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Natural biopolymers have inspired the development of synthetic analogues – i.e. foldamers – capable of adopting defined conformations and forming programmable three-dimensional architectures. These compounds are mainly based on peptides and nucleic acids, that are well understood at the molecular level. In contrast, the complexity of carbohydrate synthesis and structural analysis have prevented access to synthetic carbohydrates capable of adopting defined geometries. In the Delbianco group, we synthesize well-defined carbohydrates to understand how the primary sequence affects conformation and aggregation. [1-2]

Building on this fundamental knowledge, we present the rational design and synthesis of glycans adopting stable secondary structures, challenging the common belief that glycans are not capable of folding due to their flexibility. For example, by combining natural glycan motifs, we created a glycan hairpin, a secondary structure not present in nature. [3] Moreover, we designed glycan sequences that assemble into programmable supramolecular architectures, from fibers and particles to hydrogels. [4] Analogous to how the discovery of peptide-based foldamers launched a new field, we anticipate that carbohydrate foldamers and assemblies may find applications in areas across materials science, biology, and catalysis. [5]

[1] X. Wu, M. Delbianco, K. Anggara, T. Michnowicz, A. Pardo-Vargas, P. Bharate, S. Sen, M. Pristl, S. Rauschenbach, U. Schlickum, S. Abb, P. H. Seeberger, K. Kern, Nature 2020, 582, 375-378.

[2] G. Fittolani, D. Vargová, P. H. Seeberger, Y. Ogawa, M. Delbianco, J. Am. Chem. Soc. 2022, 144, 12469-12475.

[3] G. Fittolani, T. Tyrikos-Ergas, Y. Yu, N. Yadav, P.H. Seeberger, J. Jiménez-Barbero, M. Delbianco, Nat. Chem., 2023, 15, 1461-1469

[4] N. Hribernik, D. Vargová, M.C.S. Dal Colle, J. Hui Lim, G. Fittolani, Y. Yu, J. Fujihara, K. Ludwig, P.H. Seeberger, Y. Ogawa, M. Delbianco, Angew. Chem. Int. Ed., 2023, e202310357

[5] S. Djalali, N. Yadav, M. Delbianco, Towards glycan foldamers and programmable assemblies, Nat. Rev. Mater., 2024, 9, 190-201

Dr. Martina Delbianco studied chemistry at the University of Milan (Italy). She then moved to Durham University (UK) to pursuit a PhD under the supervision of Prof. David Parker working on emissive Eu(III) complexes. During her post doc, she explored the chemistry of carbohydrates and became familiar with automated synthesis in the group of Prof. Peter Seeberger at the Max Planck Institute for Colloids and Interfaces, MPIKG (Germany). Since 2018, Martina is the group leader of the Carbohydrate Materials at the MPIKG, supported by the German Federal Ministry of Education and Research and the ERC starting grant. Her group employs synthetic oligosaccharides as probes to study polysaccharides’ structure and their tendency to self-assemble into supramolecular materials.

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