Directing the solid-state organization of racemates via structural mutation and solution-state assembly processes

Chidambar Kulkarni, José Augusto Berrocal, Martin Lutz, Anja R.A. Palmans (Corresponding author), E.W. Meijer (Corresponding author)

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

Uittreksel

Chirality plays a central role in biomolecular recognition and pharmacological activity of drugs and can even lead to new functions such as spin filters. Although there have been significant advances in understanding and controlling the helical organization of enantiopure synthetic molecular systems, rationally dictating the assembly of mixtures of enantiomer (including racemates) is nontrivial. Here we demonstrate that a subtle change in molecular structure coupled with the understanding of assembly processes of enantiomers and racemates, in both dilute solution and concentrated gels, acts as a stepping stone to rationally control the organization in the solid-state. We have studied trans-1,2-disubstituted cyclohexanes as model systems with carboxamide, thioamide, and their combination as functional groups. On comparing the gelation propensity of individual enantiomers and racemates, we find that racemates of carboxamide, thioamide, and their combination adopt self-sorting, coassembly, and mixed organization, respectively. Remarkably, these modes of assembly of racemates were also retained in solid-state. These results point out that studying the solution-phase assembly is a key link for connecting molecular structure with the assembly in the solid-state, even for racemates.

TaalEngels
Pagina's6302-6309
Aantal pagina's8
TijdschriftJournal of the American Chemical Society
Volume141
Nummer van het tijdschrift15
DOI's
StatusGepubliceerd - 17 apr 2019

Vingerafdruk

Thioamides
Molecular Structure
Cyclohexanes
Enantiomers
Mutation
Gels
Molecular structure
Pharmacology
Pharmaceutical Preparations
Chirality
Gelation
Cyclohexane
Sorting
Functional groups

Citeer dit

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Directing the solid-state organization of racemates via structural mutation and solution-state assembly processes. / Kulkarni, Chidambar; Berrocal, José Augusto; Lutz, Martin; Palmans, Anja R.A. (Corresponding author); Meijer, E.W. (Corresponding author).

In: Journal of the American Chemical Society, Vol. 141, Nr. 15, 17.04.2019, blz. 6302-6309.

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review

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