Crystallography of Supramolecular Compounds

The Supramolecular Compounds refer to organised multi-molecular assemblies and associated phenomena. The stability and the properties of these compounds strongly involve structural three-dimensional (3D) information. The crystal itself can be considered as a giant supermolecule. Thus, a thorough understanding of crystal structures and crystal growth provides a unique information on the intermolecular interactions. Indeed, each crystal reflects in a particular way the recognition properties of molecules. More so, modern crystallography allows to study in detail two or three-component crystalline solids in which the recognition processes can be seen from the structural standpoint. Crystallography of smaller and smaller single crystals, faster and faster experiments, time-resolved x-ray crystallography, are extremely potent source of physico-chemical information. The present Advanced Study Institute (A.S.I.) - which was planned five years ago as the 22nd Course of the International School of Crystallography (director: T. L. BLUNDELL), 1-11 June 1995, E. Majorana Centre, Erice, Italy - is probably the first international meeting specifically devoted to the Crystallography of Supramolecular Compounds. The presence of crystallographers, chemists and physicists enhanced the coherence of the typical sequence: Conception and Design - Synthesis - Structure and Visualisation - Properties. The interactive and interdisciplinary character of this research is central to the development of general structural models for a large spectrum of compounds: ionophores, cryptates, fullerenes, calixarenes, cyclodextrins, cyclotriveratrylenes, pillar type compounds, zeolites, hydrates, solvates and others.

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Supramolecular compounds are multi-molecular assemblies possessing a great deal of structural, three-dimensional information. This is the first work to deal specifically with crystallographic studies combined with other methodologies, such as molecular dynamics, thermodynamics, NMR and atomic force microscopy. A wide range of supramolecular systems - ranging from atoms to single 5 kDa molecules to high polymers - involve molecular recognition based on non-covalent interactions having a precise geometry. The work focuses on general structural concepts as the basis for the chemical synthesis of preconceived compounds and devices, such as switches, sensors and biomimetic systems. Further progress will come from the imprinting of structural information into molecular components that spontaneously proceed to self-organization. The contributions of crystallographers, chemists, photochemists and physicists enhances the typical sequence: conception and design - synthesis - structure and visualization - properties - applications, taking the reader from first principles to the very forefront of the latest achievements.

Contenu
1) An introduction to the crystallography of supramolecular compounds..- 2) Association of helical peptides and ion channels..- 3) On molecular recognition in fullerene chemistry..- 4) Long range order in organized monolayers..- 5) Applications of the Cambridge Structural Database in the study of non-covalent interactions..- 6) Solvent and dynamic effects on the structure of alkali cation complexes of the t-butyl-calix[4]arene anion: MD and FEP computer investigations on the Na+/Cs+ binding affinity..- 7) Solid state NMR in inclusion compounds..- 8) The single crystal as a super molecule..- 9) New layered and pillared-type compounds, their intercalation chemistry and applications..- 10) Molecular tectonics..- 11) Symmetry in spheroalcanes, fullerenes, tubules and other column-like aggregates..- 12) Stability, solvent patterns and molecular recognition in cyclodextrins..- 13) Constitution and stability of clathrate hydrates..- 14) Cyclodextrins and fragments of starch and cellulose: crystal structures, self-assembly and hydrogen bonding..- 15) Clathration and solvation of molecules..- 16) Inclusion compounds: relating structure to kinetics and thermodynamics..- 17) The self-assembly of guanosine derivatives and folic acid..- 18) Tailor-made auxiliaries for the control of nucleation, growth and dissolution of crystals..- 19) Synthetic receptors: a modular approach to large structures..- 20) Structural models of biological significance from supramolecular systems..- 21) How DNA is recognized by proteins.- 22) Catalytic antibodies: an intriguing host-guest system..- 23) Supramolecular Organization of keratinized tissue..- 24) Molecular recognition: the lipocalins..- 25) Supramolecular photochemical reactions of organic molecules adsorbed on porous crystalline zeolites..- 26) Topics in supramolecular chemistry..- Appendix Tutorials on Molecular Modelling.- 1) Introduction to conformational analysis with the macromodel software..- A. Varnek.- G. Wipff.- 2) Display of dynamic Structures from molecular dynamics simulations in aqueous/non-aqueous solutions. Comparison with X-ray structures..- A. Varnek.- E. Engler.- M. Lauterbach.- L. Troxler.- G. Wipff.- 3) Harmony: the supramolecular database management system..- M. Bailly.- E. Eliopoulos.- G. Tsoucaris.- 4) Molecular graphics approaches in structure prediction and determination..- E. Eliopoulos.- I. M. Mavridis.- 5) An interactive-kinetic approach to the study of supramolecular structures..- E. Eliopoulos.- I. M. Mavridis.- Attached PC floppy disk.- 6) The Cambridge Structural Database. see p. 55.- F. Allen.- O. Johnson.