Oppositely Charged Homopolypeptides Form Ordered Helix Assemblies With Hierarchical Structure
7 affiliations
- 1JCNS‐1 Forschungszentrum Jülich Jülich Germany
- 2IBG‐4 Forschungszentrum Jülich Jülich Germany
- 3ERC‐1 Forschungszentrum Jülich Jülich Germany
- 4Institute For Physical Chemistry Heinrich Heine University Düsseldorf Düsseldorf Germany
- 5IBI‐7 Forschungszentrum Jülich Jülich Germany
- 6Institute For Pharmaceutical and Medicinal Chemistry Heinrich Heine University Düsseldorf Düsseldorf Germany
- 7Institute of Physical Chemistry RWTH Aachen University Aachen Germany
Abstract
Oppositely charged polyelectrolytes are known to form polyelectrolyte complexes. Polyelectrolyte complexes are typically structurally disordered. In recent years, complexes of oppositely charged polypeptides have received increasing attention. Polypeptides provide additional interaction motifs such as hydrogen bonds and salt bridges that could stabilize ordered assemblies. Under specific conditions, the formation of secondary structures has been reported. So far, it has been difficult to obtain long‐range ordered assemblies of polypeptide complexes. Here we show that liquid‐solid phase separation of oppositely charged homopolypeptides spontaneously leads to the formation of extended polypeptide helices that form highly ordered hexagonally or square‐packed helix arrays with helix–helix distances of 1.6–2.0 nm. The helices exhibit an additional periodic staggering along their axis with a periodicity of 15 – 30 nm, equal to the length of the extended helices. This hierarchical helix assembly was demonstrated for polyarginine assembled with polyaspartic acid or polyglutamic acid as examples. The materials can be shear‐aligned to achieve macroscopic uniaxial orientation of the helices. Crosslinking leads to solid elastic materials. Upon heating to temperatures above 40°C, the structure disorders due to a reversible helix‐coil transition. The structural and mechanical properties suggest a new route to synthetic peptide‐based materials.
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BibTeX
@article{buvalaia2026oppositely,
title = {{Oppositely Charged Homopolypeptides Form Ordered Helix Assemblies With Hierarchical Structure}},
author = {Ekaterina Buvalaia and Martin Dulle and Benoit David and Karoline Rengel and Michael Ohl and Beate Förster and Margarita Kruteva and Henrike Heise and Ralf Biehl and Holger Gohlke and Stephan Förster},
journal = {Small (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = sep,
doi = {10.1002/smll.75495},
url = {https://doi.org/10.1002/smll.75495},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Oppositely Charged Homopolypeptides Form Ordered Helix Assemblies With Hierarchical Structure
AU - Ekaterina Buvalaia
AU - Martin Dulle
AU - Benoit David
AU - Karoline Rengel
AU - Michael Ohl
AU - Beate Förster
AU - Margarita Kruteva
AU - Henrike Heise
AU - Ralf Biehl
AU - Holger Gohlke
AU - Stephan Förster
PY - 2026
DA - 2026/09/11
JO - Small (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/smll.75495
UR - https://doi.org/10.1002/smll.75495
AB - Oppositely charged polyelectrolytes are known to form polyelectrolyte complexes. Polyelectrolyte complexes are typically structurally disordered. In recent years, complexes of oppositely charged polypeptides have received increasing attention. Polypeptides provide additional interaction motifs such as hydrogen bonds and salt bridges that could stabilize ordered assemblies. Under specific conditions, the formation of secondary structures has been reported. So far, it has been difficult to obtain long‐range ordered assemblies of polypeptide complexes. Here we show that liquid‐solid phase separation of oppositely charged homopolypeptides spontaneously leads to the formation of extended polypeptide helices that form highly ordered hexagonally or square‐packed helix arrays with helix–helix distances of 1.6–2.0 nm. The helices exhibit an additional periodic staggering along their axis with a periodicity of 15 – 30 nm, equal to the length of the extended helices. This hierarchical helix assembly was demonstrated for polyarginine assembled with polyaspartic acid or polyglutamic acid as examples. The materials can be shear‐aligned to achieve macroscopic uniaxial orientation of the helices. Crosslinking leads to solid elastic materials. Upon heating to temperatures above 40°C, the structure disorders due to a reversible helix‐coil transition. The structural and mechanical properties suggest a new route to synthetic peptide‐based materials.
SN - 1613-6810
SN - 1613-6829
ER -