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    Calixarenes

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    Calixarenes are macrocyclic compounds formed from the reaction of phenols and aldehydes. They resemble a vase or cup shape with a hydrophobic cavity. Calixarenes can form host-guest complexes by trapping smaller guest molecules or ions in their cavity. They have applications in ion sensing and recognition, catalysis, and nanotechnology due to their cavity structure and ability to form well-defined complexes.

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    Calixarenes

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    Calixarenes are macrocyclic compounds formed from the reaction of phenols and aldehydes. They resemble a vase or cup shape with a hydrophobic cavity. Calixarenes can form host-guest complexes by trapping smaller guest molecules or ions in their cavity. They have applications in ion sensing and recognition, catalysis, and nanotechnology due to their cavity structure and ability to form well-defined complexes.

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    Calixarenes are macrocyclic compounds formed from the reaction of phenols and aldehydes. They resemble a vase or cup shape with a hydrophobic cavity. Calixarenes can form host-guest complexes by trapping smaller guest molecules or ions in their cavity. They have applications in ion sensing and recognition, catalysis, and nanotechnology due to their cavity structure and ability to form well-defined complexes.

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    16 views13 pages

    Calixarenes

    Uploaded by

    8ex5cqy8w3
    Calixarenes are macrocyclic compounds formed from the reaction of phenols and aldehydes. They resemble a vase or cup shape with a hydrophobic cavity. Calixarenes can form host-guest complexes by trapping smaller guest molecules or ions in their cavity. They have applications in ion sensing and recognition, catalysis, and nanotechnology due to their cavity structure and ability to form well-defined complexes.

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    Calixarene

    A calixarene is a macrocycle or cyclic oligomer based on a hydroxyalkylation product


    of a phenol and an aldehyde [1]. The word calixarene is derived from calix or chalice
    because this type of molecule resembles a vase and from the word arene that refers
    to the aromatic building block. Calixarenes have hydrophobic cavities that can hold
    smaller molecules or ions and belong to the class of cavitands known in Host-guest
    chemistry. Calixarene nomenclature is straightforward and involves counting the
    number of repeating units in the ring and include it in the name. A calix[4]arene has 4
    units in the ring and a calix[6]arene has 6. A substituent in the meso position Rb is
    added to the name with a prefix C- as in C-methylcalix[6]arene.
    C-Methylcalix[4]resorcinarene p-Methylcalix[6]arene
    Synthesis

    The aromatic components are derived from phenol, resorcinol or


    pyrogallol, For phenol, the aldehyde most often used is simply
    formaldehyde, while larger aldehydes (acetaldehyde, or larger) are
    generally required in condensation reactions with resorcinol and
    pyrogallol. The chemical reaction ranks under electrophilic aromatic
    substitutions followed by an elimination of water and then a second
    aromatic substitution. The reaction is acid catalyzed or base catalyzed.
    Calixarenes are difficult to produce because it is all too easy to end up
    with complex mixtures of linear and cyclic oligomers with different
    numbers of repeating units. With finely tuned starting materials and
    reaction conditions synthesis can also be surprisingly easy.
    In 2005, researchers produced a pyrogallol[4]arene by simply mixing a
    solvent-free dispersion of isovaleraldehyde with pyrogallol and a catalytic
    amount of p-toluenesulfonic acid in a mortar and pestle [2]. Calixarenes as
    parent compounds are sparingly soluble and are high melting crystalline
    solids [3].

    [2] Antesberger J, Cave GW, Ferrarelli MC, Heaven MW, Raston CL, Atwood JL (2005). "Solvent-free, direct
    synthesis of supramolecular nano-capsules". Chemical communications (Cambridge, England) . (7): 892-4. PMID
    15700072.
    Structure

    Calixarenes are characterized by a three-dimensional basket, cup or bucket


    shape. In calix[4]arenes the internal volume is around 10 cubic nanometers.
    Calixarenes are characterised by a wide upper rim and a narrow lower rim
    and a central annulus. With phenol as a starting material the 4 hydroxyl groups
    are intrannular on the lower rim. In a resorcin[4]arene 8 hydroxyl groups are
    placed extraannular on the upper ring. Calixarenes exist in different chemical
    conformations because rotation around the methylene bridge is not difficult. In
    calix[4]arene 4 up-down conformations exist: cone ( point group C2v,C4v), partial
    cone Cs, 1,2 alternate C2h and 1,3 alternate D2d. The 4 hydroxyl groups interact
    by hydrogen bonding and stabilize the cone conformation. This conformation is
    in dymamic equilibrium with the other conformations. Conformations can be
    locked in place with proper substituents replacing the hydroxyl groups which
    increase the rotational barrier. Alternatively placing a bulky substituent on the
    upper rim also locks a conformation. The calixarene based on p-tert-butyl
    phenol is also a cone [1].
    Applications

    Calixarenes are applied in enzyme mimetics, ion sensitive electrodes or sensors, selective
    membrames, non-linear optics [6]
    http://www.rsc.org/publishing/journals/CC/article.asp?doi=b502045j

    and in HPLC stationary phase [7].

    In addition, in nanotechnology calixarenes are used as negative resist for high-resolution


    electron beam lithography [8].
    A tetrathia[4]arene is found to mimic aquaporin proteins [6]. This calixarene adopts a 1,3-
    alternate conformation (methoxy groups populate the lower ring) and water is not contained
    in the basket but grabbed by two opposing tert-butyl groups on the outer rim in a pincer.
    The nonporous and hydrophobic crystals are soaked in water for 8 hours in which time the
    calixarene:water ratio nevertheless acquires the value of one.
    Calixarenes are able to accelerate reactions taking place inside the concavity by a
    combination of local concentration effect and polar stabilization of the transition state. An
    extended resorcin[4]arene cavitand is found to accelerate the reaction rate of a Menshutkin
    reaction between quinuclidine and butylbromide by a factor of 1600 [7].
    In heterocalixarenes the phenolic units are replaced by heterocycles [8], for instance by
    furans in calix[n]furanes and by pyridines in calix[n]pyridines. Calixarenes have been used
    as the macrocycle portion of a rotaxane and two calixarene molecules covalently joined
    together by the lower rims form carcerands.
    Applications: Host guest interactions

    Calixarenes are efficient sodium ionophores and are applied as such in


    chemical sensors. With the right chemistry these molecules exhibit great
    selectivity towards other cations.

    Calixarenes are used in commercial applications as sodium selective


    electrodes for the measurement of sodium levels in blood.

    Calixarenes also form complexes with cadmium, lead, lanthanides and


    actinides. [3] Calix[5]arene and the C70 fullerene in p-xylene form a ball-and-
    socket supramolecular complex. [4] calixarenes also form exo-calix
    ammonium salts with aliphatic amines such as piperidine. [4]
    Self assembly

    Resorcinarenes and pyrogallolarenes self-assembly lead to larger


    supramolecular structures [5]. Both in the crystalline state and in solution, they
    are known to form hexamers that are akin to certain Archimedean solids with an
    internal volume of around one cubic nanometer (nanocapsules).
    (Isobutylpyrogallol[4]arene)6 is held together by 48 intermolecular hydrogen
    bonds. The remaining 24 hydrogen bonds are intramolecular. The cavity is filled
    by a number of solvent molecules. [5]
    References

    • [1] Gutsche, C. David (1989). Calixarenes. Cambridge: Royal Society of Chemistry. ISBN 0-85186-385-X.
    • [2] Antesberger J, Cave GW, Ferrarelli MC, Heaven MW, Raston CL, Atwood JL (2005). "Solvent-free, direct

    synthesis of supramolecular nano-capsules". Chemical communications (Cambridge, England) . (7): 892-4.


    PMID 15700072.
    • [3] McMahon G, O’Malley S, Nolan K and Diamond D (2003). "Important Calixarene Derivatives – their

    Synthesis and Applications". Arkivoc Part (vii). Article


    • Nachtigall FF, Lazzarotto M and Braz FNJ (2002). "Interaction of Calix[4]arene and Aliphatic Amines: A
    [4]

    Combined NMR, Spectrophotometric and Conductimetric Investigation". Journal of the Brazilian Chemical
    Society 13 (3). Article
    • [5] Atwood JL, Barbour LJ, Jerga A (2002). "Organization of the interior of molecular capsules by hydrogen
    bonding". Proceedings of the National Academy of Sciences 99 (8): 4837-41. PMID 11943875.
    • [6] Thallapally PK, Lloyd GO, Atwood JL, Barbour LJ (2005). "Diffusion of water in a nonporous hydrophobic

    crystal". Angewandte Chemie (International ed. in English) 44 (25): 3848-51. PMID 15892031.
    • [7] Purse BW, Gissot A, Rebek J Jr (2005). "A deep cavitand provides a structured environment for the

    menschutkin reaction". Journal of the American Chemical Society 127 (32): 11222-3. PMID 16089433.
    Subodh Kumar, Dharam Paul, Harjit Singh (2006). "Syntheses, structures and interactions of
    [8]

    heterocalixarenes". Arkivoc 05-1699LU: 17 - 25. PMID. Article


    • Retrieved from "http://en.wikipedia.org/wiki/Calixarene"

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