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Effect of chemical structure on the crystallization kinetics of triple polymorphic high-sulfur-content polythioethers

Valentina Pirela, Leire Unanue, Justine Elgoyhen, Javier Ramos, Juan Francisco Vega, Agurtzane Mugica, Manuela Zubitur, Cuong Minh Quoc Le, Abraham Chemtob, Radmila Tomovska, Günter Reiter, Jaime Martín, Alejandro J. Müller. European Polymer Journal (2025) 113721

This work studies how the chemical structure of relatively similar high-sulfur alternating polythioether homopolymers (DMDS-alt-DVE, DMDS-alt-TEGDVE, and DMDS-alt-BDDVE) affects their structural properties, morphology, polymorphism, and crystallization kinetics. Differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM) experiments revealed a complex crystallization for the samples in which up to three different polymorphic phases were identified: a very low melting crystal form (VL-Tm form), a low melting crystal form (L-Tm form) and a high melting crystal form (H-Tm form), characterized by their corresponding melting temperature ranges and confirmed via Wide-Angle X-ray Scattering (WAXS). A coexistence of negative and positive spherulites was found, and their origin was revealed by atomic force microscopy (AFM), which showed how the lamellar arrangement varied in the samples from predominantly radial to a cross-hatched morphology. (more...)
 


Post-spin Stretch Improves Mechanical Properties, Reduces Necking, and Reverts Effects of Aging in Biomimetic Artificial Spider Silk Fibers

Gabriele Greco, Benjamin Schmuck, Fredrik G. Bäcklund, Günter Reiter and Anna Rising. ACS Appl. Polym. Mater.  6 (2024) 14342–14350

reiter-2024-05.jpgRecent biotechnological advancements in protein production and development of biomimetic spinning procedures make artificial spider silk a promising alternative to petroleum-based fibers. To enhance the competitiveness of artificial silk in terms of mechanical properties, refining the spinning techniques is imperative. One potential strategy involves the integration of post-spin stretching, known to improve fiber strength and stiffness while potentially offering additional advantages. Here, we demonstrate that post-spin stretching not only enhances the mechanical properties of artificial silk fibers but also restores a higher and more uniform alignment of the protein chains, leading to a higher fiber toughness. (more...)


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...)


 

Liste der Veröffentlichungen

Generating Nanoscopic Patterns in Conductivity Within a Poly(3-hexylthiophene) Crystal Via Bias-controlled Scanning Probe Nanolithography
Binghua Wang, Bin Zhang, Changyu Shen, Jingbo Chen, Günter Reiter. Macromolecules 51 (2018) 7692-7698
Systematic Control of Self-Seeding Crystallization Patterns of Poly(ethylene oxide) in Thin Films
Binghua Wang, Shaohua Tang, Yan Wang, Changyu Shen, Renate Reiter, Günter Reiter, Jingbo Chen, Bin Zhang. Macromolecules 51, 1626–1635 (2018)
Tuning relaxation dynamics and mechanical properties of polymer films of identical thickness
Marwa Kchaou, Pierre Alcouffe, Sivasurender Chandran, Philippe Cassagnau, Günter Reiter, and Samer Al Akhrass. Phys. Rev. E 97, 032507 (2018)
Highly n-doped graphene generated through intercalated terbium atoms
L. Daukiya, M. N. Nair, S. Hajjar-Garreau, F. Vonau, D. Aubel, J. L. Bubendorff, M. Cranney, E. Denys, A. Florentin, G. Reiter, and L. Simon. Phys. Rev. B 97, 035309 (2018)
Formation of Periodically Modulated Polymer Crystals
Purushottam Poudel. Inauguraldissertation 2018
Pneumatically Controlled Nanofluidic Devices for Contact-Free Trapping and Manipulation of Nanoparticles
Michael Adrian Gerspach, Nassir Mojarad, Deepika Sharma, Yasin Ekinci,and Thomas Pfohl. Part. Part. Syst. Charact. 2018, 1800161
Monitoring single-cell gene regulation under dynamically controllable conditions with integrated microfluidics and software
M. Kaiser, F. Jug, T. Julou, S. Deshpande, T. Pfohl, O. K. Silander, G. Myers, E. van Nimwegen, Nature Communications 9, 212 (2018)
Growth Kinetics of Stacks of Lamellar Crystals in Polymer Thin Films
Sumit Majumder. Inauguraldissertation 2018
Optical studies on indicators of order and disorder in films and crytals of a bulky substituted polythiophene
Fanuel Mugwanga Keheze. Inauguraldissertation 2018
Multiple structural transitions in Langmuir monolayers of charged soft-shell nanoparticles
Ahmed El-Tawargy, David Stock, Markus Gallei, Wael Ramadan, Mamdoh Shams El-Din, Günter Reiter, Renate Reiter. Langmuir 34, 3909−3917 (2018)
Thermodynamic origin of multi-layer structures in Langmuir polymer films
Volker Knecht, Günter Reiter, Renate Reiter. Langmuir 33 (2017) 11399–11405
Structure Formation in Langmuir Peptide Films As Revealed from Coarse-Grained Molecular Dynamics Simulations
Volker Knecht, Günter Reiter, Helmut Schlaad, and Renate Reiter. Langmuir 33 (2017) 6492-6502
Schnecken als lebende 3D-Drucker: freie Formen für die Architektur von morgen
Christoph Allgaier, Benjamin Felbrich, Frederik Wulle, Emna Khechine, James H. Nebelsick, Achim Menges, Günter Reiter, Renate Reiter, Armin Lechler, Alexander Verl, Karl-Heinz Wurst. Baubionik – Biologie beflügelt Architektur, Publisher: Naturkundemuseum Stuttgart 2017
Signatures of Melting and Recrystallization of a Bulky Substituted Poly(thiophene) Identified by Optical Spectroscopy
Fanuel Keheze, Dominic Raithel, Tianyu Wu, Daniel Schiefer, Michael Sommer, Richard Hildner, Günter Reiter. Macromolecules 50 (2017) 6829–6839
Triple-Shape Memory Materials via Thermoresponsive Behavior of Nanocrystalline Non-Isocyanate Polyhydroxyurethanes
Vitalij Schimpf, Barbara Heck, Günter Reiter, Rolf Mülhaupt. Macromolecules 50 (2017) 3598–3606
Semicrystalline long-chain polyphosphoesters from polyesterification
Hanna Busch, Sumit Majumder, Guenter Reiter, Stefan Mecking. Macromolecules 50 (2017) 2706–2713
Blocking of injected holes at the charge extracting interface
L. Govor, G. Reiter, J. Parisi. Journal of Physics, Condensed Matter 29 (2017) 025001
Relaxing Non-equilibrated Polymers in Thin Films at Temperatures Slightly Above the Glass Transition
Mithun Chowdhury, Samer Al Akhrass, Falko Ziebert, Günter Reiter. Journal of Polymer Science Part B: Polymer Physics 55 (2017) 515–523
Solvent-controlled reversible switching between adsorbed self-assembled nanoribbons and nanotubes
Asad Jamal, Irina Nyrkova, Philippe Mesini, Swann Militzer and Günter Reiter. Nanoscale 9 (2017) 3293-3303
Low Loss Optical Waveguiding in Large Single Crystals of Thiophene-Based Oligomers
Sajedeh Motamen, Christian Schörner, Dominic Raithel, Jean-Pierre Malval, Thibaut Jarrosson, Françoise Serein-Spirau, Laurent Simon, Richard Hildner, Günter Reiter. Physical Chemistry Chemical Physics 19 (2017) 15980 - 15987
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