Learning objectives
At the end of the course the studenti s expected to be able to:
- know the intermolecular forces involved in molecular recognition; understand the theory of the experimental methods used to determine the stoichiometry and the association constant of a complex; know the main classes of macrocyclic receptors (knowledge and understanding);
- determine the association constant and the stoichiometry of a supramolecular complex starting from spectroscopical data (applying knowledge and understanding);
- analyze the supramolecular structure of a complex between a receptor and a substrate and identify the interactions and forces that account for the complex stability; choose the best technique to determine stoichiometry and formation constant of a supramolecular complex; evaluate a ligand complementarity and preorganization; choose the most appropriate synthetic pathway to prepare macrocyclic receptors and self-assembled materials (making judgements);
- present and critically comment a literature paper regarding a specific supramolecular chemistry subject using the appropriate terminology (communication skills).
Prerequisites
To fruitfully follow the course it is fundamental to have a solid knowledge of General
Chemistry, Physical Chemistry and Organic Chemistry.
Course unit content
Introduction to Supramolecular Chemistry. The molecular recognition phenomena.
Intermolecular forces.
Methods for the determination of stoichiometries and stabilities of the complexes.
Methods for the synthesis of macrocyclic compounds.
Cation complexation.
Anion complexation.
Complexation of neutral molecules.
Self-assembly.
Supramolecular catalysis.
Applications of Supramolecular Chemistry to Drug-discovery.
Full programme
Introduction to Supramolecular Chemistry. Molecular recognition. Intermolecular
forces. Methods for the determination of the stoichiometries of the complexes and of
the complexation constants via different techniques (NMR, UV-vis, fluorescence,
calorimetry, potentiometry,...). Extraction percentage and distribution coefficients.
Methodologies for the synthesis of macrocyclic compounds (crown, aza-crown,
calixarenes, resorcarenes, cyclodextrins). Synthestic modifications of the
macrocycles.
Cation complexation with crown-ethers, cryptands, spherands and ciclophanes:
synthetic methodologies and complexation studies. Applications in the field of
imaging (MRI, luminescent probes , radiolabelling), of radiotherapeutics, of metal
detoxification and of the treatment of radioactive and heavy metals waste.
Neutral molecules complexation with crown-ethers, cyclodextrins and cyclophanes:
studies on the complexes, thermodynamic and kinetic parameters, effect of the
structure of the guest and of the solvent: the hydrophobic effect.
Anion complexation by natural and synthetic receptors.
Self-assembly. Supramolecular catalysis.
Cavitands from cyclotriveratrylene, resorcarenes and calixarenes in molecular
recognition. Calixarenes as molecular platform for the synthesis of receptors for
cations, anions and neutral molecules.
Discussion on some application in the field of Supramolecular Science: Ionselective
Electrodes (ISE), ion-selective membranes, chromoionophores,
piezoelectric and fluorescence sensors.
Supramolecular Catalysis.
Bioorganic supramolecular chemsitry.
Bibliography
Supramolecular Chemistry, P.D. Beer, P. A. Gale, D.K. Smith, Oxford University
Primers, OUP, 1999.Core concepts in supramolecular chemistry and nanochemistry, J. W. Steed, D. R. Turner, K. J. Wallace, Chichester : John Wiley & Sons, 2007
Additional content can be found in the following
monographies: Supramolecular Chemistry: From Molecules to Nanomaterials, J. W. Steed, P. A. Gale, Wiley 2012 (ISBN: 978-0-470-74640-0); Supramolecular Chemistry: Concepts and Perspectives. J.-M. Lehn, VCH Ed.,
Weinheim, 1985.
Comprehensive Supramolecular Chemistry. Executive editors Jerry L. Atwood...[et
al.] ; chairman of the editorial board Jean Marie Lehn. - [Oxford] : Pergamon, 1996.
- 11v.
Calixarenes Revisited. C.D. Gutsche, J.F. Stoddart Ed., Royal Society of Chemistry,
Cambridge, 1998.
Container molecules and their guests. D.J. Cram and J.M. Cram. - London : Royal
Society of Chemistry, 1994.
Crown ethers and cryptands. G.W. Gokel. - London : Royal Society of Chemistry,
1991.
Cyclophanes. F. Diederich. - London : Royal Society of Chemistry, 1991
Teaching methods
The educational activities will consist of lectures, classroom exercises and laboratory experiences. The lectures will be held with an active learning methodology. Students in the lab will work in small groups and will perform a titration using a spectroscopic technique. Classroom exercises will deal with the determination of the stoichiometry and formation constant of an host-guest complex from the titration data.The lecttures slides will be uploaded weekly on the Elly website. Course registration on Elly is required in order to download the slides.
Assessment methods and criteria
The evaluation consists in an oral exam, where the student will discuss a literature paper on a Supramolecular Chemistry subject. The student is required to demonstrate the knowledge, the ability to apply and the ability to communicate the main concepts of Supramolecular Chemistry.
Requirement to pass the exam is a deep understanding of the intermolecular interactions at the basis of supramolecular chemistry and of the methodologies used to study supramolecular complexes. Knowledge of the main classes of supramolecular receptors is also required.
It will also be evaluated the ability of the student to indicate the most efficient synthetic route for a macrocyclic receptor (up to further 6 points) and the ability to correlate the structure of supramolecular complexes with their chemical and physical properties (up to further 6 points).
Other information
The teacher is available to students for explanations and further discussion of the topics explained during the lectures.
Indicative dates of the exams are reported on Esse3, but additional dates can be requested by the students.
