Han, B. H. and M. Antonietti (2002). "Cyclodextrin-based pseudopolyrotaxanes as t emplates for the generation of porous silica materials.

" Chemistry of Materials 14(8): 3477-3485. The in situ formed supramolecular assemblies of cyclodextrins with nonio nic surfactants, poly(ethylene glycol), poly(propylene glycol), and block copoly mer, so-called pseudopolyrotaxanes, were used as porogens for the generation of porous silica materials. The resulting structures are characterized with nitroge n sorption experiments, transmission electron microscopy, and small-angle X-ray scattering. It was shown that the pore structure replicates the structure of the original supramolecular template, i.e., at pH 2.0, the cyclodextrins are thread ed by the polymer, and a short tubelike morphology of the pores is found. At hig her pH values, the aggregation of the pseudopolyrotaxanes toward bundle domains leads to larger pores. Polarz, S., B. Smarsly, et al. (2001). "From cyclodextrin assemblies to porous m aterials by silica templating." Angewandte Chemie-International Edition 40(23): 4417-+. Smarsly, B., S. Polarz, et al. (2001). "Preparation of porous silica materials v ia sol-gel nanocasting of nonionic surfactants: A mechanistic study on the selfaggregation of amphiphiles for the precise prediction of the mesopore size." Jou rnal of Physical Chemistry B 105(43): 10473-10483. Sol-gel nanocasting is used to imprint the soft-matter structures of lyo tropic phases of nonionic n-alkylpoly(ethylene oxide) amphiphiles ("CxEy") into solid porous silica. Small angle X-ray scattering (SAXS), nitrogen sorption, and transmission electron microscopy (TEM) are used to investigate the dependence o f the porosity on the block lengths or the block volumes, respectively. It is fo und that the size of the mesopores is a function of the lengths/volumes of both the alkyl chain (N-A) and the PEO block (N-B). Moreover, the materials contain a substantial degree of additional microporosity. A quantitative model is develop ed that relates the amphiphile organization during the nanocasting to the size o f the mesopores and the microporosity. In particular, it turns out that dependin g on the number of EO units a fraction of the PEO chains contributes to the meso porosity, while a significant portion leads to additional micropores. This model provides a quantitative description of the distribution of the hydrophobic and hydrophilic blocks within the lyotropic phase itself. Our findings indicate that the interface areas b(2) of single surfactant chains are a function of the bloc k lengths, which can be described by a scaling law b(2) proportional to (NANB0.4 )-N-0.16. Mixtures of chemically equivalent amphiphiles with different block rat ios are studied in further detail. It is seen that every pore size between the s ize originating from the "parent" templates can be adjusted simply by mixing var ious amounts of two surfactants, proving that true mixed phases act as a templat e for the silica pores.