Materials Science and Technology of Polymers, Faculty of Science and Technology and MESA Institute for Nanotechnology, University of Twente, PO Box 217, 7500 AE Enschede, The Netherlands.
ACS Nano. 2010 Jan 26;4(1):137-42. doi: 10.1021/nn901109x.
Supramolecular microcontact printing was used to obtain controlled patterns consisting of quantum dots (QDs) functionalized at their periphery with beta-cyclodextrin (beta-CD) in combination with adamantyl terminated dendrimeric "glues". Functionalization of core--shell CdSe/ZnS QDs was achieved by surface ligation. Immobilization of the QDs from solution onto glass substrates printed with (a) adamantyl-terminated poly(propylene imine) dendrimers and (b) via direct microcontact printing of QDs onto the dendrimer layer both yielded stable and robust multilayer structures. The stability of the patterns was primarily due to multivalent supramolecular host--guest interactions between beta-CD located at the QD surface and adamantyl groups at the dendrimer periphery as the dendrimers acted as a "supramolecular glue". The surface-immobilized QDs were capable of forming host--guest complexes with other molecules of interest at binding cavities not occupied by adamantyl groups. Complex formation with ferrocene-functionalized molecules at these sites led to partial quenching of the luminescence emission of QDs demonstrating the principle for sensing using the QD multilayer structures.
超分子微接触印刷用于获得由量子点（QD）组成的受控图案，这些量子点在其外围用β-环糊精（β-CD）功能化，并与金刚烷基末端的树枝状“胶”结合。核壳 CdSe/ZnS QD 的功能化是通过表面键合实现的。将 QD 从溶液中固定到用（a）金刚烷基末端的聚（丙烯亚胺）树枝状聚合物和（b）通过 QD 直接微接触印刷到树枝状聚合物层上印刷的玻璃基底上，都得到了稳定且坚固的多层结构。图案的稳定性主要归因于位于 QD 表面的β-CD 和树枝状聚合物外围的金刚烷基之间的多价超分子主客体相互作用，因为树枝状聚合物充当“超分子胶”。表面固定的 QD 能够与未被金刚烷基占据的结合腔内的其他感兴趣的分子形成主客体配合物。与这些位点上的二茂铁功能化分子形成配合物导致 QD 发光发射的部分猝灭，证明了使用 QD 多层结构进行传感的原理。
