Abstract
In this contribution we review our recent progress in studies that aim at the understandingof the relationship between structure and surface reactivity of organic thin films on the one hand,and at the micro- and nanofabrication of bioreactive or biocompatible platforms on the other hand.Self-assembled monolayers (SAMs) of n,n′-dithiobis(N-hydroxysuccinimidyl-n-alkanoate) exposingNHS reactive ester groups were studied as model systems for immobilization reactions of DNA, proteins,and receptors. Reaction kinetics and activation energies were determined quantitatively at lengthscales ranging from millimeters down to nanometers using, for example, surface infrared spectroscopyand in situ inverted chemical force microscopy (iCFM), respectively. The increase in conformationalorder with increasing alkane segment length was found to result in reduced reactivity due to stericcrowding. This drawback of highly organized monolayer architectures and the inherently limited loadingcan be circumvented by utilizing well-defined macromolecular thin films. Using amine-terminated polyamidoamine(PAMAM) dendrimers immobilized via soft lithography, as well as scanning probe lithography (SPL) approaches(dip-pen nanolithography, DPN) on NHS ester surfaces, robust micrometer and submicrometer patterned(bio)reactive surfaces, which allow one to achieve high molecular loading in coupling reactions forchip-based assays and sensor surfaces, were fabricated. Covalent coupling afforded the required robustnessof the patterned assemblies. Finally, we address micro- and nanopatterned bilayer-based systems.SPL was applied in order to fabricate nanoscale biocompatible supramolecular architectures on solidsupports. The adsorption of vesicles onto lipid bilayers was spatially controlled and directed insitu with nanometer-scale precision using SPL. This methodology, which provides a platform forresearch on proteins incorporated in the lipid bilayers comprising the vesicles, does not requirethat the vesicles are chemically labeled in order to guide their deposition.
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Acknowledgments
The authors would like to thank Dr. Mark A. Hempenius, Dr. Kenichi Morigaki, Dr. Toby Jenkins, Prof. Dr. Stephen D. Evans, Dr. Joseph M. Johnson, Dr. Peter Lenz, Prof. Dr. Curtis W. Frank, Prof. Dr. Steven G. Boxer, Dr. Victor Chechik, and Prof. Dr. Helmut Ringsdorf for very fruitful and stimulating discussions. This work has been financially supported in part by the European Community's Human Potential Programme under contract HPRN-CT-1999-00151 (G.J.V.), the EU Socrates program (D.I.R.), the MESA+ Institute for Nanotechnology of the University of Twente, the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (CW-NWO) (B.D.), also in the framework of the vernieuwingsimpuls program (H.S., C.L.F., A.S.).
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Schönherr, H. et al. (2005). Organic and Macromolecular Films and Assemblies as (Bio)reactive Platforms: From Model Studies on Structure–Reactivity Relationships to Submicrometer Patterning. In: Vancso, G.J. (eds) Ordered Polymeric Nanostructures at Surfaces. Advances in Polymer Science, vol 200. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_014
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