Enantioselective Recognition and Separation of Symmetric Substances via Chiral Metal-Organic Frameworks.

ACS Appl Mater Interfaces

Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.

Published: August 2021

A promising route toward the enantioselective recognition and separation of racemic molecules is the design of chiral metal-organic frameworks (CMOFs) with high enantioselectivity and stability. Herein, we report porous CMOFs Δ- and Λ-RuEu-MOFs constructed from the -symmetry helical chiral Ru(phen)-derived tricarboxylate ligand and Eu units, which can be utilized as adsorbents for the enantioselective recognition and separation of 1,1'-bi-2-naphthol (BINOL) derivatives. Investigation of the circular dichroism enantiodifferentiation between the host and guest suggested that Δ- and Λ-RuEu-MOFs can be employed as chiral sensors to discriminate axial enantiomers due to their diastereomeric host-guest relationship. Density functional theory calculations reveal that chiral recognition is attributed to the distinguishing binding affinities stemming from N···H-O hydrogen bonds and π-π stacking between the host and guest. Moreover, the reticulate structure of Δ- and Λ-RuEu-MOFs can be readily recycled and reused for the successive enantioselective separation of BINOL up to 80% ee.

Download full-text PDF

Source
http://dx.doi.org/10.1021/acsami.1c10626DOI Listing

Publication Analysis

Top Keywords

enantioselective recognition
12
recognition separation
12
Δ- Λ-rueu-mofs
12
chiral metal-organic
8
metal-organic frameworks
8
host guest
8
chiral
5
enantioselective
4
separation
4
separation symmetric
4

Similar Publications

Chiral discrimination is an indispensable tool that has pivotal importance in the assignment of absolute configuration and determination of enantiomeric excess in chiral compounds. A series of enantiomerically pure -1,2-diaminocyclohexane (-DACH)-derived benzamides were first synthesized by simple chemical steps, and 14 variated derivatives have been assessed as NMR chiral solvating agents (CSAs) for discrimination of the signals of mandelic acid (MA) in H NMR analysis. The highly efficient chiral recognition of CSA on different substrates, including MAs, carboxylic acids, amino acid derivatives, and phosphoric acids (32 examples), was expanded via H, F, and P NMR spectroscopy.

View Article and Find Full Text PDF

Despite having identical physicochemical properties, chiral molecules require effective separation techniques due to their distinct pharmacological effects. Polysaccharide-based chiral stationary phases (CSPs) are widely used for chiral separations in liquid chromatography; however, the mechanisms of chiral recognition are not well understood. This research explored the adsorption, retention, and chiral recognition mechanisms of three amylose-based CSPs: Chiralpak ID, IF, and IG.

View Article and Find Full Text PDF

Cooperative Anion-π Catalysis with Chiral Molecular Cages toward Enantioselective Desymmetrization of Anhydrides.

J Am Chem Soc

January 2025

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.

Exploiting novel noncovalent interactions for catalysis design represents a fascinating direction. For the flexible and relatively weak anion-π interactions, manipulation of two or more π-acidic surfaces for cooperative activation is highly desirable. Here, we demonstrate the strategy of cooperative anion-π catalysis based on chiral molecular cages with V-shaped electron-deficient cavities for synergic binding and activation of dicarbonyl electrophiles toward highly enantioselective desymmetrization transformation.

View Article and Find Full Text PDF

Chiral synthetic hosts for efficient enantioselective molecular recognition. Design principles and synthetic aspects.

Chem Commun (Camb)

January 2025

Institut de Química Computacional i Catàlisi (IQCC), Universitat de Girona, Maria Aurèlia Capmany 69, 17003 Girona, Spain.

Discrimination of enantiomeric substrate molecules is one of the fundamental properties of biological hosts. Replicating enantioselective molecular recognition with synthetic receptors is a topic of interest with implications in diverse applications such as bioinspired enantioselective catalysis, enantiomer separation, or sensing. In this review, five different systems reported in the literature are discussed, and their performance and versatility are analyzed.

View Article and Find Full Text PDF

Recent Applications of Pillararene-Inspired Water-Soluble Hosts.

Chemistry

January 2025

Center for Supramolecular Chemistry & Catalysis and Department of Chemistry, Institution College of Science, Shanghai University, Shanghai, 200444, China.

Pillararenes and their derivatives have emerged in supramolecular chemistry as unique macrocycles for applications in host-guest chemistry, materials science and biomimetics. Many variations have been conceived and synthesized in recent years and in this review, we relate progress in water-soluble versions: leaning towerarenes, extended-pillararenes, biphenarenes, helicarenes and octopusarenes. These are applied in targeted drug delivery, selective uptake and release of aromatic guests, fabrication of gold/silver and mesoporous silica nanoparticles, cell imaging, pollutant separation, biomedicine (e.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!