Table of Contents
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FOREWORD
PREFACE
List of Contributors
Luminescent Cyclodextrin Systems and Their Applications
Abstract
INTRODUCTION
HOST-GUEST SYSTEMS
LUMINESCENT CYCLODEXTRINS
FLUORESCENT SENSORS
BIOSENSORS
THERAPEUTIC APPLICATION
CONCLUSION
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Calixarene Based Luminescent Systems
Abstract
INTRODUCTION
LUMINESCENT HOST-GUEST SYSTEMS
Fluorescent Calixarene
ION SENSING APPLICATIONS
Anion Sensors
Solid State Sensor
MOLECULAR RECOGNITION
LUMINESCENT LANTHANOID CALIXARENE COMPLEXES
CONCLUSION
CONSENT OF PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Resorcinarene Crowns as Versatile Host Molecules and Their Potential Applications
Abstract
INTRODUCTION
Synthesis of Resorcinarenes
Selective Functionalization of Upper Rim Resorcinarene Crowns
Selective functionalization of lower rim resorcinarene crowns
APPLICATIONS OF RESORCINARENE CROWNS
Chemical Separations
Chemical Sensors
Catalytic Activity
Lithographic Application
Antioxidant and Antibacterial Applications
CONCLUSION
CONSENT OF PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Pillararenes: Younger Luminescent Supramolecular Systems
Abstract
INTRODUCTION
Pillararenes
Structure of Pillararenes
Synthesis of Pillararenes
Host-Guest Binding Behaviours of Pillararenes
Photophysical Behaviours of Pillararenes
Pillararenes Based Luminescence Systems
Pillararenes in Sensors Applications
Pillararenes in Metal Ions Scavenging
Pillararenes Derived Stimuli Luminescent Materials
CONCLUSIONS
CONSENT OF PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENT
REFERENCES
Cucurbit[n]urils Based Molecular Recognition with Fluorescence Signalling
Abstract
INTRODUCTION
Cucurbituril CB[n]
Structural Features of CB[n]s
Physical Properties of CB[n]s
CB[n] Based Sensors
Detection Mechanism
Direct Binding Assay
Associative Binding Assay
Indicator Displacement Assay (IDA)
Detection of Metal Ions
Detection of Amino Acids and Peptide Molecules
Detection of Biomolecules
Detection of Organic Compound
Cucurbit[n]urils in Imaging and in Photodynamic Therapy
CONCLUSION
CONSENT OF PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENT
REFERENCES
Rhenium(I)-Based Metallacycles for Sensing Applications
Abstract
INTRODUCTION
Rhenium(I)-Based Metallacycles
Binuclear Re(I) Complex
Trinuclear Re(I) Complex
Tetranuclear Re(I) Complex
Hexanuclear Re(I) Complex
Octanuclear Re(I) Complex
CONCLUSIONS
CONSENT FOR PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGEMENTS
REFERENCES
Recent Developments in the Dynamics of Fluorescently Labelled Macromolecules
Abstract
INTRODUCTION
POLY(ACRYLIC ACIDS) – STRUCTURAL TRANSITION AND DYNAMICS
PHOTOPHYSICS OF FLUOROPHORES IN POLYELECTROLYTES
PHOTOPHYSICS OF EXCITED STATE FLUOROPHORES
IMPORTANCE OF PHOTOPHYSICS AND PHOTOCHEMISTRY OF POLYMERIC MATERIALS
PHOTOPHYSICS AND CONFORMATIONAL DYNAMICS OF POLYELECTROLYTES
STEADY STATE FLUORESCENCE STUDIES AND FLUORESCENCE QUENCHING
EXCITED STATE ENERGY AND ELECTRON TRANSFER
EXCIMER AND EXCIPLEX FORMATION
TIME–RESOLVED FLUORESCENCE STUDIES AND SOLVATION DYNAMICS
POLYMER COMPLEXES
INTERPOLYMER COMPLEXES
HYDROGEN BONDED INTERPOLYMER COMPLEXES
CONCLUSION
CONSENT OF PUBLICATION
CONFLICT OF INTEREST
ACKNOWLEDGMENT
REFERENCES
Photophysics of Supramolecular Architectures
Edited by
Paulpandian Muthu Mareeswaran
Department of Industrial Chemistry
School of Chemical Sciences
Alagappa University, Karaikudi – 630 003
Tamilnadu, India
Palaniswamy Suresh
Department of Natural Products Chemistry
School of Chemistry, Madurai Kamaraj University
Madurai – 625 021, Tamilnadu, India
&
Seenivasan Rajagopal
Department of Physical Chemistry
School of Chemistry, Madurai Kamaraj University
Madurai – 625 021, Tamilnadu, India
BENTHAM SCIENCE PUBLISHERS LTD.
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FOREWORD
The introduction of surfactants and micelles to study the photophysics and photochemistry of molecules opened up a new approach to mimick the reactions taking place in nature. The opening of new horizons in molecular science after the introduction of surfactants brought a new approach to the field of molecular assemblies. The intense research in the fields of photochemistry and its applications in understanding the photosynthetic processes and solar energy conversion via chemical routes led to the growth of ‘supramolecular chemistry’, known as ‘chemistry beyond the molecule’. The last four decades witnessed an explosion of research activities in the application of supramolecular assemblies in photophysics and photochemistry of molecules and the importance of supramolecular chemistry was understood after the award of 1987 Nobel Prize for Chemistry (Nobel Laureates: Donald J. Cram, Jean-Marie Lehn and Charles J. Pedersen) in this area of research.
The editors have chosen the interesting theme of ‘Photophysics of Supramolecular Architectures’ and presented a collection of important topics covering a wide variety of molecular assemblies and their applications, in particular, in the field of sensors and allied topics. The senior editor Prof. S. Rajagopal with his four decades of intense research in the fields of electron transfer reactions and photochemistry and his experienced co-editors are able to bring together a spectrum of scientists working in the areas of supramolecular systems and their applications. The authors of eight chapters put their efforts to update the knowledge gained in the fields of supramolecular chemistry and their applications in photophysics and photochemistry. The scientists and the young researchers working in the areas of photophysics and photochemistry of molecules in supramolecular assembly can immensely benefit from the book ‘Photophysics of Supramolecular Architectures 2021’ published by the editors. The editors have made an effort to cover a wide range of supramolecular systems from the conventionally known cyclodextrin systems to calixarene, resorcinarene crowns, pillararene, cucurbit[n]urils, cavitands, metallacycles and fluorescently labelled macromolecules and presented their variety of applications related to photophysics and photochemistry, in particular, the luminescent sensor systems for a wide range of analyte molecules. This book is a single source of collection of literature on the chosen topic and will help the young researchers to understand the field of research, up-to-date literature and design their future plan of action in the areas of supramolecular systems and their applications in photophysics and photochemistry.
Dr. R. Ramaraj
Department of Physical Chemistry
School of Chemistry
Madurai Kamaraj University
Madurai-625021, Tamilnadu
India
PREFACE
Supramolecular architectures, the prevalent architectures in nature, are designed through a variety of non-bonding interactions like hydrogen bonding, π-π staking, self-assembly, etc. From physics to biology, the functionalities of supramolecular architectures play an important role. For example, life is not possible without a DNA folding or protein self-assembly. This book mainly focuses on cavities containing supramolecular hosts and their photophysical properties by attaching luminescent molecules as guests. The host-guest chemistry is a widely established subject that can expand as an individual field of research with respect to the cavitand. The host-guest chemistry is envisaged as mimic for enzymatic catalysis. Also, they are used as drug delivery vehicles for the targeted payload delivery in biochemistry and biotechnology. The study of the interaction of guest molecules with light in the presence of host molecule opens a research opportunity to develop advanced research like optical tweezers.
The recent studies of photophysics of guest molecules with various cavitands like cylclodextrin, calixarene and their derivatives, cucurbiturils are highlighted in this book. The cyclodextrin complexes having different cavities and encapsulation of fluorescent guest molecules and applications of these systems are elaborately discussed in Chapter 1. Chapter 2 deals with the interaction of fluorescent guest molecules with calixarenes and their applications towards (as) sensors. The photophysical properties of coordinations complexes of calixarene-lanthanide systems are also discussed in this chapter.
Resorcinarenes, one of the important molecules in the calixarene family, receive importance for their hydroxyl group containing upper rim, which makes them suitable for catalysis applications. Chapter 3 mainly focuses on the upper rim modification at hydroxyl group to achieve crown ethers. Eventhough the crown ethers are separately known as supramolecules, this chapter discusses upper rim modified resorcinarene-crown and their applications using optical spectral techniques. Chapter 4 deals with the pillararenes, which are considered as young cavitand molecular system, reported only in 2008. This chapter focuses on the host-guest chemistry of pillararenes with fluorescent guest molecules. The self-assembly of pillarene derivative is also discussed to achieve sensor applications.
Chapter 5 is concerned with the molecular recognition of fluorescent guest molecules encapsulated cucurbiturils and their applications as sensors. The application of imaging and photodynamic therapy using cucurbiturils systems is also discussed. Chapter 6 deals with the control of photophysical properties and photochemical events of various cavities and capsules. Chapter 7 mainly focuses on the cavity containing rhenium(I) metallasupramolecules, i.e., metallacycles. The synthesis, photophysical properties and host-guest behavior of rhenium metallacycles ranging from simple to complex topologies are discussed in detail. Chapter 8 deals with the dynamics of macromolecules functionalized with fluorescent molecules. The macrocyclic environment acts as a host molecule and influences the optical properties of the functionalized fluorescent molecule. The folding and unfolding of macrocycles exhibit substantial variations in the fluorescent molecules.
This book strives to give collectively the applications of host-guest chemistry with recent applications. The recent advancements in the various host-guest systems will provide newer insights to readers into both conventional host molecules like cyclodextrin as well as young host molecules like pillararenes.
Paulpandian Muthu Mareeswaran
Department of Industrial Chemistry
School of Chemical Sciences
Alagappa University, Karaikudi – 630 003
Tamilnadu, IndiaPalaniswamy Suresh
Department of Natural Products Chemistry
School of Chemistry, Madurai Kamaraj University
Madurai – 625 021, Tamilnadu, India&Seenivasan Rajagopal
Department of Physical Chemistry
School of Chemistry, Madurai Kamaraj University
Madurai – 625 021, Tamilnadu, India
List of Contributors
Bosco Christin Maria Arputham AshwinDepartment of Chemistry, Pioneer Kumaraswamy College, Nagercoil 629 003, Tamilnadu, IndiaE. RajkumarBiomimetic and Biosensor Lab, Department of Chemistry, Madras Christian College (Autonomous), Affiliated to University of Madras, Chennai-600 059, Tamilnadu, IndiaJeyaraj Belinda AshaSupramolecular and Catalysis Lab, Dept. of Natural Products Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai-625021, Tamilnadu, IndiaKandhasamy Durai MuruganDepartment of Bioelectronics and Biosensors, Alagappa University, Karaikudi-630003, Tamilnadu, IndiaLiju R.Biomimetic and Biosensor Lab, Department of Chemistry, Madras Christian College (Autonomous), Affiliated to University of Madras, Chennai-600 059, Tamilnadu, IndiaMurugesan VelayudhamDepartment of Chemistry, Thiagarajar College of Engineering, Madurai-625015, Tamilnadu, IndiaPalaniswamy SureshSupramolecular and Catalysis Lab, Dept. of Natural Products Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai-625021, Tamilnadu, IndiaPandi MuthirulanDepartment of Chemistry, Lekshmipuram College of Arts and Science, (Affiliated to MS University, Tirunelveli), Neyyoor-629802, Tamilnadu, IndiaPaulpandian Muthu MareeswaranDepartment of Industrial Chemistry, Alagappa University, Karaikudi 630 003, Tamilnadu, IndiaPounraj ThanasekaranDepartment of Chemistry, Pondicherry University, Kalapet, Puducherry -605 014, IndiaSelvaraj DeviP. G. Department of Chemistry, Cauvery College for Women, Tiruchirappalli-620018, Tamilnadu, IndiaSomasundaram Anbu Anjugam VandarkuzhaliDepartment of Chemistry, Saveetha School of Engineering, Saveetha Institute of Medical and Technical Sciences, Saveetha University, Chennai-600005, Tamilnadu, IndiaVairaperumal TharmarajEnvironmental Science and Technology Research Group, Department of Chemical Engineering, SRM Institute of Science and Technology, Kattankulathur-603203, Tamilnadu, IndiaVenkatesan SethuramanDepartment of Industrial Chemistry, Alagappa University, Karaikudi 630 003, Tamilnadu, IndiaVijayanand ChandrasekaranDepartment of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore-632014, Tamilnadu, India
Luminescent Cyclodextrin Systems and Their Applications
Bosco Christin Maria Arputham Ashwin1,Venkatesan Sethuraman2,Paulpandian Muthu Mareeswaran2,*
1 Department of Chemistry, Pioneer Kumaraswamy College, Nagercoil 629 003, Tamilnadu, India
2 Department of Industrial Chemistry, Alagappa University, Karaikudi 630 003, Tamilnadu, India
Abstract
This chapter explains the most recent development on different luminophore tethered cyclodextrin (CD), a cyclic polysaccharide and these applications in distinct areas. The host-guest inclusion complexation studies of CD with different guest molecules using fluorescence techniques are discussed. The hybrid materials of CD in the detection of biological analytes, toxic compounds and in-vivo bio-imaging applications are discussed. The compatibility nature of CD leads to its usage in drug delivery and the controlled drug dosage using CDs is explained. The interesting usage of CDs in counterfeit recognition and tunable emission are emphasised. The dimers and self-assemblies of CDs utilized for the enhancement of photophysical properties are discussed in detail. The CD hybrid materials exhibited numerous usage in essential needs.
Keywords: Aggregation, Amino acids, Anion, Bioimaging, Biomolecule, Cyclodextrin, Chemosensor, Dimer, Drug, Dye, Emission, Fluorescence, Host-guest, Interaction, Lanthanoids, Luminescence, Macrocycle, Recognition, Nanocarrier, Nanoparticles.
*Corresponding author Paulpandian Muthu Mareeswaran: Department of Industrial Chemistry, Alagappa University, Karaikudi 630 003, Tamilnadu, India; Tel: +919790963437; E-mails:
[email protected] and
[email protected]CONSENT FOR PUBLICATION
Not applicable.
CONFLICT OF INTEREST
The author declares no conflict of interest, financial or otherwise.
ACKNOWLEDGEMENTS
This research work was supported by the Department of Science and Technology (DST INSPIRE) [Project number – IFA14/CH-147], India. We also thank RUSA 2.0 (MHRD, India) grant sanctioned vide Letter No. F. 24-51/2014-U, Policy (TNMulti-Gen), Dept. of Edn. Govt. of India, Dt. 09.10.2018 for the additional financial support.
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