Browse
Submit Data
Databases
API
Help

Dataset Information

25 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Enantioselective assembly and recognition of heterochiral porous organic cages deduced from binary chiral components.

ABSTRACT: Chiral recognition and discrimination is not only of significance in biological processes but also a powerful method to fabricate functional supramolecular materials. Herein, a pair of heterochiral porous organic cages (HPOC-1), out of four possible enantiomeric products, with mirror stereoisomeric crystal structures were cleanly prepared by condensation occurring in the exclusive combination of cyclohexanediamine and binaphthol-based tetraaldehyde enantiomers. Nuclear magnetic resonance and luminescence spectroscopy have been employed to monitor the assembly process of HPOC-1, revealing the clean formation of heterochiral organic cages due to the enantioselective recognition of (S,S)-binaphthol towards (R,R)-cyclohexanediamine derivatives and vice versa. Interestingly, HPOC-1 exhibits circularly polarized luminescence and enantioselective recognition of chiral substrates according to the circular dichroism spectral change. Theoretical simulations have been carried out, rationalizing both the enantioselective assembly and recognition of HPOC-1.

SUBMITTER: Liu C

PROVIDER: S-EPMC9200113 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Enantioselective Recognition of Ammonium Carbamates in a Chiral Metal-Organic Framework.

Project description:Chiral metal-organic frameworks have attracted interest for enantioselective separations and catalysis because of their high crystallinity and pores with tunable shapes, sizes, and chemical environments. Chiral frameworks of the type M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) seem particularly promising for potential applications because of their excellent stability, high internal surface areas, and strongly polarizing open metal coordination sites within the channels, but to date these materials have been isolated only in racemic form. Here, we demonstrate that when appended with the chiral diamine trans-1,2-diaminocyclohexane (dach), Mg2(dobpdc) adsorbs carbon dioxide cooperatively to form ammonium carbamate chains, and the thermodynamics of CO2 capture are strongly influenced by enantioselective interactions within the chiral pores of the framework. We further show that it is possible to access both enantiomers of Mg2(dobpdc) with high enantiopurity (≥90%) via framework synthesis in the presence of varying quantities of d-panthenol, an inexpensive chiral induction agent. Investigation of dach-M2(dobpdc) samples following CO2 adsorption-using single-crystal and powder X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory calculations-revealed that the ammonium carbamate chains interact extensively with each other and with the chiral M2(dobpdc) pore walls. Subtle differences in the non-covalent interactions accessible in each diastereomeric phase dramatically impact the thermodynamics of CO2 adsorption.

| S-EPMC8230736 | biostudies-literature

Core-Shell Crystals of Porous Organic Cages.

Project description:The first examples of core-shell porous molecular crystals are described. The physical properties of the core-shell crystals, such as surface hydrophobicity, CO2 ?/CH4 selectivity, are controlled by the chemical composition of the shell. This shows that porous core-shell molecular crystals can exhibit synergistic properties that out-perform materials built from the individual, constituent molecules.

| S-EPMC6120484 | biostudies-literature

Porous Organic Cages for Sulfur Hexafluoride Separation.

Project description:A series of porous organic cages is examined for the selective adsorption of sulfur hexafluoride (SF6) over nitrogen. Despite lacking any metal sites, a porous cage, CC3, shows the highest SF6/N2 selectivity reported for any material at ambient temperature and pressure, which translates to real separations in a gas breakthrough column. The SF6 uptake of these materials is considerably higher than would be expected from the static pore structures. The location of SF6 within these materials is elucidated by X-ray crystallography, and it is shown that cooperative diffusion and structural rearrangements in these molecular crystals can rationalize their superior SF6/N2 selectivity.

| S-EPMC5101576 | biostudies-literature

Water-stable hydrazone-linked porous organic cages.

Project description:Although porous organic cages (POCs), particularly imine-linked (C[double bond, length as m-dash]N) ones, have advanced significantly over the last few decades, the reversible nature of imine linkages makes them prone to hydrolysis and structural collapse, severely limiting their applications under moist or water conditions. Herein, seven water-stable hydrazone-linked (C[double bond, length as m-dash]N-N) POCs are prepared through a simple coupling of the same supramolecular tetraformylresorcin[4]arene cavitand with different dihydrazide linkers. Their structures are all determined by single-crystal X-ray crystallography, demonstrating rich structural diversity from the [2 + 4] lantern, [3 + 6] triangular prism, and unprecedented [4 + 8] square prism to the extra-large [6 + 12] octahedron. In addition, they respectively exhibit tunable window diameters and cavity volumes ranging from about 5.4 to 11.1 nm and 580 to 6800 Å3. Moreover, their application in the water environment for pollutant removal was explored, indicating that they can effectively eliminate various types of contaminants from water, including radionuclide waste, toxic heavy metal ions, and organic micropollutants. This work demonstrates a convenient method for rationally constructing versatile robust POCs and presents their great application potentialities in water medium.

| S-EPMC8528071 | biostudies-literature

Porous organic cages as synthetic water channels.

Project description:Nature has protein channels (e.g., aquaporins) that preferentially transport water molecules while rejecting even the smallest hydrated ions. Aspirations to create robust synthetic counterparts have led to the development of a few one-dimensional channels. However, replicating the performance of the protein channels in these synthetic water channels remains a challenge. In addition, the dimensionality of the synthetic water channels also imposes engineering difficulties to align them in membranes. Here we show that zero-dimensional porous organic cages (POCs) with nanoscale pores can effectively reject small cations and anions while allowing fast water permeation (ca. 109 water molecules per second) on the same magnitude as that of aquaporins. Water molecules are found to preferentially flow in single-file, branched chains within the POCs. This work widens the choice of water channel morphologies for water desalination applications.

| S-EPMC7530991 | biostudies-literature

Ultra-Fast Molecular Rotors within Porous Organic Cages.

Project description:Using variable temperature 2 H static NMR spectra and 13 C spin-lattice relaxation times (T1 ), we show that two different porous organic cages with tubular architectures are ultra-fast molecular rotors. The central para-phenylene rings that frame the "windows" to the cage voids display very rapid rotational rates of the order of 1.2-8×106 ?Hz at 230?K with low activation energy barriers in the 12-18?kJ?mol-1 range. These cages act as hosts to iodine guest molecules, which dramatically slows down the rotational rates of the phenylene groups (5-10×104 ?Hz at 230?K), demonstrating potential use in applications that require molecular capture and release.

| S-EPMC5813266 | biostudies-literature

SO<sub>2</sub> Capture Using Porous Organic Cages.

Project description:We report the first experimental investigation of porous organic cages (POCs) for the demanding challenge of SO2 capture. Three structurally related N-containing cage molecular materials were studied. An imine-functionalized POC (CC3) showed modest and reversible SO2 capture, while a secondary-amine POC (RCC3) exhibited high but irreversible SO2 capture. A tertiary amine POC (6FT-RCC3) demonstrated very high SO2 capture (13.78 mmol g-1 ; 16.4 SO2 molecules per cage) combined with excellent reversibility for at least 50 adsorption-desorption cycles. The adsorption behavior was investigated by FTIR spectroscopy, 13 C CP-MAS NMR experiments, and computational calculations.

| S-EPMC8361948 | biostudies-literature

Porous metal-organic alloys based on soluble coordination cages.

Project description:Diverse strategies for the preparation of mixed-metal three-dimensional porous solids abound, although many of them lend themselves only moderate levels of tunability. Herein, we report the design and synthesis of surface functionalized permanently microporous coordination cages and their use in the isolation of mixed metal solids. Judicious alkoxide-based ligand functionalization was utilized to tune the solubility of starting copper(ii)-based cages and their resulting compatibility with the mixed-cage approach described here. We further prepared a family of isostructural molybdenum(ii) cages for a subset of the ligands. The preparation of mixed-metal cage solids proceeds under facile conditions where solutions of parent cages are mixed and product phases isolated. A suite of spectroscopic and characterization tools confirm the starting cages are intact in the amorphous product. Finally, we show that utilization of precise ligand functional groups can be used to prepare mixed cage solids that can be easily and cleanly separated into their constituent components through simple solvent washing or solvent extraction techniques.

| S-EPMC8163318 | biostudies-literature

Enantioselective recognition at mesoporous chiral metal surfaces.

Project description:Chirality is widespread in natural systems, and artificial reproduction of chiral recognition is a major scientific challenge, especially owing to various potential applications ranging from catalysis to sensing and separation science. In this context, molecular imprinting is a well-known approach for generating materials with enantioselective properties, and it has been successfully employed using polymers. However, it is particularly difficult to synthesize chiral metal matrices by this method. Here we report the fabrication of a chirally imprinted mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and chiral template molecules. The porous platinum retains a chiral character after removal of the template molecules. A matrix obtained in this way exhibits a large active surface area due to its mesoporosity, and also shows a significant discrimination between two enantiomers, when they are probed using such materials as electrodes.

| S-EPMC3948375 | biostudies-literature

An evolutionary algorithm for the discovery of porous organic cages.

Project description:The chemical and structural space of possible molecular materials is enormous, as they can, in principle, be built from any combination of organic building blocks. Here we have developed an evolutionary algorithm (EA) that can assist in the efficient exploration of chemical space for molecular materials, helping to guide synthesis to materials with promising applications. We demonstrate the utility of our EA to porous organic cages, predicting both promising targets and identifying the chemical features that emerge as important for a cage to be shape persistent or to adopt a particular cavity size. We identify that shape persistent cages require a low percentage of rotatable bonds in their precursors (<20%) and that the higher topicity building block in particular should use double bonds for rigidity. We can use the EA to explore what size ranges for precursors are required for achieving a given pore size in a cage and show that 16 Å pores, which are absent in the literature, should be synthetically achievable. Our EA implementation is adaptable and easily extendable, not only to target specific properties of porous organic cages, such as optimal encapsulants or molecular separation materials, but also to any easily calculable property of other molecular materials.

| S-EPMC6251339 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data