Synthesis, aggregation, and binding behavior of synthetic amphiphilic receptors.
Amphiphilic bowl-shaped receptor molecules have been synthesized starting from diphenylglycoluril. Upon dispersion in water, these molecules self-assemble to form vesicles that bind neutral guests and alkali metal ions. In the case of bis(alkylester)-modified receptor compound 4, electron microscopy reveals that an increase in the size of the alkali metal ion (from Na(+) or K(+) to Rb(+) and to Cs(+)) leads to a change in the shape of the aggregates, viz. from vesicles to tubules. Monolayer experiments suggest that this behavior is due to a change in the conformation of this amphiphilic receptor. In water, molecules of 4 have an elongated conformation that changes to a sandwich-like one upon binding of alkali metal ions. Binding studies with vesicles from the bis-ammonium receptors 6 and 9 and the guest 4-(4-nitrophenylazo)resorcinol (Magneson) reveal that below the critical aggregation concentration (CAC) of the amphiphile 1:1 host-guest complexes are formed with high host-guest association constants. Above the CAC, a host-guest ratio of 2:1 was observed that indicates that only the cavities on the outside of the vesicle can be occupied. In the case of the naphthalene walled compound 8 changes in the vesicle structure are induced by the organic guest Magneson.
Department of Organic Chemistry, NSR Center, University of Nijmegen, Toernooiveld, 6525 ED Nijmegen, The Netherlands.
A P
AP
Schenning
B
B
Escuder
J L
JL
van Nunen
B
B
de Bruin
D W
DW
Löwik
A E
AE
Rowan
S J
SJ
van der Gaast
M C
MC
Feiters
R J
RJ
Nolte
D002725:Chloroform / Q000737:chemistry; D004553:Electric Conductivity; D006863:Hydrogen-Ion Concentration; D008670:Metals / Q000737:chemistry; D008854:Microscopy, Electron; D010316:Particle Size; D011485:Protein Binding; D011487:Protein Conformation; D011956:Receptors, Cell Surface / Q000737:chemistry* / Q000378:metabolism*; D013501:Surface-Active Agents / Q000378:metabolism*; D014867:Water / Q000737:chemistry; D014961:X-Ray Diffraction
D008670:Metals; D011956:Receptors, Cell Surface; D013501:Surface-Active Agents; D014867:Water; D002725:Chloroform