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Mechanistically Different Mechanochromophores Enable Calibration and Validation of Molecular Forces in Glassy Polymers and Elastomeric Networks

Raphael Hertel, Maximilian Raisch, Michael Walter, Günter Reiter, Michael Sommer. Angew. Chem. Int. Ed. 2024, e202409369

sommer.jpgSterically distorted donor-acceptor p‑systems, termed DA springs, can be progressively planarized under mechanical load causing a bathochromic shift of the photoluminescence (PL) spectrum. By combining theory and experiment, we here use a simple linear force calibration for two different conformational mechanochromophores to determine molecular forces in polymers from the mechanochromic shift in PL wavelength during multiple uniaxial tensile tests. Two systems are used, i) a highly entangled linear glassy polyphenylene and ii) a covalent elastomeric polydimethylsiloxane network. The mean forces estimated by this method are validated using known threshold forces for the mechanochemical ring-opening reactions of two different spiropyran force probes. The agreement between both approaches underlines that these DA springs provide the unique opportunity for the online monitoring of local molecular forces present in diverse polymer matrices.(more...)



"Printing" on Polymer Single Crystals through Microregional Heating

Tianyu Wu, Haimu Ye, Xinyi Pan, Yaning He, Jun Xu, Günter Reiter. ACS Appl. Polym. Mater. 2024, 6, 14, 7969–7977

tianyu.jpgPolymer single crystals are composed of well-ordered polymer chains and possess a characteristic symmetric shape. If one can precisely control the microregional morphology, polymer single crystals have the potential to be used as functional templates for applications like information storage or cell culture. However, with current experimental approaches, it is rather difficult to generate predictable structures of defined size within polymer single crystals. Here, we propose a research strategy based on a combination of fluorescence labeling and microregional heating by irradiation with focused red light. This approach enabled us to locally heat single crystals while simultaneously following the thereby induced changes via fluorescence imaging with a micrometer lateral resolution. We found that polymers diffused out of the heated region within a stacked single crystal and thereby produced a hole at the irradiated location. (more...)


Mechanism for the Formation of Millimeter-Long Solid Filaments by Spin Coating Dilute Solutions of a Crystallizable Polymer

Da Huang, Thorsten Hugel, and Günter Reiter. Macromolecules 2024, 57, 3696–3705

huang.jpgWe have investigated the formation of millimeter-long filaments induced by spin-coating ca. 130 °C dilute para-xylene solutions of rapidly crystallizable polyethylene chains with a contour length in the micrometer range onto ca. 80 °C mica substrates. These filaments were radially oriented and accumulated on the periphery of the substrate. Our observations can be explained by the stretching of polymers through the flow field induced by spinning the solution on a solid substrate. The corresponding loss in conformational entropy emphasized attractive interactions between polymers, which resulted in the formation of bundles and their assembly into long filaments. Caused by a Plateau–Rayleigh-type instability of a liquid coating on a solid filament and due to crystallization, these filaments were decorated with various small-scale structures. (more...)


 

Liste der Veröffentlichungen

Transient cooperative processes in dewetting polymer melts
Sivasurender Chandran, Günter Reiter, PRL 116 (2016) 088301
Crystallization and Resulting Optical Properties of Thiophene-Based Oligomers
Sajedeh Motamen. Inaugural-Dissertation zur Erlangung des Doktorgrads der Fakultät für Mathematik und Physik der Universität Freiburg, 2016
Large area crystal surfaces of precisely sidebranched polyethylenes: Preparation, surface order and functionalization
Rainhard Machatschek. Inaugural-Dissertation zur Erlangung des Doktorgrades der Fakultät für Chemie und Pharmazie der Albert-Ludwigs-Universität Freiburg im Breisgau, 2016
Probing the Elasticity of Langmuir Polymer Films of High Molecular Weight Poly (γ-benzyl-L-glutamate)
Emna Khechine. Master Thesis im Studiengang M.Sc. Sustainable Materials, 2016
Self-assembled nanotubes and nanoribbons of aromatic diamide-esters
Asad Jamal. Inaugural-Dissertation zur Erlangung des Doktorgrads der Fakultät für Mathematik und Physik der Universität Freiburg, 2016
Formation and Optical Characterization of Single Crystals of Poly(3-Hexylthiophene) (P3HT), a Model Conjugated Polymer
John O. Agumba. Inaugural-Dissertation zur Erlangung des Doktorgrads der Fakultät für Mathematik und Physik der Universität Freiburg, 2016
History Dependent Temporal Changes of Properties of Thin Polymer Films
Günter Reiter. In: Non-equilibrium Phenomena in Confined Soft Matter. Ed. Simone Napolitano. Springer 2015
Consequences of a Single Double Bond within a Side-Group on the Ordering of Supra-Molecular Polymers
Roozbeh Shokri, Olga Guskova, Asad Jamal, Kaiwan Jahanshahi, Benjamin Isare, Laurent Bouteiller, Laurent Simon, Jens-Uwe Sommer, Günter Reiter. The Journal of Physical Chemistry, Part C 119 (2015) 22596–22603
Different surface sensing of the cell body and nucleus in healthy primary cells and in a cancerous cell line on nanogrooves
Patricia Davidson, Maxence Bigerelle, Günter Reiter and Karine Anselm. Biointerphases 10, 031004 (2015) / DOI: 10.1116/1.4927556
How Chain-Folding Crystal Growth Determines Thermodynamic Stability of Polymer Crystals
Xiaoming Jiang, Günter Reiter, Wenbing Hu. J. Phys. Chem. B, 120 (2016) 566–571
Stabilization of nuclei of lamellar polymer crystals: Insights from a comparison of the Hoffman-Weeks line with the crystallization line
Jun Xu, Barbara Heck, Hai-Mu Ye, Jing Jiang, Yi-Ren Tang, Jin Liu, Bao-Hua Guo, Renate Reiter, Dongshan Zhou, Günter Reiter. Macromolecules 49 (2016) 2206–2215
Role of Preparation Pathways and Tacticity on the Non-Equilibrium Dynamcis of Polystyrene Films
Rishab Handa. Master Thesis im Studiengang M.Sc. Sustainable Materials, 2016
Variation of the contact resistance with electric current for gold electrodes on a squaraine single crystal
Leonid Govor, Guenter Reiter, and Jurgen Parisi. Phys. Status Solidi A 212 (2015) 2738–2746, DOI 10.1002/pssa.201532241
Simulation of secondary nucleation of polymer crystallization via a model of microscopic kinetics
Kun-Lun Xu, Bao-Hua Guo, Renate Reiter, Günter Reiter, Jun Xu. Chinese Chemical Letters 26, 1105–1108 (2015) / DOI: 10.1016/j.cclet.2015.06.002
From holes to drops to toroids: Conditions for the transcription of surface patterns into three-dimensional morphologies via rim instabilities in the course of dewetting
Samer Al Akhrass, Laurent Vonna and Günter Reiter. In: Polymer Surfaces in Motion: Unconventional Patterning Methods, Eds. Juan Rodriguez-Hernandez and Carlos Drummond. Springer 2015
Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States
Sivasurender Chandran, Stefanie Dold, Amaury Buvignier, Kai-Steffen Krannig, Helmut Schlaad, Günter Reiter, and Renate Reiter. Langmuir 2015, 31, 6426−6435. DOI: 10.1021/acs.langmuir.5b01212
High Temperature Stability of Dewetting-Induced Thin Polyethylene Filaments
Bin Zhang, Jingbo Chen, Paul Freyberg, Renate Reiter, Rolf Mülhaupt, Jun Xu, Günter Reiter. Macromolecules 48, 1518–1523 (2015)
Triangular dewetting by symmetry breaking in blends of stiff and flexible polymers
Paul Freyberg. Inaugural-Dissertation zur Erlangung des Doktorgrades der Fakultät für Mathematik und Physik der Albert-Ludwigs-Universität Freiburg, 2015
Conductive atomic force microscopy measurements on organic nanocrystals
Sven Renkert. Master Thesis, Fakultät für Mathematik und Physik der Albert-Ludwigs-Universität Freiburg, 2014
The influence of the additive composition on degradation induced changes in poly(ethylene-co-vinyl acetate) during photochemical aging
Angelika Beinert, Cornelia Peike, Ines Dürr, Michael D. Kempe, Günter Reiter, Karl-Anders Weiß. 29th European PV Solar Energy Conference and Exhibition, 22-26 Sept. 2014, Amsterdam, The Netherlands
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