Bilayer Vesicles of Amphiphilic Cyclodextrins: Host Membranes That Recognize Guest Molecules

Patrick Falvey, C.W. Lim, Raphael Darcy, T. Revermann, U. Karst, Marcel Giesbers, Antonius T.M. Marcelis, Adina Lazar, Anthony W. Coleman, David Reinhoudt, B.J. Ravoo

    Research output: Contribution to journalArticleAcademicpeer-review

    151 Citations (Scopus)

    Abstract

    A family of amphiphilic cyclodextrins (6, 7) has been prepared through 6-S-alkylation (alkyl=n-dodecyl and n-hexadecyl) of the primary side and 2-O-PEGylation of the secondary side of a-, B-, and Y-cyclodextrins (PEG=poly(ethylene glycol)). These cyclodextrins form nonionic bilayer vesicles in aqueous solution. The bilayer vesicles were characterized by transmission electron microscopy, dynamic light scattering, dye encapsulation, and capillary electrophoresis. The molecular packing of the amphiphilic cyclodextrins was investigated by using small-angle X-ray diffraction of bilayers deposited on glass and pressure-area isotherms obtained from Langmuir monolayers on the air-water interface. The bilayer thickness is dependent on the chain length, whereas the average molecular surface area scales with the cyclodextrin ring size. The alkyl chains of the cyclodextrins in the bilayer are deeply interdigitated. Molecular recognition of a hydrophobic anion (adamantane carboxylate) by the cyclodextrin vesicles was investigated by using capillary electrophoresis, thereby exploiting the increase in electrophoretic mobility that occurs when the hydrophobic anions bind to the nonionic cyclodextrin vesicles. It was found that in spite of the presence of oligo(ethylene glycol) substituents, the B-cyclodextrin vesicles retain their characteristic affinity for adamantane carboxylate (association constant Ka=7.1×103 M-1), whereas -cyclodextrin vesicles have less affinity (Ka=3.2×103 M-1), and a-cyclodextrin or non-cyclodextrin, nonionic vesicles have very little affinity (Ka100 M-1). Specific binding of the adamantane carboxylate to B-cyclodextrin vesicles was also evident in competition experiments with B-cyclodextrin in solution. Hence, the cyclodextrin vesicles can function as host bilayer membranes that recognize small guest molecules by specific noncovalent interaction.
    Original languageUndefined
    Pages (from-to)1171-1180
    Number of pages10
    JournalChemistry: a European journal
    Volume11
    Issue number4
    DOIs
    Publication statusPublished - 2005

    Keywords

    • Amphiphiles
    • vesicles
    • Membranes
    • IR-53672
    • METIS-226788
    • Cyclodextrins
    • Molecular recognition

    Cite this

    Falvey, P., Lim, C. W., Darcy, R., Revermann, T., Karst, U., Giesbers, M., ... Ravoo, B. J. (2005). Bilayer Vesicles of Amphiphilic Cyclodextrins: Host Membranes That Recognize Guest Molecules. Chemistry: a European journal, 11(4), 1171-1180. https://doi.org/10.1002/chem.200400905
    Falvey, Patrick ; Lim, C.W. ; Darcy, Raphael ; Revermann, T. ; Karst, U. ; Giesbers, Marcel ; Marcelis, Antonius T.M. ; Lazar, Adina ; Coleman, Anthony W. ; Reinhoudt, David ; Ravoo, B.J. / Bilayer Vesicles of Amphiphilic Cyclodextrins: Host Membranes That Recognize Guest Molecules. In: Chemistry: a European journal. 2005 ; Vol. 11, No. 4. pp. 1171-1180.
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    abstract = "A family of amphiphilic cyclodextrins (6, 7) has been prepared through 6-S-alkylation (alkyl=n-dodecyl and n-hexadecyl) of the primary side and 2-O-PEGylation of the secondary side of a-, B-, and Y-cyclodextrins (PEG=poly(ethylene glycol)). These cyclodextrins form nonionic bilayer vesicles in aqueous solution. The bilayer vesicles were characterized by transmission electron microscopy, dynamic light scattering, dye encapsulation, and capillary electrophoresis. The molecular packing of the amphiphilic cyclodextrins was investigated by using small-angle X-ray diffraction of bilayers deposited on glass and pressure-area isotherms obtained from Langmuir monolayers on the air-water interface. The bilayer thickness is dependent on the chain length, whereas the average molecular surface area scales with the cyclodextrin ring size. The alkyl chains of the cyclodextrins in the bilayer are deeply interdigitated. Molecular recognition of a hydrophobic anion (adamantane carboxylate) by the cyclodextrin vesicles was investigated by using capillary electrophoresis, thereby exploiting the increase in electrophoretic mobility that occurs when the hydrophobic anions bind to the nonionic cyclodextrin vesicles. It was found that in spite of the presence of oligo(ethylene glycol) substituents, the B-cyclodextrin vesicles retain their characteristic affinity for adamantane carboxylate (association constant Ka=7.1×103 M-1), whereas -cyclodextrin vesicles have less affinity (Ka=3.2×103 M-1), and a-cyclodextrin or non-cyclodextrin, nonionic vesicles have very little affinity (Ka100 M-1). Specific binding of the adamantane carboxylate to B-cyclodextrin vesicles was also evident in competition experiments with B-cyclodextrin in solution. Hence, the cyclodextrin vesicles can function as host bilayer membranes that recognize small guest molecules by specific noncovalent interaction.",
    keywords = "Amphiphiles, vesicles, Membranes, IR-53672, METIS-226788, Cyclodextrins, Molecular recognition",
    author = "Patrick Falvey and C.W. Lim and Raphael Darcy and T. Revermann and U. Karst and Marcel Giesbers and Marcelis, {Antonius T.M.} and Adina Lazar and Coleman, {Anthony W.} and David Reinhoudt and B.J. Ravoo",
    year = "2005",
    doi = "10.1002/chem.200400905",
    language = "Undefined",
    volume = "11",
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    Falvey, P, Lim, CW, Darcy, R, Revermann, T, Karst, U, Giesbers, M, Marcelis, ATM, Lazar, A, Coleman, AW, Reinhoudt, D & Ravoo, BJ 2005, 'Bilayer Vesicles of Amphiphilic Cyclodextrins: Host Membranes That Recognize Guest Molecules', Chemistry: a European journal, vol. 11, no. 4, pp. 1171-1180. https://doi.org/10.1002/chem.200400905

    Bilayer Vesicles of Amphiphilic Cyclodextrins: Host Membranes That Recognize Guest Molecules. / Falvey, Patrick; Lim, C.W.; Darcy, Raphael; Revermann, T.; Karst, U.; Giesbers, Marcel; Marcelis, Antonius T.M.; Lazar, Adina; Coleman, Anthony W.; Reinhoudt, David; Ravoo, B.J.

    In: Chemistry: a European journal, Vol. 11, No. 4, 2005, p. 1171-1180.

    Research output: Contribution to journalArticleAcademicpeer-review

    TY - JOUR

    T1 - Bilayer Vesicles of Amphiphilic Cyclodextrins: Host Membranes That Recognize Guest Molecules

    AU - Falvey, Patrick

    AU - Lim, C.W.

    AU - Darcy, Raphael

    AU - Revermann, T.

    AU - Karst, U.

    AU - Giesbers, Marcel

    AU - Marcelis, Antonius T.M.

    AU - Lazar, Adina

    AU - Coleman, Anthony W.

    AU - Reinhoudt, David

    AU - Ravoo, B.J.

    PY - 2005

    Y1 - 2005

    N2 - A family of amphiphilic cyclodextrins (6, 7) has been prepared through 6-S-alkylation (alkyl=n-dodecyl and n-hexadecyl) of the primary side and 2-O-PEGylation of the secondary side of a-, B-, and Y-cyclodextrins (PEG=poly(ethylene glycol)). These cyclodextrins form nonionic bilayer vesicles in aqueous solution. The bilayer vesicles were characterized by transmission electron microscopy, dynamic light scattering, dye encapsulation, and capillary electrophoresis. The molecular packing of the amphiphilic cyclodextrins was investigated by using small-angle X-ray diffraction of bilayers deposited on glass and pressure-area isotherms obtained from Langmuir monolayers on the air-water interface. The bilayer thickness is dependent on the chain length, whereas the average molecular surface area scales with the cyclodextrin ring size. The alkyl chains of the cyclodextrins in the bilayer are deeply interdigitated. Molecular recognition of a hydrophobic anion (adamantane carboxylate) by the cyclodextrin vesicles was investigated by using capillary electrophoresis, thereby exploiting the increase in electrophoretic mobility that occurs when the hydrophobic anions bind to the nonionic cyclodextrin vesicles. It was found that in spite of the presence of oligo(ethylene glycol) substituents, the B-cyclodextrin vesicles retain their characteristic affinity for adamantane carboxylate (association constant Ka=7.1×103 M-1), whereas -cyclodextrin vesicles have less affinity (Ka=3.2×103 M-1), and a-cyclodextrin or non-cyclodextrin, nonionic vesicles have very little affinity (Ka100 M-1). Specific binding of the adamantane carboxylate to B-cyclodextrin vesicles was also evident in competition experiments with B-cyclodextrin in solution. Hence, the cyclodextrin vesicles can function as host bilayer membranes that recognize small guest molecules by specific noncovalent interaction.

    AB - A family of amphiphilic cyclodextrins (6, 7) has been prepared through 6-S-alkylation (alkyl=n-dodecyl and n-hexadecyl) of the primary side and 2-O-PEGylation of the secondary side of a-, B-, and Y-cyclodextrins (PEG=poly(ethylene glycol)). These cyclodextrins form nonionic bilayer vesicles in aqueous solution. The bilayer vesicles were characterized by transmission electron microscopy, dynamic light scattering, dye encapsulation, and capillary electrophoresis. The molecular packing of the amphiphilic cyclodextrins was investigated by using small-angle X-ray diffraction of bilayers deposited on glass and pressure-area isotherms obtained from Langmuir monolayers on the air-water interface. The bilayer thickness is dependent on the chain length, whereas the average molecular surface area scales with the cyclodextrin ring size. The alkyl chains of the cyclodextrins in the bilayer are deeply interdigitated. Molecular recognition of a hydrophobic anion (adamantane carboxylate) by the cyclodextrin vesicles was investigated by using capillary electrophoresis, thereby exploiting the increase in electrophoretic mobility that occurs when the hydrophobic anions bind to the nonionic cyclodextrin vesicles. It was found that in spite of the presence of oligo(ethylene glycol) substituents, the B-cyclodextrin vesicles retain their characteristic affinity for adamantane carboxylate (association constant Ka=7.1×103 M-1), whereas -cyclodextrin vesicles have less affinity (Ka=3.2×103 M-1), and a-cyclodextrin or non-cyclodextrin, nonionic vesicles have very little affinity (Ka100 M-1). Specific binding of the adamantane carboxylate to B-cyclodextrin vesicles was also evident in competition experiments with B-cyclodextrin in solution. Hence, the cyclodextrin vesicles can function as host bilayer membranes that recognize small guest molecules by specific noncovalent interaction.

    KW - Amphiphiles

    KW - vesicles

    KW - Membranes

    KW - IR-53672

    KW - METIS-226788

    KW - Cyclodextrins

    KW - Molecular recognition

    U2 - 10.1002/chem.200400905

    DO - 10.1002/chem.200400905

    M3 - Article

    VL - 11

    SP - 1171

    EP - 1180

    JO - Chemistry: a European journal

    JF - Chemistry: a European journal

    SN - 0947-6539

    IS - 4

    ER -