99127 - BIOMIMETIC SUPRAMOLECULAR CHEMISTRY

Learning outcomes

At the end of the course the student has acquired knowledge of the properties and transformations of the main classes of supramolecular systems, the biomimetic approach to their design and application, the main techniques used for their characterization.

Course contents

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
• 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

• Approximations

• 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 – TOWARDS COMPLEXITY: SYSTEMS CHEMISTRY
• Definitions
• Dynamic Covalent Chemistry
• Thermodynamic vs. kinetic control: self assembly
• Out-of-equilibrium supramolecular systems
• Chemical fuels for the self-assembly and molecular motions
• Light as a chemical fuel

F – SUPRAMOLECULAR CHEMISTRY IN THE BIO-WORLD
• Complexation of biochemically relevant molecules
• Signalling in supramolecular chemistry: background
• Signalling and detection of biomolecules and metal ions
• Examples and outlook
• Applications of bio-inspired supramolecular systems
• Imaging
• Photodynamic therapy and theranostics
• Radiotherapy and tumor imaging
• Bionanotechnology: present and future applications

Readings/Bibliography

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"

• Schneider (ed.). “Supramolecular Systems in Biomedical Fields”

• Goodsell, "Bionanotechnology"

Teaching methods

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, iv) application of the basic concepts of supramolecular chemistry to natural and artificial biomimetic systems.

As per the teaching methods of this course unit, all students must attend Module 1, 2 on Health and Safety (online).

Assessment methods

Oral examination: discussion on a case study

Teaching tools

Video projector and blackboard for lectures.

Electronic handouts and pdf notes will be distributed via Virtuale.

Office hours

See the website of Andrea Fermi