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Instructor: Dr. Marinella Sandros

Nanochemistry NAN 601. Instructor: Dr. Marinella Sandros. Lecture 8: Supramolecular Chemistry. What is Supramolecular Chemistry ?. “Supramolecular chemistry is the chemistry of the intermolecular bond, covering the structures and functions of the entities formed by the association

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Instructor: Dr. Marinella Sandros

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  1. Nanochemistry NAN 601 • Instructor: • Dr. MarinellaSandros Lecture 8: Supramolecular Chemistry

  2. What is Supramolecular Chemistry ? “Supramolecular chemistry is the chemistry of the intermolecular bond, covering the structures and functions of the entities formed by the association of two or more chemical species” J.-M- Lehn "Supramolecular chemistry is defined as chemistry ‘beyond the Molecule’, as chemistry of tailor shaped inter-molecular interaction.” F. Vögtle http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  3. What is Supramolecular Chemistry? • “Chemistry beyond the molecule” • “Chemistry of molecular assemblies and of the intermolecular bond.” • “The Chemistry of non-covalent bond.”

  4. Supramolecular chemistry involves investigating molecular systems in which the most important feature is that components are held together by intermolecular forces, not by covalent bonds. Atoms Molecules Molecules Supermolecules Covalent Interactions Non-Covalent Interactions

  5. Supramolecular Chemistry http://www.tfp.uni-karlsruhe.de/Summerschool/Lectures/voegtle1.pdf

  6. Supramolecular Chemistry • Where did it come from? Inspired from biology and built on the shoulders of traditional synthetic organic chemistry. • Why does it deserve to be a field of study all its own? The next logical step in synthetic chemistry; understanding and interface with the biological world; nanotechnology http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  7. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  8. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  9. Lock and Key Principle http://www.waltry.f2s.com/lectures/supra-lec2.pdf

  10. Beyond Host/Guest Chemistry • Molecular Self-Assembly: Process by which 2 or more molecules interact from a larger structure or organization. • Super-Molecule: A complex formed by molecular self-assembly which contains a discrete number of subunits. http://www.waltry.f2s.com/lectures/supra-lec2.pdf

  11. Covalent Bond Energies http://www.waltry.f2s.com/lectures/supra-lec2.pdf

  12. Non-Covalent Interactions: Electrostatic

  13. Hydrogen-Bonded Interactions

  14. Hydrogen Bond http://www.waltry.f2s.com/lectures/supra-lec2.pdf

  15. -  Interactions http://www.waltry.f2s.com/lectures/supra-lec2.pdf

  16. Dispersion Forces http://www.waltry.f2s.com/lectures/supra-lec2.pdf

  17. Hydrophobic Effect http://www.waltry.f2s.com/lectures/supra-lec2.pdf

  18. Coordination Bonds http://www.waltry.f2s.com/lectures/supra-lec2.pdf

  19. Supramolecular: Biology • The study of non-covalent interactions is crucial to understanding many biological processes from cell structure to vision that rely on these forces for structure and function. Biological systems are often the inspiration for supramolecular research. http://en.wikipedia.org/wiki/Supramolecular_chemistry

  20. Example :DNA

  21. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  22. How to make a receptor ? people.bio.aau.dk/.../PowerPoint/Supramolecular%20chemistry.ppt

  23. Biotin-Streptavidin malina.ichf.edu.pl/educ/.../WYKLAD_SUPRA_NANO1_2005.ppt

  24. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  25. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  26. Answer??? http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  27. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  28. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  29. Forces Involved in Self-Assembly: http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  30. Interaction Energies http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  31. Chelate Effect • Two donor atoms linked together = a chelate (claw) • Chelate ligands form much more stable metal complexes than monodentate related ligands (up to 105 times as stable) • Ni2+ + L Formation Constants: • L = NH3 en trien 2,3,2 • 8.12 13.54 13.8 16.4 better complementarity faculty.swosu.edu/tim.hubin/InorganicLects/InorgCh12.2.ppt

  32. Chelate Effect Why is favorable?? Thermodynamic Reasons for the Chelate Effect = Entropy

  33. Macrocylic Effect Macrocyclicchelate complexes are up 107 times more stable than non-cyclic chelates with the same number of donors • Ni(trien)2+ + H+ Ni2+ + H4trien4+ t½ = 2 seconds • Ni(cyclam)2+ + H+ Ni2+ + H4cyclam4+ t½ = 2 years • Connecting all of the donors (having no end group) makes k-2 important • Breaking the first M—L bond requires major ligand deformation • The increase in Ea required greatly slows down k-2 faculty.swosu.edu/tim.hubin/InorganicLects/InorgCh12.2.ppt

  34. Macrocylic Effect • The result is a very stable complex as kd becomes miniscule

  35. http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  36. Valinomycin http://www.waltry.f2s.com/lectures/supra-lec1.pdf

  37. Self-Assembly http://www.ciam.unibo.it/photochem/Ri.mo_03.pdf

  38. Supramolecular Assembly • They allow access to nanoscale objects using a bottom-up approach in far fewer steps than a single molecule of similar dimensions. • The process by which a supramolecular assembly forms is called molecular self-assembly. Some try to distinguish self-assembly as the process by which individual molecules form the defined aggregate. Self-organization, then, is the process by which those aggregates create higher-order structures. http://en.wikipedia.org/wiki/Supramolecular_assembly

  39. http://www.ciam.unibo.it/photochem/Ri.mo_03.pdf

  40. Self-Organization and Self-Assembly http://www.ciam.unibo.it/photochem/Ri.mo_03.pdf

  41. Important Features http://www.ciam.unibo.it/photochem/Ri.mo_03.pdf

  42. Molecular Imprinting http://www.esonn.fr/0oldweb/ESONN04/Lectures/esonn_2004_Mascini3.pdf

  43. Imprinted Polymer-coated QCM Sensors

  44. Molecular Imprinted Polymers http://www.google.com/search?client=safari&rls=en&q=molecular+imprinting+ppt&ie=UTF-8&oe=UTF-8

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