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Helical supramolecular polymers with rationally designed binding sites for chiral guest recognition.

ABSTRACT: Since various helical supramolecular polymers became available, their application to molecular chirality recognition have been anticipated but not extensively studied. So far, only a few examples of chiral reactions have been reported, but none for chiral separation. Here, we report the application of a helical supramolecular polymer to the enantio-separation of chiral guest molecules. The monomer of this supramolecular polymer is the salt-pair of a dendritic carboxylic acid with an enantiopure amino alcohol. In an apolar solvent, this salt-pair stacks via hydrogen bonds to form a helical polymer. In conjunction with this carboxylic acid, various amino alcohols afford supramolecular polymers, whose helical handedness is determined by the stereochemistry of the amino alcohols. When two salts with the same chirality are mixed, they undergo copolymerization, while those with opposite chirality do not. Owing to this stereoselective copolymerizability, the helical supramolecular polymer could bias the enantiomeric composition of chiral amino alcohols.

SUBMITTER: Salikolimi K

PROVIDER: S-EPMC7210886 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Helical supramolecular polymers with rationally designed binding sites for chiral guest recognition.

Salikolimi Krishnachary K Praveen Vakayil K VK Sudhakar Achalkumar Ammathnadu AA Yamada Kuniyo K Horimoto Noriko Nishizawa NN Ishida Yasuhiro Y

Nature communications 20200508 1

Since various helical supramolecular polymers became available, their application to molecular chirality recognition have been anticipated but not extensively studied. So far, only a few examples of chiral reactions have been reported, but none for chiral separation. Here, we report the application of a helical supramolecular polymer to the enantio-separation of chiral guest molecules. The monomer of this supramolecular polymer is the salt-pair of a dendritic carboxylic acid with an enantiopure ...[more]

PMID: 32385267

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Project description:We report kinetically controlled chiral supramolecular polymerization based on ligand-metal complex with a 3 : 2 (L : Ag+) stoichiometry accompanying a helical inversion in water. A new family of bipyridine-based ligands (d-L1, l-L1, d-L2, and d-L3) possessing hydrazine and d- or l-alanine moieties at the alkyl chain groups has been designed and synthesized. Interestingly, upon addition of AgNO3 (0.5-1.3 equiv.) to the d-L1 solution, it generated the aggregate I composed of the d-L1AgNO3 complex (d-L1 : Ag+ = 1 : 1) as the kinetic product with a spherical structure. Then, aggregate I (nanoparticle) was transformed into the aggregate II (supramolecular polymer) based on the (d-L1)3Ag2(NO3)2 complex as the thermodynamic product with a fiber structure, which led to the helical inversion from the left-handed (M-type) to the right-handed (P-type) helicity accompanying CD amplification. In contrast, the spherical aggregate I (nanoparticle) composed of the d-L1AgNO3 complex with the left-handed (M-type) helicity formed in the presence of 2.0 equiv. of AgNO3 and was not additionally changed, which indicated that it was the thermodynamic product. The chiral supramolecular polymer based on (d-L1)3Ag2(NO3)2 was produced via a nucleation-elongation mechanism with a cooperative pathway. In thermodynamic study, the standard ΔG° and ΔH e values for the aggregates I and II were calculated using the van't Hoff plot. The enhanced ΔG° value of the aggregate II compared to that of the formation of aggregate I confirms that aggregate II was thermodynamically more stable. In the kinetic study, the influence of concentration of AgNO3 confirmed the initial formation of the aggregate I (nanoparticle), which then evolved to the aggregate II (supramolecular polymer). Thus, the concentration of the (d-L1)3Ag2(NO3)2 complex in the initial state plays a critical role in generating aggregate II (supramolecular polymer). In particular, NO3 - acts as a critical linker and accelerator in the transformation from the aggregate I to the aggregate II. This is the first example of a system for a kinetically controlled chiral supramolecular polymer that is formed via multiple steps with coordination structural change.

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Helical supramolecular polymers with rationally designed binding sites for chiral guest recognition.

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Helical supramolecular polymers with rationally designed binding sites for chiral guest recognition.

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