Mechanochemically Driven Covalent Self-Assembly of a Chiral Mono-Biotinylated Hemicucurbit[8]Uril
Cell Reports Physical Science
2024
Elina Suut-Tuule,
Tatsiana Jarg,
Priit Tikker,
Ketren-Marlein Lootus,
Jevgenija Martōnova,
Rauno Reitalu,
Lukas Ustrnul,
Jas S. Ward,
Vitālijs Rjabovs,
Kirill Shubin,
Jagadeesh V. Nallaparaju,
Marko Vendelin,
Sergei Preis,
Mario Öeren,
Kari Rissanen,
Dzmitry Kananovich,
Riina Aav
Solution-based synthesis of complex molecules with high efficiency leverages supramolecular control over covalent bond formation. Herein, we present the mechanosynthesis of chiral mono-biotinylated hemicucurbit[8]urils (mixHC[8]s) via the condensation of D-biotin, (R,R)- or (S,S)-cyclohexa-1,2-diylurea, and paraformaldehyde. The selectivity of self-assembly is enhanced through mechanochemistry and by fostering non-covalent interactions, achieved by eliminating solvents and conducting the reaction in the solid state. Rigorous analysis of intermediates reveals key processes and chemical parameters influencing dynamic covalent chemistry. The library of ca. 50,000 theoretically predicted intermediates and products leads to covalent self-assembly of chiral hemicucurbiturils. Mechanochemically prepared diastereomeric (−)- and (+)-mixHC[8]s are suitable for anion binding and derivatization. Immobilization of the macrocycles on aminated silica produces a functional material capable of selective capture of anions, as demonstrated by efficient perchlorate removal from a spiked mineral matrix.
Atslēgas vārdi
mechanochemistry, covalent self-assembly in solid state, dynamic covalent chemistry, hemicucurbituril, macrocycle, mechanistic study, anion binding, functionalized silica, perchlorate removal, solid-phase extraction
DOI
10.1016/j.xcrp.2024.102161
Hipersaite
https://www.sciencedirect.com/science/article/pii/S2666386424004466?via%3Dihub#kwrds0010
Suut-Tuule, E., Jarg, T., Tikker, P., Lootus, K., Martōnova, J., Reitalu, R., Ustrnul, L., Ward, J., Rjabovs, V., Shubin, K., Nallaparaju, J., Vendelin, M., Preis, S., Öeren, M., Rissanen, K., Kananovich, D., Aav, R.
Mechanochemically Driven Covalent Self-Assembly of a Chiral Mono-Biotinylated Hemicucurbit[8]Uril. Cell Reports Physical Science, 2024, Vol. 5, No. 9, Article number 102161. e-ISSN 2666-3864. Pieejams: doi:10.1016/j.xcrp.2024.102161
Publikācijas valoda
English (en)