Anno Accademico 2022/2023
- Docente: Andrea Fermi
- Crediti formativi: 6
- SSD: CHIM/03
- Lingua di insegnamento: Inglese
- Modalità didattica: Convenzionale - Lezioni in presenza
- Campus: Bologna
- Corso: Laurea Magistrale in Photochemistry and Molecular Materials (cod. 9074)
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dal 19/09/2022 al 09/01/2023
Conoscenze e abilità da conseguire
The students will acquire the fundamentals at the basis of supramolecular chemistry, and they will be familiar with the properties and transformations of the main classes of supramolecular systems. The course will present also the most recent developments in the field, characterization techniques and potential applications.
Contenuti
A – INTRODUCTION - HISTORY
• First examples - historical overview
• Zeolites
• Clathrates
• Observations of self-assembled systems
• Intra/Intermolecular interactions
• M+L coordinative binding
• H-bonding
• Halogen bonding
• VdW forces
• Concepts
• HG interactions; receptors
• Lock + key
• Non-covalency
• Old school Supramolecular Chemistry
• Pedersen's macrocycles
• Lehn's cryptands
• Cram's spherands
• Supramolecular Chemistry Today
• Materials
• Nanomaterials
• Engineering and practical uses
• Nomenclature
B – INTRODUCTION: EXPERIMENTAL TECHNIQUES
• NMR
• Basics
• MAS
• NOESY, ROESY
• DOSY
• Examples of uses
• Absorption and emission spectroscopies
• Basics
• Examples of uses in Supramolecular Chemistry
• Examples of uses in Biochemistry
• Calorimetry
• Basics
• Examples of uses in Supramolecular Chemistry
• Examples of uses in Biochemistry
C – BINDING THEORY
• Definitions
• Equilibrium
• Thermodynamic treatise
• The role of ΔG
• Binding isotherms
• Titrations
• The role of Kass
• Practical example
• Calculation of the binding constant
• Old methods: pros/cons
• Non-linear regression
• Example: UV asbsorption, titration
• HG system vs. choice of the analytical method
• p factor
• Examples
• Kass regime
• Analytical methods: pros/cons
• NMR
• UV-vis + luminescence
• ITC
• Binding stoichiometry
• Job's method
• Kass dependence
• Pros/cons
• Considerations on molecular structure
• Concentration range dependence
D – COOPERATIVITY AND MULTIVALENCY
• Definitions
• Examples
• Supramolecular materials: example
• Biochemistry: example
• Cooperativity
• Allostery
• Chelating
• Allostery
• Definitions
• The case of hemoglobin
• Allostery vs. a reference system
• Cooperativity: details
• Microscopic vs macroscopic level
• Hill plot
• Effective molarity
• Thermodynamic considerations
• Example: Lehn's CuI helicates
E – SELF ASSEMBLY
• Definitions
• Design principles
• Directional approach
• Symmetry approach
• Panelling
• Examples
• Fujita's macrocycles
• Anderson's wheels
• Covalent preorganisation
• Thermodynamic considerations
• Dynamic covalent chemistry: overview
Testi/Bibliografia
Suggested readings:
• Atwood & Steed, "Encyclopedia of Supramolecular Chemistry"• Fabbrizzi, "From simple to complex compounds"
• Lehn, Science 2002, 295, 2400-2403.
• Schalley (ed.), "Analytical Methods in Supramolecular Chemistry"
• Goodsell, "Bionanotechnology"
Metodi didattici
Lectures will focus on the fundamental concepts of modern supramolecular chemistry, by describing i) the equilibria involved in intermolecular interactions, ii) the thermodynamics aspects of binding events, iii) the main analytical methods employed to describe and quantify supramolecular interactions
As concerns the teaching methods of this course unit, all students must attend Module 1, 2 on Health and Safety, online.
Modalità di verifica e valutazione dell'apprendimento
Oral examination: discussion on a case study
Strumenti a supporto della didattica
Video projector and blackboard for lectures.
Electronic handouts and pdf notes will be distributed via Virtuale.Orario di ricevimento
Consulta il sito web di Andrea Fermi