Encoding stability and dynamics in hydrogen-bonded octameric capsules through amino acid α-position design.
4 affiliations
- 1Center for Advanced Technologies, Adam Mickiewicz University Uniwersytetu Poznańskiego 10 61-614 Poznań Poland [email protected].
- 2Faculty of Chemistry, Adam Mickiewicz University Uniwersytetu Poznańskiego 8 61-614 Poznań Poland.
- 3Department of Chemistry, Molecular Sciences Research Hub, Imperial College London 82 Wood Lane London W12 0BZ UK.
- 4Department of Chemistry, University College London Christopher Ingold Building 20 Gordon St London WC1H 0AJ UK.
Abstract
How local molecular determinants encode stability and dynamics in supramolecular assemblies remains a central challenge in adapting biological design principles for synthetic systems. Here, we systematically investigate eleven amino acid-functionalized benzene-1,3,5-tricarboxamides to elucidate how chirality, α-substitution, and side-chain architecture control the formation, stability and function of noncovalent octameric capsules. Achiral derivatives lacking an α-hydrogen exhibit poor solubility in noncompetitive solvents and preferentially form extended polymeric aggregates, highlighting the role of the α-H motif in mediating solvation and preorganization of hydrogen-bonding networks. In contrast, chiral analogues retaining the α-H group readily self-assemble into discrete, D2-symmetric octameric capsules. Substitution of the α-hydrogen with a methyl group disrupts solubility and capsular stability; however, introduction of long aliphatic side chains partially restores capsule formation, albeit with increased dynamics. Moreover, α-methylation profoundly affects capsule function, leading to a complete loss of fullerene encapsulation ability compared to the corresponding α-H-containing capsules. Overall, these results reveal how subtle variations at the α-position translate into emergent differences in stability, dynamics, function and architecture of hydrogen-bonded supramolecular capsules.
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BibTeX
@article{perlitius2026encoding,
title = {{Encoding stability and dynamics in hydrogen-bonded octameric capsules through amino acid α-position design.}},
author = {Filip Perlitius and Grzegorz Markiewicz and Mateusz Gołdyn and Gokay Avci and Kim E Jelfs and Artur R Stefankiewicz},
journal = {Organic chemistry frontiers : an international journal of organic chemistry},
year = {2026},
month = nov,
doi = {10.1039/d6qo01259k},
url = {https://europepmc.org/article/MED/42997531},
note = {CC BY},
}
RIS
TY - JOUR
TI - Encoding stability and dynamics in hydrogen-bonded octameric capsules through amino acid α-position design.
AU - Filip Perlitius
AU - Grzegorz Markiewicz
AU - Mateusz Gołdyn
AU - Gokay Avci
AU - Kim E Jelfs
AU - Artur R Stefankiewicz
PY - 2026
DA - 2026/11/06
JO - Organic chemistry frontiers : an international journal of organic chemistry
DO - 10.1039/d6qo01259k
UR - https://europepmc.org/article/MED/42997531
AB - How local molecular determinants encode stability and dynamics in supramolecular assemblies remains a central challenge in adapting biological design principles for synthetic systems. Here, we systematically investigate eleven amino acid-functionalized benzene-1,3,5-tricarboxamides to elucidate how chirality, α-substitution, and side-chain architecture control the formation, stability and function of noncovalent octameric capsules. Achiral derivatives lacking an α-hydrogen exhibit poor solubility in noncompetitive solvents and preferentially form extended polymeric aggregates, highlighting the role of the α-H motif in mediating solvation and preorganization of hydrogen-bonding networks. In contrast, chiral analogues retaining the α-H group readily self-assemble into discrete, D2-symmetric octameric capsules. Substitution of the α-hydrogen with a methyl group disrupts solubility and capsular stability; however, introduction of long aliphatic side chains partially restores capsule formation, albeit with increased dynamics. Moreover, α-methylation profoundly affects capsule function, leading to a complete loss of fullerene encapsulation ability compared to the corresponding α-H-containing capsules. Overall, these results reveal how subtle variations at the α-position translate into emergent differences in stability, dynamics, function and architecture of hydrogen-bonded supramolecular capsules.
SN - 2052-4110
SN - 2052-4129
ER -