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Molecular Bottle Brushes with Positioned Selenols: Extending the Toolbox of Oxidative Single Polymer Chain Folding with Conformation Analysis by Atomic Force Microscopy
Authors:Emmanuelle Schué  Alexey Kopyshev  Jean-François Lutz  Hans G. Börner
Affiliation:1. Laboratory for Organic Synthesis of Functional Systems, Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany;2. Institute of Physics and Astronomy, University of Potsdam, 14476 Potsdam, Germany;3. Universiteć de Strasbourg, CNRS, Institut Charles Sadron UPR22, 23 rue du Loess, Strasbourg 67034 Cedex 2, France
Abstract:A synthesis route to controlled and dynamic single polymer chain folding is reported. Sequence-controlled macromolecules containing precisely located selenol moieties within a polymer chain are synthesized. Oxidation of selenol functionalities lead to diselenide bridges and induces controlled intramolecular crosslinking to generate single chain collapse. The cyclization process is successfully characterized by SEC as well as by 1H NMR and 2D HSQC NMR spectroscopies. In order to gain insight on the molecular level to reveal the degree of structural control, the folded polymers are transformed into folded molecular brushes that are known to be visualizable as single molecule structures by AFM. The “grafting onto” approach is performed by using triazolinedione−diene reaction to graft the side chain polymers. A series of folded molecular brushes as well as the corresponding linear controls are synthesized. AFM visualization is proving the cyclization of the folded backbone by showing globular objects, where non-folded brushes show typical worm-like structures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 154–162
Keywords:atomic force microscopy (AFM)  diselenide  grafted polymers  molecular bottle brushes  sequence-controlled polymers  single chain folding
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