1. Precise supramolecular control of surface coverage densities on polymer micro- and nanoparticles
- Author
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Zoe Domínguez, Khaleel I. Assaf, Werner M. Nau, Uwe Schedler, Shuai Zhang, Uwe Pischel, Mohamed Nilam, Andreas Hennig, and Thomas Thiele
- Subjects
Quantitative Biology::Biomolecules ,010405 organic chemistry ,Chemistry ,technology, industry, and agriculture ,Supramolecular chemistry ,Nanoparticle ,General Chemistry ,macromolecular substances ,Supramolecular control ,010402 general chemistry ,Mole fraction ,01 natural sciences ,0104 chemical sciences ,Quantitative Biology::Subcellular Processes ,Rhodamine ,chemistry.chemical_compound ,Chemical engineering ,Surface coverage densities ,Click chemistry ,Particle ,Surface modification ,Nanoparticles ,Azide ,Polymer - Abstract
Competitive occupation of surface-bound supramolecular hosts allows precise control of surface coverage densities on particles., We report herein the controlled surface functionalization of micro- and nanoparticles by supramolecular host–guest interactions. Our idea is to exploit the competition of two high-affinity guests for binding to the surface-bound supramolecular host cucurbit[7]uril (CB7). To establish our strategy, surface azide groups were introduced to hard-sphere (poly)methylmethacrylate particles with a grafted layer of poly(acrylic acid), and a propargyl derivative of CB7 was coupled to the surface by click chemistry. The amount of surface-bound CB7 was quantified with the high-affinity guest aminomethyladamantane (AMADA), which revealed CB7 surface coverage densities around 0.3 nmol cm–2 indicative of a 3D layer of CB7 binding sites on the surface. The potential for surface functionalization was demonstrated with an aminoadamantane-labeled rhodamine (Ada-Rho) as a second high-affinity guest. Simultaneous incubation of CB7-functionalized particles with both high-affinity guests, AMADA and Ada-Rho, revealed a simple linear relationship between the resulting surface coverage densities of the model fluorescent dye and the mole fraction of Ada-Rho in the incubation mixture. This suggests a highly modular supramolecular strategy for the stable immobilization of application-relevant molecules on particle surfaces and a precise control of their surface coverage densities.
- Published
- 2018