions 58
Macrocyclic Receptors for Cs+ Ions 60
Macrocyclic Receptors for Alkaline Earth Metal Ions 62
Macrocyclic Receptors for Mg2+ Ions 64
Macrocyclic Receptors for Ca2+ Ions 65
Macrocyclic Receptors for Sr2+ Ions 66
Macrocyclic Receptors for Ba2+ Ions 66
Macrocyclic Receptors for Transition and Heavy Metal Ions 67
Macrocyclic Receptors for Fe3+ Ions 69
Macrocyclic Receptors for Cu2+ Ions 71
Macrocyclic Receptors for Zn2+ Ions 72
Macrocyclic Receptors for Cd 2+ Ions 74
Macrocyclic Receptors for Hg2+ Ions 75
Macrocyclic Receptors for Pb2+ Ions 78
Macrocyclic Receptors for Tl + Ions 79
Macrocyclic Receptors for Lanthanide and Actinide Ions 80
Conclusion 90
References 91
Chapter 3 Macrocyclic Receptors for Precious Metal Ions 99
Introduction 99
Macrocyclic Receptors for Ag+ Ions 100
Macrocyclic Receptors for Au3+ Ions 110
Macrocyclic Receptors for Pd2+ Ions 114
Conclusion 120
References 120
Contents vii
Chapter 4 Macrocyclic Anion Receptors 124
Introduction 124
Parameters that Affect Anion Complexation 125
Receptors for Anions 126
Measurement Techniques 127
Bile Acid-based Macrocycles as Anion Receptors 128
Calix[4]pyrroles Based Macrocycles as Anion Receptors 133
Redox-active Receptors as Anion Receptors 151
Porphyrin Cages Based Macrocycles as Anion Receptors 153
Conclusions 155
References 155
Chapter 5 Macrocyclic Receptors for Sensing the Environmentally
Important Gaseous Molecules 162
Introduction 162
Definition 162
Challenges 163
Role of Macrocyclic Compounds in Gas Sensing 163
Overview of a Few Different Types of Sensing Techniques 164
Quartz Micro Balance (QMB) 164
Langmuir–Blodgett Method (LB) 165
Surface Acoustic Wave Oscillator (SAW) 165
Thin-film Bulk Acoustic Resonator (FBAR or TFBAR) 166
Surface Plasmon Resonance 167
Solid-Phase Micro Extraction (SPME) 167
Evanescent Field Wave Sensor 168
Sensing of Environmentally Important Gases 169
Volatile Organic Compounds 170
BTEX 171
Cyclodextrins 171
Calixarenes 178
Other Cavitands 184
Nitrogen-containing Basic Gases and Volatile Compounds 186
Cyclodextrin 186
Calixarenes 187
Acidic Vapours 191
Hydrochloric Acid 191
Nitrogen Oxides NOx 192
Calix[4]arenes 192
Cucurbituril 199
Carbon Dioxide (CO) 200
2
Organic Carboxylic Acid Vapors 202
Neutral Gaseous Molecules 202
Conclusion 202
References 203
Chapter 6 pH-Responsive Pseudorotaxanes and Rotaxanes 214
Introduction 214
Pseudorotaxane 219
viii Macrocyclic Receptors for Environmental and Biosensing Applications
Cucurbiturils CB[n] based pH Responsive Pseudorotaxanes 220
Pillar[5]arene based pH Responsive Pseudorotaxanes 228
Cyclodextrin based pH Responsive Pseudorotaxanes 232
Rotaxanes 232
pH-responsive [2]rotaxane 234
pH-responsive [3]rotaxane 244
pH-responsive [4]rotaxane 246
pH-responsive [c2]daisy Chain Rotaxanes 246
pH-responsive Rotaxane based Polymers/Gel/Rotaxane Immobilized
into the Framework 248
Interconversion of Pseudorotaxane and Rotaxanes on the
Addition of Acid/Base 251
Conclusion 254
References 254
Chapter 7 Macrocyclic Receptors for Biomolecules and Biochemical
Sensing 266
Introduction 266
Introduction to Structure and Properties: Nucleotides, Nucleosides
and Nucleic Acid 266
Nucleosides and Nucleotides 266
Oligonucleotides and Nucleic Acids 269
Macrocyclic Receptors for Nucleotides, Nucleosides and
Nucleic Acid 271
Introduction to Structure and Properties of
Sugars/Carbohydrates 276
Macrocyclic Receptors for Carbohydrates 278
Introduction to Structure and Properties of Amino Acid,
Peptide and Proteins 280
Macrocyclic Receptors for Amino Acids, Peptides, and Proteins 282
Introduction to Structure and Function of Biological Lipids 285
Macrocyclic Receptors for Molecular Recognition of Lipids 287
Conclusion and Outlook 289
References 289
Chapter 8 Macrocyclic Receptors for Biologically Relevant Metal Ions 294
Introduction 294
Metallocycles as an Anticancer Drug 295
Metallo-macrocycle as Magnetic Resonance Imaging (MRI)
Contrast Agent 301
Metallomacrocycles as Synthetic Enzyme 307
Conclusion and Outlook 309
References 309
Chapter 9 Molecular Machines based on Macrocyclic Receptors:
Switches and Motors 314
Introduction 314
Terminology 314
Contents ix
Macrocycles Hosts: Implements of the Trade 315
Cyclodextrins (CDs) 315
Coronands and Cryptands 316
Cyclic Arenes and Analogous Deep Cavitands 317
Cucurbituril 319
Blue Box and its Derivatives (Exboxes) 320
Stimuli-Responsive Molecular Switches 322
Mechanically Interlocked Molecular Structures 324
Rotaxane 324
Pseudorotaxane 326
Molecular Switches 326
Conformational Control using Host-guest Interaction 326
Using Capping on the Macrocyclic Hosts 328
pH-Driven Threading and Dethreading (Pseudorotaxane) 328
Redox Driven Threading and Dethreading 330
Light-driven Switching 330
Molecular Tweezers 333
Orthogonal Control over Switching 334
Intramolecular Translocation of Ions with Stimuli 336
Excited-State Intramolecular Proton Transfer (ESIPT) 337
Self-complexing Pseudorotaxanes 338
Gated regulation of the Binding Site of the Host in Self-inclusive
Pseudorotaxanes 339
Self-inclusive Pseudorotaxnes with an Externally Switchable
Configuration of the Pendant for Gated Regulation
of Binding Site 342
Allosteric Regulation of Linker Controlled Gated Regulation
of Binding Site 343
Shuttling in Rotaxanes 343
Degenerate Molecular Shuttles with two Stations 344
Stimuli-responsive Molecular Shuttles 344
Stimuli-Responsive Molecular Shuttles with two or More Stations 345
Molecular Shuttles Driven by pH Change 346
Redox Driven Molecular Shuttling 346
Photodriven Molecular Shuttles 347
Ion-Induced Changes driving Molecular Shuttles 348
Shuttling Driven by Reversible Covalent Modification 349
Molecular Motors 350
Directional Motion and Work under Brownian Motion 350
Molecular Ratchet based on Rotaxanes/Pseudorotaxanes 351
Conclusion 352
References 353
Chapter 10 Role of Macrocyclic Receptors in Surface Self-assembly 366
Introduction 366
Macrocyclic Amphiphilic Structures 368
Macrocyclic Amphiphilic Structures based on Calix[n]arenes and
Resorcinarenes 369
