title: A new family of nonionic dendritic amphiphiles displaying unexpected packing parameters in micellar assemblies.
abstract: In this paper we report on the synthesis of a new family of nonionic dendritic amphiphiles that self-assemble into defined supramolecular aggregates. Our approach is based on a modular architecture consisting of different generations of hydrophilic polyglycerol dendrons [G1-G3] connected to hydrophobic C(11) or C(16) alkyl chains via mono- or biaromatic spacers, respectively. All amphiphiles complex hydrophobic compounds as demonstrated by solubilization of Nile Red or pyrene. The structure of the supramolecular assemblies as well as the aggregation numbers are strongly influenced by the type of the dendritic headgroup. While the [G1] amphiphiles form different structures such as ringlike and fiberlike micelles, the [G2] and [G3] derivatives aggregate toward spherical micelles of low polydispersity clearly proven by transmission electron microscopy (TEM) measurements. In the case of the biaromatic [G2] derivative, the structural persistence of the micelles allowed a three-dimensional structure determination from the TEM data and confirmed the aggregation number obtained by static light scattering (SLS) measurements. On the basis of these data, molecular packing geometries indicate a drastic mass deficit of alkyl chains in the hydrophobic core volume of spherical micelles. It is noteworthy that these highly defined micelles contain as little as 15 molecules and possess up to 74% empty space. This behavior is unexpected as it is very different from classical detergent micelles such as sodium dodecyl sulfate (SDS), where the hydrophobic core volume is completely filled by alkyl chains.
authors.affiliation: Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin, Germany.
authors.forename: Britta
authors.initials: B
authors.lastname: Trappmann
authors.forename: Kai
authors.initials: K
authors.lastname: Ludwig
authors.forename: Michał R
authors.initials: MR
authors.lastname: Radowski
authors.forename: Anuj
authors.initials: A
authors.lastname: Shukla
authors.forename: Andreas
authors.initials: A
authors.lastname: Mohr
authors.forename: Heinz
authors.initials: H
authors.lastname: Rehage
authors.forename: Christoph
authors.initials: C
authors.lastname: Böttcher
authors.forename: Rainer
authors.initials: R
authors.lastname: Haag
mesh_terms: D050091:Dendrimers / Q000138:chemical synthesis / Q000737:chemistry*; D005990:Glycerol / Q000138:chemical synthesis / Q000737:chemistry; D057927:Hydrophobic and Hydrophilic Interactions; D008027:Light; D008823:Micelles; D046529:Microscopy, Electron, Transmission; D008958:Models, Molecular; D008968:Molecular Conformation; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry; D012542:Scattering, Radiation
chemical_list: D050091:Dendrimers; D008823:Micelles; D011108:Polymers; C043941:polyglycerol; D005990:Glycerol