SUPRAMOLECULAR CHEMISTRY
cod. 1004772

Academic year 2023/24
2° year of course - First semester
Professor
Laura BALDINI
Academic discipline
Chimica organica (CHIM/06)
Field
Discipline chimiche organiche
Type of training activity
Characterising
55 hours
of face-to-face activities
6 credits
hub: PARMA
course unit
in ITALIAN

Learning objectives

At the end of the course the student is expected to:

- Knowledge and understanding: know the supramolecular interactions used in the complexation of cations, anions, neutral molecules and in self-assembly; know the relationship between structure and recognition properties of host systems; know the theory of the methods used to study the complexes stoichiometries and the association constants; know the synthetic methods to obtain the main classes of macrocyclic compounds used as hosts; understand in details molecular recognition phenomena in the biomolecular field.

- Applying knowledge and understanding: plan and perform a UV-vis or NMR titration to determine the association constant, also working in groups; determine the association constant and the stoichiometry of a complex from spectroscopic data applying nonlinear regression methods; collect all the literature information required to plan and perform the synthesis of macrocyclic compounds; understand and predict the relationship between structure and properties of supramolecular systems; understand problems related to molecular recognition phenomena, critically evaluate them and propose specific solutions.

- Making judgements: analyze the structure of a supramolecular complex, identifying the interactions involved in the complex formation and evaluating the kinetic and thermodynamic aspects; evaluate the complementarity and preorganization of a supramolecular host; identify appropriate synthetic pathways to prepare macrocyclic compounds; plan a UV-vis or NMR titration considering the duration and methodology; collect and analyze spectroscopic data for the determination of association constants and autonomously evaluate the results; find and evaluate literature articles in the field of supramolecular chemistry; critically evaluate his knowledge, abilities and results; organize his work and the work of his team.

- Communication skills: present a supramolecular chemistry article from the literature using the appropriate terminology; collaborate con other students and work in teams to plan and perform a UV-vis or NMR titration and use the spectroscopic data to determine an association constant.

- Learning skills: critically discuss the design and the realization of a current research work aimed at synthesizing new molecular receptors, at studying the efficiency and selectivity in the complexation of guests and at the preparation of devices exploiting supramolecular interactions; interpret through the supramolecular chemistry concepts frontier research works in the field, for example, of crystal engineering, supramolecular catalysis, molecular machines, nanotechnology, recognition and mimicking of biomacromolecules; easily collect supramolecular chemistry information from literature, databases and internet.

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

The course will provide the students the knowledge of the fundaments of Supramolecular Chemistry (molecular recognition, intermolecular forces, thermodynamics of binding processes, synthesis of macrocyclic compounds, complexation of cations, anions, and neutral molecules, interaction with biomacromolecules, self-assembly, supramolecular catalysis) and the ability to apply those concepts in all the chemical fields where molecular recognition phenomena play a key role.

Full programme

Introduction to Supramolecular Chemistry. Molecular recognition. Intermolecular
forces.
Thermodynamics of association processes (Ka, deltaG, deltaH, deltaS). Methods for the determination of the stoichiometries of the complexes and of the complexation constants via different techniques (NMR, UV-vis, fluorescence, calorimetry,...).
Methodologies for the synthesis of macrocyclic compounds (crown, aza-crown,
calixarenes, resorcarenes, cyclodextrins, cucurbiturils). Synthetic modifications of the
macrocycles.
Cation complexation with crown-ethers, cryptands, spherands, calixarenes 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.
Cavitands from cyclotriveratrylene, resorcarenes and calixarenes in molecular
recognition. Calixarenes as molecular platform for the synthesis of receptors for
cations, anions, neutral molecules and biomacromolecules.
Supramolecular catalysis.

Discussion on some application in the field of Supramolecular Science.

Bibliography

Supramolecular Chemistry textbooks:
Supramolecular Chemistry, P.D. Beer, P. A. Gale, D.K. Smith, Oxford University
Primers, OUP, 1999.
Supramolecular chemistry, J.W. Steed, J.L. Atwood. - 2. ed
Chichester : Wiley, ©2009
Core concepts in supramolecular chemistry and nanochemistry , J.W. Steed, D.R. Turner, K.J. Wallace
Chichester : John Wiley & Sons, 2007

Other texts and monographies:
Supramolecular Chemistry: From Molecules to Nanomaterials, J. W. Steed, P. A. Gale, Wiley 2012 (ISBN: 978-0-470-74640-0);

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

All the books can be found in the chemistry library.

Teaching methods

The educational activities include lessons (5 CFU), and laboratory experiences (1 CFU).
The lessons will deal, both with a traditional and an active-learning approach, the theoretical part of the program. Critical discussion of literature articles and exercises on the determination of binding constants from spectroscopic data will also be performed.
In the lab experiences, the students, working in small groups, will perform the synthesis of a molecular host and a spectrioscopic titration to determine the association constant of a complex. A report of the lab experiences is required at the end of the course.
The slides of the lessons will be uploaded every week on the Elly website. To download the slides, registration on the website is required.

Assessment methods and criteria

The evaluation consists in the assessment of the lab report (weight 20%) and in an oral exam where the student will demonstrate the understanding and ability to apply the fundamental concepts of the course (weight 80%). Both marks will be out of 30.
In particular, the oral is divided in three parts:
1)the presentation and discussion of a literature article previously assigned by the teacher. The knowledge of the concepts of supramolecular chemistry will be evaluated, together with ability to communicate using the appropriate terminology.
2) the discussion of one of the lab reports or of an example from the literature paper where a determination of the binding constant is reported, with the aim of verifying the knowledge of the theoretical and practical aspects of the thermodynamics of association processes;
3) a few questions on the course subjects with the aim of verifying the knowledge of the key concepts on the complexation of cations, anions, neutral molecules, self-assembly and on the synthesis of macrocycles.
Each part will be evaluated on a 1-10 scale. The final mark will be obtained by the sum of the three evaluations.

Other information

The dates of the oral exams are indicated on the web but additional dates can be requested by the students.
Before the exam, the student will ask the teacher the article to present at the exam.

2030 agenda goals for sustainable development

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