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Aadil Ali Wani
1
INTRODUCTION
 Chemistry beyond the molecule. (J.-M. Lehn 1978)
 Chemistry of molecular assemblies and intermolecular
bond.
 The Chemistry of non-covalent bond.
 Supramolecular systems are the bridge between nonliving
and living matter and the principal bases of life.
 Supramolecular systems are result of self-organization of
molecules.
 Inspired from biology and built on the shoulders of
traditional synthetic organic chemistry.
 Deserve to be a field of study on its own due to the
interdisciplinary nature.
2
.
3
Ways of studying Supramolecular chemistry
Synthetic Supramolecular systems:
 Investigation of Supramolecular systems of different architectures with
different functions created on the basis of synthetic components.
Natural Supramolecular systems:
 Investigation of architectures and functions of Supramolecular systems and
their components separated from biological objects.
4
HISTORY
 Nobel laureate Herman Emil Fischer developed philosophical roots
‘of Supramolecular chemistry.
 In 1987 , Nobel prize for chemistry was awarded to Donald J. Cram,
Jean-Marie Lehn, and Charles J. Pedersen in the development of
Supramolecular chemistry.
 Pedersen observed crown ethers and are states as the first artificial
compounds to show molecular recognition.
5
K+
HOST-GUEST CHEMISTRY
Definitions:
HOST Organic molecule containing convergent
binding sites.
 Synthetic counterparts to receptor sites in enzymes,
genes.
 antibodies and ionophores.
GUEST :Molecules or ions containing divergent binding
sites.
 Counterparts to substrates, inhibitors, cofactors,
antigens
6
Complex:
 Complexes: Hosts and guests held together in solution in definable
structure.
 Relationships by electrostatic forces (enthalpy component) such as ion
pairing,
 Hydrogen bonding, metal ion-to -ligand attraction, π-π-stacking,
 dipole-dipole interactions, and van der Waals attraction, and
 the entropic component of desolvation
7
Host-Guest Chemistry
8
CLASSIFICATION OF SUPRAMOLECULAR HOST - GUEST
CHEMISTRY
Divided into two main classes according to type of the host - guest
aggregate:
 Cavitand= host with intramolecular cavities, host-guest aggregate is
cavitate
 Clathrand =host with extramolecular cavities, host –guest aggregate
is clatherate
9
Beyond Host-Guest Chemistry
Molecular Self-Assembly:
 Process by which two or more interact to form a larger
structure or organization.
Supra Molecular Assembly:
 A complex formed by molecular self –assembly which
contains a discrete number of subunits.
10
.
11
Supramolecular Assembly
12
Supramolecular Interactions
 Supramolecular chemistry is the chemistry of weak
interactions i.e. noncovalent intermolecular forces;
Categories:
Ion-ion interactions.
Ion-dipole interactions.
Dipole-dipole interactions.
Hydrogen bonding.
Vanderwaals force.
Hydrophobic effects.
13
Nature of non covalent Forces
14
 Ion-ion interaction
 Ion-dipole interaction
 Dipole-dipole interaction
 Hydrogen bond
 Cation –π interaction
 π-π interaction
 Vander-Waals interaction
 Hydrophobic effects
200-300 kJ/mol
50-200 kJ/mol
5-50 kJ/mol
4-120 kJ/mol
5-80 kJ/mol
0-50 kJ/mol
(<5 kJ/mol)
Entropy
.
15
Applications
16
Sensing
Supramolecular chemistry addresses fundamental
questions about the sensing of ions and biological
molecules, e.g. glucose or RNA detection.
Recently in 2015, James and co-workers were able to
introduce another sensor known as Glysure Continuous
Intravascular Glucose Monitoring Sensor (CIGMS) for
glucose monitoring in patients with intensive care.
17
Drug Delivery
18
Molecular Imaging
19
Metal Extraction
20
Conclusions
 The approach of supramolecular chemistry is based on the ability to
self-assemble readily available molecules or ions in many novel ways
through the use of non-covalent interactions.
 Need to carry out the interdisciplinary research in wider sense.
 Having promising role in the field of drug delivery makes its relevance
to biological systems..
 Need to develop novel receptors making use of anion-π interactions
along with hydrogen bonding.
21
References
B. C. Crane, N. P. Barwell, P. Gopal, M. Gopichand, T. Higgs, T. D. James, C.
M. Jones, A. Mackenzie, K. P. Mulavisala and W. Paterson, J. Diabetes Sci.
Technol., 2015, 9, 751–761.
B. D. Smith, Beilstein J. Org. Chem., 2015, 11, 2540–2548.
J. R. Turkington, P. J. Bailey, J. B. Love, A. M. Wilson and P. A. Tasker,
Chem. Commun., 2013, 49, 1891–1899.
A. M. Wilson, P. J. Bailey, P. A. Tasker, J. R. Turkington,R. A. Grant and J. B.
Love, Chem. Soc. Rev., 2014, 43, 123–134.
22
P. A. Tasker, P. G. Plieger and L. C. West, in Comprehensive Coordination
Chemistry II, ed. J. A. McCleverty and T. J. Meyer, Pergamon
A. M. Wilson, P. J. Bailey, P. A. Tasker, J. R. Turkington,R. A. Grant and J.
B. Love, Chem. Soc. Rev., 2014, 43, 123–134.
P. V. Bonnesen, L. H. Delmau, B. A. Moyer and R. A. Leonard,Solvent
Extr. Ion Exch., 2000, 18, 1079–1107.
Ariga,K.,Kunitake,T.(2006) Supramolecular Chemistry- Fundamentals and
Applications Advanced Textbook. Springer
23
24

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Supramolecular chemistry

  • 2. INTRODUCTION  Chemistry beyond the molecule. (J.-M. Lehn 1978)  Chemistry of molecular assemblies and intermolecular bond.  The Chemistry of non-covalent bond.  Supramolecular systems are the bridge between nonliving and living matter and the principal bases of life.  Supramolecular systems are result of self-organization of molecules.  Inspired from biology and built on the shoulders of traditional synthetic organic chemistry.  Deserve to be a field of study on its own due to the interdisciplinary nature. 2
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  • 4. Ways of studying Supramolecular chemistry Synthetic Supramolecular systems:  Investigation of Supramolecular systems of different architectures with different functions created on the basis of synthetic components. Natural Supramolecular systems:  Investigation of architectures and functions of Supramolecular systems and their components separated from biological objects. 4
  • 5. HISTORY  Nobel laureate Herman Emil Fischer developed philosophical roots ‘of Supramolecular chemistry.  In 1987 , Nobel prize for chemistry was awarded to Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen in the development of Supramolecular chemistry.  Pedersen observed crown ethers and are states as the first artificial compounds to show molecular recognition. 5 K+
  • 6. HOST-GUEST CHEMISTRY Definitions: HOST Organic molecule containing convergent binding sites.  Synthetic counterparts to receptor sites in enzymes, genes.  antibodies and ionophores. GUEST :Molecules or ions containing divergent binding sites.  Counterparts to substrates, inhibitors, cofactors, antigens 6
  • 7. Complex:  Complexes: Hosts and guests held together in solution in definable structure.  Relationships by electrostatic forces (enthalpy component) such as ion pairing,  Hydrogen bonding, metal ion-to -ligand attraction, π-π-stacking,  dipole-dipole interactions, and van der Waals attraction, and  the entropic component of desolvation 7
  • 9. CLASSIFICATION OF SUPRAMOLECULAR HOST - GUEST CHEMISTRY Divided into two main classes according to type of the host - guest aggregate:  Cavitand= host with intramolecular cavities, host-guest aggregate is cavitate  Clathrand =host with extramolecular cavities, host –guest aggregate is clatherate 9
  • 10. Beyond Host-Guest Chemistry Molecular Self-Assembly:  Process by which two or more interact to form a larger structure or organization. Supra Molecular Assembly:  A complex formed by molecular self –assembly which contains a discrete number of subunits. 10
  • 11. . 11
  • 13. Supramolecular Interactions  Supramolecular chemistry is the chemistry of weak interactions i.e. noncovalent intermolecular forces; Categories: Ion-ion interactions. Ion-dipole interactions. Dipole-dipole interactions. Hydrogen bonding. Vanderwaals force. Hydrophobic effects. 13
  • 14. Nature of non covalent Forces 14  Ion-ion interaction  Ion-dipole interaction  Dipole-dipole interaction  Hydrogen bond  Cation –π interaction  π-π interaction  Vander-Waals interaction  Hydrophobic effects 200-300 kJ/mol 50-200 kJ/mol 5-50 kJ/mol 4-120 kJ/mol 5-80 kJ/mol 0-50 kJ/mol (<5 kJ/mol) Entropy
  • 15. . 15
  • 17. Sensing Supramolecular chemistry addresses fundamental questions about the sensing of ions and biological molecules, e.g. glucose or RNA detection. Recently in 2015, James and co-workers were able to introduce another sensor known as Glysure Continuous Intravascular Glucose Monitoring Sensor (CIGMS) for glucose monitoring in patients with intensive care. 17
  • 21. Conclusions  The approach of supramolecular chemistry is based on the ability to self-assemble readily available molecules or ions in many novel ways through the use of non-covalent interactions.  Need to carry out the interdisciplinary research in wider sense.  Having promising role in the field of drug delivery makes its relevance to biological systems..  Need to develop novel receptors making use of anion-π interactions along with hydrogen bonding. 21
  • 22. References B. C. Crane, N. P. Barwell, P. Gopal, M. Gopichand, T. Higgs, T. D. James, C. M. Jones, A. Mackenzie, K. P. Mulavisala and W. Paterson, J. Diabetes Sci. Technol., 2015, 9, 751–761. B. D. Smith, Beilstein J. Org. Chem., 2015, 11, 2540–2548. J. R. Turkington, P. J. Bailey, J. B. Love, A. M. Wilson and P. A. Tasker, Chem. Commun., 2013, 49, 1891–1899. A. M. Wilson, P. J. Bailey, P. A. Tasker, J. R. Turkington,R. A. Grant and J. B. Love, Chem. Soc. Rev., 2014, 43, 123–134. 22
  • 23. P. A. Tasker, P. G. Plieger and L. C. West, in Comprehensive Coordination Chemistry II, ed. J. A. McCleverty and T. J. Meyer, Pergamon A. M. Wilson, P. J. Bailey, P. A. Tasker, J. R. Turkington,R. A. Grant and J. B. Love, Chem. Soc. Rev., 2014, 43, 123–134. P. V. Bonnesen, L. H. Delmau, B. A. Moyer and R. A. Leonard,Solvent Extr. Ion Exch., 2000, 18, 1079–1107. Ariga,K.,Kunitake,T.(2006) Supramolecular Chemistry- Fundamentals and Applications Advanced Textbook. Springer 23
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