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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

Hydro-elastic interactions for shaping hydrodynamic properties in microfluidic flows
Claas-Hendrik Stamp, Inauguraldissertation der Fakultät für Mathematik und Physik, 2024
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
Mechanism for the formation of millimeter-long solid filaments by spin coating dilute solutions of a crystallizable polymer
Da Huang, Thorsten Hugel, Günter Reiter. Macromolecules 57 (2024) 3696–3705
Competing influences of cooling rate and diluent concentration on crystallization of poly(3-hexylthiophene)
Mina Alizadehaghdam, Farhang Abbasi, Günter Reiter. J. Phys. Chem. C 128 (2024) 4757–4765
“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
Identifying a Mesomorphic Boundary Zone within Polybutene-1 Single Crystals Emerging during a Crystal-Crystal Transformation
Jinlong Chen, Binghua Wang, Changyu Shen, Jingbo Chen, Günter Reiter, Bin Zhang. Macromolecules 56 (2023) 5050–5057
Determining the maximum melting temperature of polymer crystals from a change in morphology of dewetting rims
Gang Wang, Guotao Shi, Anchenyi Yang, Binghua Wang, Changyu Shen, Jingbo Chen, Günter Reiter, Bin Zhang. Polymer 274 (2023) 125874
Unraveling the complex polymorphic crystallization behavior of the alternating copolymer DMDS-alt-DVE
Valentina Pirela, Justine Elgoyhen, Radmila Tomovska, Jaime Martin Perez, Cuong Minh Quoc Le, Abraham Chemtob, Brahim Bessif, Barbara Heck, Günter Reiter, and Alejandro Müller. ACS Appl. Polym. Mater. 5 (2023) 5260–5269
Nucleation Assisted through the Memory of a Polymer Melt: A Different Polymorph Emerging from the Melt of another One
Brahim Bessif, Barbara Heck, Thomas Pfohl, Cuong Minh Quoc Le, Abraham Chemtob, Valentina Pirela, Justine Elgoyhen, Radmila Tomovska, Alejandro Müller, Günter Reiter. Macromolecules 56 (2023) 1461–1470
Tuning the hydraulic resistance by swelling-induced buckling of membranes in high-aspect-ratio microfluidic devices
Claas-Hendrik Stamp, Binyam Solomon, Friederike Lang, Efstathios Mitropoulos and Thomas Pfohl. Lab Chip 23 (2023) 3662-3670
Reversible Dehydration-Hydration of Poly(ethylene glycol) in Langmuir Monolayers of a Diblock Copolymer Inferred from Changes in Filament Curvature
Emna Khechine, Sebastian Noack, Helmut Schlaad, Jun Xu, Günter Reiter, Renate Reiter. Langmuir 39 (2023) 2710–2718
Improving the order of crystalline regions of poly(3-hexylthiophene) by crystallization from the self-nucleation domains
Mina Alizadehaghdam, Farhang Abbasia, and Günter Reiter. Thermochimica Acta 717 (2022) 179352
Determining Entanglement Molar Mass of Glassy Polyphenylenes Using Mechanochromic Molecular Springs
Maximilian Raisch, Günter Reiter, Michael Sommer. ACS Macro Lett. 11, 760–765, 2022
Editorial on the Special Topic “Polymer Crystallization”
Jun Xu, Günter Reiter, and Rufina G. Alamo. Crystals 12, 618 (2022)
In situ dissolution and swelling of confined lamellar polymer crystals through exposure to humid air
Brahim Bessif, Thomas Pfohl, Barbara Heck, Yaser Alshetwi, Emna Khechine, Jun Xu, and Günter Reiter. Macromolecules 55, 6015–6022, 2022
The memory of thin polymer films generated by spin coating
Günter Reiter, Farzad Ramezani, Jörg Baschnagel. EPJE 45 (2022) 51
Bacteria-on-a-bead: probing the hydrodynamic interplay of dynamic cell appendages during cell separation
Nora Sauter, Matteo Sangermani, Isabelle Hug, Urs Jenal, and Thomas Pfohl. Biology Communications 5 (2022) 1093
Crystallization of copolymers: formation of alternating periodic structures and concepts for their modification
Brahim Bessif. Inaugural-Dissertation der Fakultät für Mathematik und Physik, 2022
Illumination of a Conjugated Polymer with Visible Light to Control Crystallization and Enhance Photoluminescence
Yaser AlShetwi. Inaugural-Dissertation zur Erlangung des Doktorgrads der Fakultät für Chemie und Pharmazie, 2022
Semi-crystalline poly(thioether) prepared by visible-light-induced organocatalyzed thiol-ene polymerization in emulsion
Cuong Minh Quoc Le, Gautier Schrodj, Ibrahima Ndao, Brahim Bessif, Barbara Heck, Thomas Pfohl, Günter Reiter, Justine Elgoyen, Radmila Tomovaska and Abraham Chemtob. Macromol. Rapid Commun. 43 (2022) 2100740
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