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SUPRAMOLECULAR CHEMISTRY AND ITS APPLICATION

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PRAYAS - An International Journal of Multidisciplinary Studies

SUPRAMOLECULAR CHEMISTRY AND ITS APPLICATION

Suman Adhikari*, Arijit Das** & Basu Maan Daas***
*, **, *** Assistant Professor, Department of Chemistry, Govt. Degree College, Dharmanagar, Tripura,
India
Corresponding author: Suman Adhikari
Abstract
Supramolecular chemistry refers to the study of supramolecular assemblies. Traditional chemistry generally
focuses on the covalent bonding but supramolecular chemistry monitored by weak interactions of
noncovalent bonds; exist extensively in numerous vital biological processes. The origin of supramolecular
chemistry was from the living biological systems to some extent. This critical review highlights recent
advances in supramolecular chemistry and its application.
Key words: Supramolecular chemistry, noncovalent bonds, host, guest, recognition, complexation.
*******
Introduction
Supramolecular Chemistry is one of the most popular and rapid growing areas of chemistry which emphases
going "beyond" molecular chemistry or “Chemistry of molecular assemblies and of the intermolecular
bond”. It is the study of systems which contain more than one molecular assembly, and it aims to understand
the structure, function, and properties of these assemblies. Supramolecular chemistry studies the phenomena
such as molecular self-assembly, protein folding, molecular recognition, host-guest chemistry,
mechanically-interlocked molecular architectures, and dynamic covalent chemistry. It is highly
interdisciplinary in nature and attracts not just chemists but biologists, environmental scientists, physicists,
biochemists, theoreticians, crystallographers. In 1987 the supramolecular Chemistry came of age when
Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen were jointly awarded the Nobel Prize for
Chemistry in recognition of their work on "host-guest" assemblies. The study of supramolecular Chemistry
covers a set of phenomena that are monitored by specific noncovalent interactions between molecules
like ion-dipole, dipole-dipole interactions, hydrogen bonding, metal coordination, hydrophobic forces, van
der Waals forces, pi-pi interactions and electrostatic effects. These phenomena are crucial in biological
systems, such as enzyme action, molecular transport, genetic information and processing, protein assembly,
etc. Biological systems are often the inspiration for supramolecular research.
Supramolecular Chemistry gives idea how molecules interact with each other. Among these interactions,
‘molecular recognition’ is the way that molecules can recognize each other.
Design Principle of Supramolecular Host
Generally a ‘host’ molecule binds a ‘guest’ molecule to produce ‘Host-Guest’ complex or supramolecule.

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Noncovalent interaction plays most crucial rule in the binding processes. Generally the host is a large molecule or
aggregates possessing a sizeable central hole or cavity and also possessing convergent binding site. The guest may be
cation or anion or molecules like hormones, pheromone or neurotransmitter and possesses divergent binding site. In
order to bind a host molecule must have binding positions to interact with the guest molecule. The binding sites must
be spaced out on the host in such a way to make it possible for the host to interact with guest molecule. There are two
major classes of host, cyclic and acyclic. Host-guest interaction occur through binding sites (Figure 1). Selective
and efficient recognition depends on cooperative contribution from both host and guest molecules and also
careful consideration of the target molecule.

Figure 1. Design Principle. Here. R= Reporter group: fluorogenic, Chromogenic or Redox active, B=
Binding site, S= Spacer- separates binding site and reporter group, G= Guest molecule.

In recent times synthetic receptors of specific structural properties are being used as sensors. Sensor must be
selective for a particular guest and not only report the presence of guest molecules, but also allow
determining its concentration. Some molecular binding can induce signal output, such as light emission.
Recently fluorometric technique, is widely used as it is more sensitive and very useful in the field of
supramolecular chemistry
Supramolecular chemistry in Nature
Nature exhibits rich and versatile examples of supramolecular chemistry. Origins of supramolecular
chemistry come from the chemistry found in living biological system. The concept of recognition to form
supramolecule is an integral part in both living and nonliving system. Nature has evolved an enormous
amount of highly selective, specific and cooperative chemistry that enables living system to maintain them
in the environment to feed, respire, reproduce and respond to external stimuli. Here some examples, which
play crucial role in living system, are briefly discussed.
Several key nucleoside binding proteins use both hydrogen bonding and π - π stacking forces to provide
strong and selective complexation. For example, ribonuclease T1 binds guanine via two hydrogen bonds
between the peptide backbone and O (6) and NH (1) groups of guanine. The stacking interaction between a

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tyrosine residue (Tyr-45) and purine plane also enhance the binding. An ‘induced fit recognition’ is further
exemplified here from the fact that Tyr-45 swings from an ‘unbound’ conformation into a stacking position
on guanine binding. In the double helical structure of deoxyribonucleic acid (DNA), the vertical base-base
interaction through hydrogen bonding is a stabilizing force of the double helix. The noncovalent interactions
that exist between the individual subunits in haemoglobin, controls both structure and function.
Valinomycine is a naturally occurring macrocyclic antibiotic, first isolated in 1955. It can selectively
transports K+ and H+ ion across mitochondrial membranes in the presence of Na+ ion. It has a cyclic
structure consisting of three identical repeated fragments of four amino acids each containing D-
hydroxyisovaleric acid, D-valine, L-lactic acid and L-valine (Figure 2). Valinomycine is selective for K+
ion. It complexes K+ ion by the electronegative oxygen atoms of the antibiotic ester groups and once it is
encapsulated within the macrocycle it can be efficiently transported through the hydrophobic membrane.
The conformation adopted by Valinomycin on K+ complexation is stabilized by six –NCO…HN- hydrogen
bonds around the periphery of the macrocycle.

Me MeMe Me Me Me
Me
H H
O N O N

D O D O LO LO 3

Figure 2. Valinomycin.

Application
1. In transport process
Ion recognition, extraction and transport through membrane plays vital role in many biological processes.
Large quantities of sodium, potassium, magnesium and calcium ions, in particular, are all critical to life. The
design and synthesis of host molecules that can bind selectively guest molecules have made a range of
compounds that may become carrier receptors. If the molecules are membrane soluble, they induce the
selective transport of substrate through permeable membrane. Suitably modified receptors act as carriers for
the selective transport of various types of ions and neutral guest molecules through artificial or biological
membranes. Natural acyclic and macrocyclic ligands such as valinomycin, nonactin etc.are found to act as
selective ion carriers (ionophores). Another classical example is Haemoglobin, playing important roles in
uptake and transport of oxygen, are the iron complex supermolecules of porphyrin ring.
2. In Medicines
Supramolecular chemistry can help to understand better how to make effective drugs. Supramolecules drug are

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formed by two or more molecules through noncovalent bonds. Binding of small molecules to complex
proteins that are complementary in shape and charge to the biomolecular target with which they interact and
therefore will bind to it, forms the basis of modern drug design. Drug molecules are specifically designed to
recognize only those particular enzymes or receptors involved in the disease process and as such drugs must
be highly discriminating at the molecular level so that the disease can be controlled without side effects.
Supramolecular chemistry methods create nanoparticles that significantly enhanced antitumor activity with
decreased toxicity in breast and ovarian cancer. The area of drug delivery has also made critical advances as
a result of supramolecular chemistry providing encapsulation and targeted release mechanisms.
Thus the artificial recognition of important biomolecules (peptides, nucleotides, drugs etc) may lead to the
development of new pharmaceutical strategies, drug delivery systems or chemical sensor design. Such
studies are directed at the recognition of the ground state structures of the target substrates. For instance,
Parkinson’s disease is caused by a lack of the transmitter dopamine in the brain. A common approach
involves the administration of dihydroxy phenylalanine (DOPA), a common biosynthetic precursor of
dopamine. DOPA can cross the blood brain barrier while dopamine cannot. Another treatment for
Parkinson’s disease in some cases is the administration of biopterine, which is one of the co-factors in the
biosynthesis of dopamine. Supramolecular drugs playing crucial roles in many medicinal such as antitumor,
anti-inflammatory, analgesic, antimalarial, antibacterial, antifungal, antivirus, antiepileptic, cardiovascular
agents and magnetic resonance imaging agents etc.
3. In Supramolecular catalysis
The beginnings of supramolecular chemistry may be traced back to Fisher’s lock and key model of
enzymatic catalysis. Enzyme catalysis shows the preferential complexation and stabilization of the transition
states over the corresponding starting materials and products. Binding occurs by three dimensional contacts
between enzyme and substrate by intermolecular interaction. Enzyme catalysts can accelerate the rate of a
chemical reaction up to 1020 times than the rate of the uncatalyzed reaction in water. The development of
small synthetic receptors which bind transition states or which lower the activation energy of a reaction by
introducing alternative pathways has been considerably more difficult. The success of this approach depends
on the precise positioning of binding groups in a receptor to bind more strongly the transition state than the
substrate and is expected to increase the rate of reaction. Supramolecular chemistry has therefore been to
utilize these supramolecular interactions for the development of highly efficient catalysts for organic
transformations.
4. In Nanotechnology and molecular devices
Supramolecular chemistry will be the main tool used in the development of nanotechnology.
Nanotechnology and molecular devices are expected to play a major role in many future technologies. The

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fascinating benefits of supramolecular chemistry are the construction of defined nanostructures from small,
preferably synthetically easily accessible molecules. The main unifying theme is the control of matter on a
scale smaller than 1 micrometer, normally approximately 1 to 100 nanometers, as well as the fabrication of
devices of this size. The development of ultra-small molecular devices is predicted to enhance our standard
of living. Molecular devices are functional materials that are structurally precise down to the molecular level
that are constructed using the concepts of supramolecular chemistry. Molecular electronic devices,
molecular photonic devices, molecular computer, molecular machines are the examples of molecular devices.
Examples of nanotechnology in modern use are the manufacture of polymers based on molecular structure,
and the design of computer chip layouts based on surface science. Technology based on devices with
nanomaterial properties is predicted to revolutionize our lives in the near future.
Conclusion
Modern research is inspired by the prospect that supramolecular chemistry could lead to new technologies.
Supramolecular chemistry is still a new field, developing quickly due to contributions from a variety of
related fields. At the end of this century, Supramolecular Chemistry appears as a revolutionary way of
dealing with chemical compounds and concepts, exploiting the properties beyond the frontiers of the
isolated molecules. Supramolecular Chemistry has already discovered the great possibilities for the design of
intelligent molecules and devices. Molecular electronics and photonics are being expected as the next
generation of advanced machine. Recently the development of molecular devices capable of sensing, photo
switching, separation, motion and transport have become major focus of this field. Biotechnology and
nanotechnology are expected to lead to technological revolutions in near future that will dramatically affect
our lifestyles. Supramolecular chemistry is a necessary tool in these technologies.
Acknowledgements
We thank UGC NERO, Government of India for financial support. S.A expresses his gratitude and sincerest
thanks to Dr. Kumaresh Ghosh, University of Kalyani, India and Prof. Chang He Lee, Kangwon National
University, South Korea, for valuable guidance, helpful discussions and constant encouragement.
References
Atwood, J. L., Davies, J. E. D., MacNicol, D. D. & Vogtle, F. (1996). Comprehensive Supramolecular
Chemistry, ed. Pergamon, Oxford, II.
Pedersen, C. J. (1967). Journal of American Chemical Society 89, 2495.
Atwood, J. L., Koutsantonis, G. A. & Raston, C. L. (1994). Nature 368, 229.
Beijer, F. H., Kooijman, H., Spek, A. L., Sijbesma, R. P. & Meijer, E. W. (1998). Angew.Chem. Int. 37. 75.
Bromfield, S.M., Wilde, E. & Smith. D.K. (2013). Chem. Soc. Rev., DOI: 10.1039/C3CS60278H.
Busschaert, N. & Gale, P. A. (2013). Angewandte Chemie International Edition 52 (5), 1374.

ONLINE ISSN No. : 2348-618X Page 5

PRAYAS - An International Journal of Multidisciplinary Studies

Chia, P. S. K., Lindoy, L. F., Walker, G. W. & Everett, G. W. J. (1991). Journal of American Chemical
Society 113, 2533.
Cram, D. J. (1988). Angew. Chem. Int. 27, 109.
Diederich, F. Cyclophanes, (1991).RSC: Cambridge.
Schneider, H.-J.; Dürr, H. (1991). Frontiers in Supramolecular Organic Chemistry and Photochemistry.
VCH: New York.
Djurdjevic, S., Leigh, D. A., McNab, H., Parsons, S., Teobaldi, G. & Zerbetto, F. (2007). Journal of
American Chemical Society 129, 476.
Dugas, H. (1989). Bioorganic Chemistry: A Chemical Approach to Enzyme Action. second ed.; Springer-
Verlag: New York.
Fischer, F. (1894). Ber. Deutsch. Chem. Ges. 27, 2985.
G.A. Jeffrey, (1997). An introduction to hydrogen bonding.
Gale, P. A. (2011). Accounts of Chemical Research 44, (3), 216.
Ghosh, K. & Adhikari, S. (2006). Tetrahedron Lett., 47, 3577.
J.W. Steed & J.L. Atwood, (2000). Supramolecular Chemistry, John Wiley & Sons Ltd, Chichester,
England.
H. J. Schneider & A. Yatsimirsky (2000). Principles and Methods in Supramolecular Chemistry. John
Wiley & Sons Ltd, Chichester, England.
Holland, B.T., Abrams, L. & Stein, A. J. (1999). Journal of American Chemical Society 121, 4308.
Irie, M. & Kato, M. (1985). ). Journal of American Chemical Society 107, 1024.
Kim, S. K., Hay, B. P., Kim, J. S., Moyer & B. A., Sessler, J. L. Chem Comm, 2013, 49, 2112.
Kim, S. K & Sessler, J. L. (2010). Chem. Soc. Rev., 39, 3784.
Lehn, J. M. (1988). Angew. Chem. Int. 27, 89.
Lehn, J. M. (1990). Angew. Chem. Int. 29, 1304.
Lehn, J. M. (1988). Angew. Chem., Int. 112, 90.
Lehn, J. M. (1995). Supramolecular Chemistry: Concepts and Perspectives. VCH, Weinhein.
Lehn, J. M. (1988). Angew. Chem. Int. Ed. 27, 89.
Lehn, J. M. (1990). Angew. Chem. Int. Ed. 29, 1304.
Lehn, J. M. (1995). Supramolecular Chemistry Concepts and Perspectives.
Lehn, J. M. (2002). Proc. Natl. Acad. Sci. U. S. A., 99, 4763.
Park, I. W., Yoo, Y., Adhikari, S., Park, J.S., Sessler, J.L. & Lee, C. H. (2012). Chemistry - A European
Journal 47, 15073.
Schwartz, M., Miehe, G., Zerr, A, Krohe, E., Poe, B.T., Fuess, H. & Riedel, R. (2000). Adv.Mater. 12, 883.

ONLINE ISSN No. : 2348-618X Page 6

PRAYAS - An International Journal of Multidisciplinary Studies

Seel, C. & Vögtle, F. Angew. (1992). Chem., Int. Ed. Engl. 31, 528.
Taylor, E. W. (1993). Science 261, 35.
Vögtle, F. (1993). Supramolecular Chemistry. John Wiley and Son: Chichester.

ONLINE ISSN No. : 2348-618X Page 7

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