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    Chap4 - Autoassemblage Chimie Supramoléculaire

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    Paul
    This document discusses molecular machines and rotaxanes. It describes how catenanes and rotaxanes are formed through the inclusion of cyclodextrins on guest molecules. Various strategies for synthesizing rotaxanes are presented, including the use of pseudorotaxanes and stoppers. Applications of rotaxanes include their use in molecular muscles, drug delivery, recognition, hydrogels, and as templates for nanoporous materials. Diagrams illustrate the structures of rotaxanes and how they self-assemble.

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    Chap4 - Autoassemblage Chimie Supramoléculaire

    Uploaded by

    Paul
    23 views26 pages
    This document discusses molecular machines and rotaxanes. It describes how catenanes and rotaxanes are formed through the inclusion of cyclodextrins on guest molecules. Various strategies for synthesizing rotaxanes are presented, including the use of pseudorotaxanes and stoppers. Applications of rotaxanes include their use in molecular muscles, drug delivery, recognition, hydrogels, and as templates for nanoporous materials. Diagrams illustrate the structures of rotaxanes and how they self-assemble.

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    This document discusses molecular machines and rotaxanes. It describes how catenanes and rotaxanes are formed through the inclusion of cyclodextrins on guest molecules. Various strategies for synthesizing rotaxanes are presented, including the use of pseudorotaxanes and stoppers. Applications of rotaxanes include their use in molecular muscles, drug delivery, recognition, hydrogels, and as templates for nanoporous materials. Diagrams illustrate the structures of rotaxanes and how they self-assemble.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    23 views26 pages

    Chap4 - Autoassemblage Chimie Supramoléculaire

    Uploaded by

    Paul
    This document discusses molecular machines and rotaxanes. It describes how catenanes and rotaxanes are formed through the inclusion of cyclodextrins on guest molecules. Various strategies for synthesizing rotaxanes are presented, including the use of pseudorotaxanes and stoppers. Applications of rotaxanes include their use in molecular muscles, drug delivery, recognition, hydrogels, and as templates for nanoporous materials. Diagrams illustrate the structures of rotaxanes and how they self-assemble.

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    © All Rights Reserved
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    of 26

    Un exemple de machine moléculaire

    (Stoddart, UCLA, USA)


    Les catenanes
    Vers des « muscles » moleculaires
    Formation des rotaxanes
    par complexes d’inclusion
    de cyclodextrines
    Stratégies de synthèse des Rotaxanes

    Pseudo rotaxanes
    complexation stopper

    Rotaxanes
    Un exemple de Rotaxane

    Selected CD rotaxanes. (X-ray structure of 5 ) Stannier et al, Chem. Commun,


    2001, 493
    Changes in the fluorescence of an azobenzene
    rotaxane(F395 ) emission at 395 nm; F520 ) emission at 520
    nm) along with irradiation time. Light sources of 360 and
    430 nm were
    alternated every 2 min.

    45%
    25%

    Amplification
    Répétabilité
    Qu, D. H.; Wang, G. C.; Ren, J.; Tian, H. Org. Lett. 2004, 6, 2085.
    Daisy chain inclusion compounds and rotaxanes (E ) end group): (a) cyclic monomer ([1]-
    rotaxane); (b) cyclic dimer ([2]-rotaxane); (c) cyclic trimer ([3]-rotaxane); (d) polymer (daisy chain
    polyrotaxane).

    Pseudo-rotaxanes Par association


    Supra Moleculaire
    Pseudo-rotaxanes: un exemple
    De polymère supramoléculaire

    Groupement cinnamoyl
    a-
    CD
    b-CD
    Adamantane

    Miyauchi, M.; Harada, A. J. Am. Chem. Soc. 2004, 1267, 2984


    General reaction scheme for the
    synthesis of CD polyrotaxanes

    Insertion le long du polymère


    Ex: aCD/ PEO

    Polymérisation du complexe d’inclusion


    Ex 4,4’bipyridine/ bCD et Ni2+
    Formation de pseudorotaxane et de rotaxanes

    PEO

    Stopper

    Harada, A., Acc. Chem. Res, 2001, 34, 456-464


    STM picture of a single aCD-PEO
    polyrotaxane;
    single a-CD rings are visible

    Molecular abacus 2. A cyclodextrin bead (or two) can be manipulated along a polymer
    chain by means of scanning tunneling microscopy.

    Shigekawa, H.; Miyake, K.; Sumaoka, J.; Harada, A.; Komiyama, M. J. Am.
    Chem. Soc. 2000, 122, 5411.
    (a) TEM of a single bCD pseudopolyrotaxane
    created by coordination of 4,4’-bipyridine by
    Ni2+.

    Ni2+
    +

    b-CD

    Liu, Y.; Zhao, Y. L.; Zhang, H. Y.; Song, H. B. Angew. Chem.,


    Int. Ed. Engl. 2003, 42, 3260
    STM picture of single polyazomethine
    polyrotaxane 9

    Liu, Y.; Zhao, Y.-L.; Zhang, H.-Y.; Li, X.-Y.;


    Liang, P.; Zhang, X.-Z.; Xu, J.-J. Macromolecules
    2004, 37, 6362
    Synthesis of polyrotaxane 9 by
    polycondensation of the CD inclusion
    compounds of a benzidine derivative and
    terephthalaldehyde
    Polymères supra-moléculaires à base cyclodextrines

    Schematic illustration of supramolecular gels formed from polymers with


    azobenzene and aCD side groups

    Takashima, Y.; Nakayama, T.; Miyauchi, M.; Kawaguchi, Y.; Yamaguchi, H.; Harada,
    A. Chem. Lett. 2004, 33, 890.
    Synthesis of Novel Supramolecular
    Assemblies Based on Hyaluronic Acid
    Derivatives Bearing Bivalent b-Cyclodextrin
    and Adamantane Moieties
    Aurelia Charlot and Rachel Auzely-Velty,
    Macromolecules 2007, 40, 1147-1158

    Schematic representation of the targeted physical networks in which


    monovalent and divalent bCD/adamantane complexes play the role of
    junction points.
    Tubular CD polymers: principe

    aCD
    PEO Polyrotaxane
    stoppers

    Epichlorohydrine
    NaOH(10%)

    NaOH 25%
    STM pictures of single a-CD molecular tubes
    threaded on linear polymer (left) and star-shaped
    polymer (right).

    Okumura, Y.; Ito, K.; Hayakawa, R.; Nishi, T. Langmuir 2000, 16, 10278.
    Applications

    •Solubilisation de polymères
    •Protection des polymères polyconjugués
    •Drug Delivry
    •Reconnaissance et targeting
    •Hydrogels et formation de réseaux
    •Template pour la synthèse de systèmes nanoporeux
    Schematic drawing of physical cross-linking by molecular tubes leading to hydrogels.
    Ikeda, T.; Ooya, T.; Yui, N. Macromol. Rapid Commun. 2000, 21, 1257.
    (left) TEM image of silica materials templated by pseudopolyrotaxanes of a-CD and
    poly(imino-hexamethyleneiminodecamethylene).
    (right) Corresponding pore size distribution, derived from nitrogen adsorption-desorption
    isotherms.

    Han, B.-H.; Smarsly, B.; Gruber, C.; Wenz, G. Microporous Mesoporous


    Mater. 2003, 66, 127.

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