title: Size-selective shell cross-linked interior functionalized siloxane nanocages.
abstract: A new structure, consisting of a shell cross-linked, 2 nm size siloxane nanocage containing propylamine groups tethered to the interior face of the shell was synthesized, starting with micelles of the surfactant molecule, (triethoxysilyl)propylcetylcarbamate. After hydrolysis of the ethoxysilyl groups and condensation and capping of the silanols to form a cross-linked, one-atom-layer-thick siloxane shell, the carbamate was converted to amine, releasing the cetyl group from the structure and resulting in the desired spherical nanocage. The intermediates in the synthesis process and the final structure were characterized by 1H and 29Si NMR, DLS, TEM, and mass spectroscopy. The amine groups tethered to the interior surface of the shell react readily with ninhydrin but do not interact with the larger ZnTPP, indicating molecular size selectivity by the cross-linked shell. The structure also exhibits confinement effect in the amine-catalyzed decarboxylation of acetoacetic acid, exhibiting higher activity and higher selectivity for acetal than (aminopropyl)triethoxysilane.
authors.affiliation: Department of Chemical and Biological Engineering, and Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208-3120, USA.
authors.forename: Young-Woong
authors.initials: YW
authors.lastname: Suh
authors.forename: Mayfair C
authors.initials: MC
authors.lastname: Kung
authors.forename: Yingmin
authors.initials: Y
authors.lastname: Wang
authors.forename: Harold H
authors.initials: HH
authors.lastname: Kung