Linker, loading, and reaction scale influence automated glycan assembly DOI Creative Commons
Marlene C. S. Dal Colle, Manuel G. Ricardo, Nives Hribernik

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 19, P. 1015 - 1020

Published: July 6, 2023

Automated glycan assembly (AGA) affords collections of well-defined glycans in a short amount time. We systematically analyzed how parameters connected to the solid support affect AGA outcome for three different sequences. showed that, while loading and reaction scale did not significantly influence outcome, chemical nature linker dramatically altered isolated yields. identified that major determinants yields are cleavage from post-AGA purification steps.

Language: Английский

Synthesis of a glycan hairpin DOI Creative Commons
Giulio Fittolani, Theodore Tyrikos‐Ergas, Ana Poveda

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(10), P. 1461 - 1469

Published: July 3, 2023

Abstract The primary sequence of a biopolymer encodes the essential information for folding, permitting to carry out sophisticated functions. Inspired by natural biopolymers, peptide and nucleic acid sequences have been designed adopt particular three-dimensional (3D) shapes programmed exert specific In contrast, synthetic glycans capable autonomously folding into defined 3D conformations so far not explored owing their structural complexity lack design rules. Here we generate glycan that adopts stable secondary structure present in nature, hairpin, combining motifs, stabilized non-conventional hydrogen bond hydrophobic interactions. Automated assembly enabled rapid access analogues, including site-specific 13 C-labelled ones, nuclear magnetic resonance conformational analysis. Long-range inter-residue Overhauser effects unequivocally confirmed folded conformation hairpin. capacity control shape across pool available monosaccharides has potential afford more foldamer scaffolds with programmable properties

Language: Английский

Citations

20
Dissecting the Conformational Stability of a Glycan Hairpin DOI Creative Commons

Nishu Yadav,

Surusch Djalali,

Ana Poveda

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6369 - 6376

Published: Feb. 20, 2024

Systematic structural studies of model oligopeptides revealed important aspects protein folding and offered design principles to access non-natural materials. In the same way, rules that regulate glycan could be established by studying synthetic oligosaccharide models. However, their analysis is often limited due analytical complexity. By utilizing a capable spontaneously into hairpin conformation as system, we investigated factors contribute its conformational stability in aqueous solution. The modular featured trisaccharide turn unit two β-1,4-oligoglucoside stacking strands allowed for systematic chemical modifications sequence, including introduction NMR labels staples. Nuclear magnetic resonance assisted molecular dynamics simulations stereoelectronic effects multiple glycan–glycan interactions are major determinants stabilization. Chemical primary sequence (e.g., strand elongation) can employed fine-tune rigidity motifs distant from modification sites. These results inspire other architectures, with implications glycobiology material sciences.

Language: Английский

Citations

7
Controlling Glycan Folding with Ionic Functional Groups DOI Creative Commons

Nishu Yadav,

Ana Poveda,

Yadiel Vázquez Mena

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Glycans are intrinsically flexible molecules that can adopt many conformations. These often carry ionic functional groups influence glycan's conformational preferences, dynamics, and aggregation tendencies. Inspired by these mechanisms, we have engineered a glycan sequence whose secondary structure be precisely manipulated using groups. We strategically incorporated substituents into adopting hairpin conformation. Complementary stabilized the closed conformers, while repulsions shifted populations toward open forms. External stimuli, such as pH variations or enzyme addition, enabled us to dynamically control hairpin's opening closing. Additionally, changes in protonation states led aggregation, suggesting opportunities for creation of responsive glycan-based materials.

Language: Английский

Citations

0
Phosphates as Assisting Groups in Glycan Synthesis DOI Creative Commons
Eric T. Sletten, Giulio Fittolani, Nives Hribernik

et al.

ACS Central Science, Journal Year: 2023, Volume and Issue: 10(1), P. 138 - 142

Published: Dec. 20, 2023

In nature, phosphates are added to and cleaved from molecules direct biological pathways. The concept was adapted overcome limitations in the chemical synthesis of complex oligosaccharides. Phosphates were chemically placed on synthetic glycans ensure site-specific enzymatic elongation by sialylation. addition, deliberate placement helped solubilize isolate aggregating glycans. Upon traceless removal treatment with alkaline phosphatase, native glycan structure revealed, assembly nanostructures triggered.

Language: Английский

Citations

8
Linker, loading, and reaction scale influence automated glycan assembly DOI Creative Commons
Marlene C. S. Dal Colle, Manuel G. Ricardo, Nives Hribernik

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 19, P. 1015 - 1020

Published: July 6, 2023

Automated glycan assembly (AGA) affords collections of well-defined glycans in a short amount time. We systematically analyzed how parameters connected to the solid support affect AGA outcome for three different sequences. showed that, while loading and reaction scale did not significantly influence outcome, chemical nature linker dramatically altered isolated yields. identified that major determinants yields are cleavage from post-AGA purification steps.

Language: Английский

Citations

4