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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 Applied Polymer Materials, published online

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...)


"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

Crystal nucleation enhanced at the diffusive interface of immiscible polymer blends
Yu Ma, Liyun Zha, Wenbing Hu, Günter Reiter, Charles C. Han. Phys. Rev. E 77, 061801 (2008)
Semicrystalline Macromolecular Design by Nitroxide-Mediated Polymerization
Khaled Karaky, Gérald Clisson, Günter Reiter, Laurent Billon. Macromol. Chem. Phys. 209, 715–722 (2008)
Viscoelastic Thin Polymer Films under Transient Residual Stresses: Two-Stage Dewetting on Soft Substrates
S. Al Akhrass, G. Reiter, S.Y. Hou, M. H. Yang, Y. L. Chang, F. C. Chang, C. F. Wang, A. C.-M. Yang. Phys. Rev. Lett. 100, 178301 (2008)
The Influence of Protic Non-Solvents Present in the Environment on Structure Formation of Poly(γ-benzyl-L-glutamate) in Organic Solvents
Ioan Botiz, Nikolay Grozev, Helmut Schlaad, Günter Reiter. Soft Matter, 4, 993-1002 (2008)
Influence of Progressive Cross-Linking on Dewetting of Polystyrene Thin Films
Samer Al Akhrass, Roxana-Viorela Ostaci, Yves Grohens, Eric Drockenmuller, Günter Reiter. Langmuir 24, 1884-1890 (2008)
Tuning the surface/bulk properties by the control of the amphiphilic profile in gradient copolymer
K. Karaky, C. Derail, G. Reiter, et al. Conference Information: 46th Microsymposium on Macromolecules - Nanostructured Polymers and Polymer Nanocomposites, Jul.08 - Aug.12, 2007 Prague, Czech Republic, Macromolecular Symposia 267, 31-40 (2008)
Characterizing and modeling the tensile deformation of polyethylene: The temperature and crystallinity dependences
Ke Hong, Gert Strobl. Polymer Science Series A 50, 483-493 (2008)
Zero Growth Temperature of Crystallizing Polyethylene
T. Y. Cho, W. Stille, G. Strobl. Macromolecules 40, 2596 (2007)
Zero growth temperature and growth kinetics of crystallizing poly(ε-caprolactone)
T.-Y. Cho, W. Stille, G. Strobl. Colloid Polym. Sci. 285, 931 (2007)
Progress in Understanding Polymer Crystallization
Editors: Günter Reiter and Gert Strobl. Lecture Notes in Physics 714 (2007), Springer Berlin/Heidelberg ISSN: 978-3-540-47305-3
Formation of low-dimensional close-packed arrays of nanoparticles in a dewetting water layer
Leonid V. Govor, Günter Reiter, Gottfried H. Bauer, Jürgen Parisi. Phys. Rev. E 76, 041609 (2007)
Thin Film Morphology in Triblock Terpolymers with One and Two Crystallizable Blocks
Adriana Boschetti-de-Fierro, Lea Spindler, Günter Reiter, Dania Olmos, Sergei Magonov, Volker Abetz. Macromolecules 40, 5487-5496 (2007)
Stable dispersions of highly anisotropic nanoparticles formed by cocrystallization of enantiomeric diblock copolymers
D. Portinha, F. Boue, L. Bouteiller, G. Carrot, C. Chassenieux, S. Pensec, G. Reiter. Macromolecules 40, 4037- 4042 (2007)
Cooperative Rearrangements Leading to Long Range Order in Monolayers of Supramolecular Polymers
F. Vonau, D. Aubel, L. Bouteiller, G. Reiter, L. Simon. Phys. Rev. Lett. 99, 086103 (2007)
Relaxation of Residual Stress and Reentanglement of Polymers in Spin-Coated Films
Pascal Damman, Sylvain Gabriele, Séverine Coppée, Sylvain Desprez, Didier Villers, Thomas Vilmin, Elie Raphaël, Moustafa Hamieh, Samer Al Akhrass, Günter Reiter. Phys. Rev. Lett. 99, 036101 (2007)
Switching layer stability in a polymer bilayer by thickness variation
J. P. de Silva, M. Geoghegan, A. M. Higgins, G. Krausch, M.-O. David, G. Reiter. Phys. Rev. Lett. 98, 267802 (2007)
Avantages de la réflectometrie des neutrons pour l’étude des polymères en couches minces
Günter Reiter, Mark Geoghegan. Collection SFN 8, 103-113 (2007)
Morphologies of Polymer Crystals in Thin Films
Günter Reiter, Ioan Botiz, Laetitia Graveleau, Nikolay Grozev, Krystyna Albrecht, Ahmed Mourran, Martin Möller. In "Progress in Understanding Polymer Crystallization". Eds. Günter Reiter and Gert Strobl, Lect. Notes Phys. 714, 179-200 (2007)
Influence of Substrate Properties on the Dewetting Dynamics of Viscoelastic Polymer Films
Moustafa Hamieh, Samer Al Akhrass, Tayssir Hamieh, Pascal Damman, Sylvain Gabriele, Thomas Vilmin, Elie Raphaël, Günter Reiter. J. Adhes. 83, 367-381 (2007)
The Physics of Polymers, Concepts for Understanding Their Structures and Behavior.
Gert Strobl. Third Revised and Expanded Edition, Springer 2007, ISBN 978-3-540-25278-8
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