Chiral metal–organic frameworks constructed from four-fold helical chain SBUs for enantioselective recognition of α-hydroxy/amino acids

Yao, Ru‐Xin; Fu, Huanhuan; Yu, Bin; Zhang, Xianming

doi:10.1039/c7qi00615b

Cited by 26 publications

(16 citation statements)

References 62 publications

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“…Both frameworks crystallize in the chiral I 4 1 22 system and are isostructural to the reported (Al, In, Mg, Ni, etc.) MOFs. − These frameworks have shown excellent adsorption ability or enantioselective recognition, but proton-conductive properties have not been reported yet. The asymmetry unit of InOF-1 consists of an In(III) ion, a quarter of BPTC 4– ligand, half of a hydroxide anion.…”

Section: Resultsmentioning

confidence: 99%

In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

Gao

Hou

et al. 2021

ACS Appl. Mater. Interfaces

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Proton-conductive materials have attracted increasing attention because of their broad explorations in chemical sensors, water electrolysis, fuel cells, and biological systems. Especially, metal–organic frameworks (MOFs) have been demonstrated to be extremely promising candidates as proton-exchange membrane (PEM) fuel cells. Compared with other configurations, MOFs with one-dimensional (1D) channels have the characteristics of enhancing the host–guest interaction and promoting the anisotropic motion of proton carriers in restricted volume, which are beneficial for acquiring rich proton sources and forming successive hydrogen bonds to improve proton conductivity. We are endeavored to screen and find a helical three-dimensional (3D) framework InOF-1, namely, [In2(OH)2(BPTC)]·6H2O (BPTC4– = 3,3′,5,5′-biphenyl tetracarboxylate), as a typical 1D-channel MOF, which is pristinely grafted with spirally distributed −OH groups on the channel surface. Accompanied by an aliovalent substitution Ni(II) for In(III), isostructural NiOF-1 ([Ni2(BPTC)(HCOOH)2]·3H2O) is successfully prepared and massive formic acids are anchored at interior walls, which are interacted with adsorbed water molecules via the formation of stronger O–H···O bonds. This interaction between host–guest molecules and dynamics of lattice water has already led to a remarkable conductivity of InOF-1 (σ = 7.86 × 10–3 S/cm at 328 K under 95% RH). The synergistic effect of the acidic-modified nanowall, contracted volume, and enhanced adsorption of water molecules in the NiOF-1 channel contributes to a high conductivity value of 3.41 × 10–2 S/cm (at 328 K under 95% RH). Moreover, the proton conduction mechanism is further visually presented by molecular dynamic (MD) simulation. In contrast to InOF-1, aliovalent-substituted and acidic-modified NiOF-1 has a stronger host–guest interaction and more abundant hydrogen-bond networks, resulting in shorter proton migration distances and more frequent proton hopping, in agreement with the experimental results.

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Section: Resultsmentioning

confidence: 99%

In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

Gao

Hou

et al. 2021

ACS Appl. Mater. Interfaces

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“…A small number of studies reported chiral MOF sensors exhibiting initial CD signals, which could be applied for the recognition of specific enantiomers of chiral compounds by analyzing the difference in CD signal intensities. [ 69,70 ] Nonetheless, observation of the intensity variations is not always a precise recognition method, as changes in the local environment of the species may lead to erroneous determination. An appearance of a new peak in the CD sensing would be a more efficient and reliable approach.…”

Section: Introductionmentioning

confidence: 99%

Homochiral MOF as Chiroptical Sensor for Determination of Absolute Configuration and Enantiomeric Ratio of Chiral Tryptophan

Zhu

Zhou

Zhang

et al. 2021

Advanced Optical Materials

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The development of a highly selective and sensitive optical method for quantitative enantioselective sensing of chiral amino acids in the presence of other amino acid interferences has remained a major challenge to date. Herein, a homochiral metal–organic framework (MOF), [Zn(L)(2,2′‐bipy)]·H2O (LNNU‐1) (H2L = HOOCC6H4CH2PO(OH)(OC2H5), 2,2′‐bipy = 2,2′‐bipyridine), is designed to interact with tryptophan via multiple noncovalent interactions. The interactions result in the emergence of a strong induced circular dichroism signal. This enables accurate determination of the absolute configuration and enantiomeric ratio of chiral tryptophan in water, mixed natural amino acids, and blood plasma components without any interference from other coexistent species. A simple device with advantageous characteristics of reusability and simple manipulation is designed for enantioselective sensing assay. The obtained results suggest that the rationally designed homochiral MOF is a promising candidate for enantioselective sensing of chiral species.

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“…Utilizing chiral sources to design helical complexes can result in inherent chirality. Also, symmetry breaking with an achiral source can produce a helical structure [ 54 ]. [ZnLBr] was synthesized using a homochiral precursor, N –(4–Pyridylmethyl)- L -leucine·HBr, the aperture size was calculated around 9.8 A°.…”

Section: Mixed Matrix Membranes In Various Combinationsmentioning

confidence: 99%

Enantioselective Mixed Matrix Membranes for Chiral Resolution

2021

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Most pharmaceuticals are stereoisomers that each enantiomer shows dramatically different biological activity. Therefore, the production of optically pure chemicals through sustainable and energy-efficient technology is one of the main objectives in the pharmaceutical industry. Membrane-based separation is a continuous process performed on a large scale that uses far less energy than the conventional thermal separation process. Enantioselective polymer membranes have been developed for chiral resolution of pharmaceuticals; however, it is difficult to generate sufficient enantiomeric excess (ee) with conventional polymers. This article describes a chiral resolution strategy using a composite structure of mixed matrix membrane that employs chiral fillers. We discuss several enantioselective fillers, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), zeolites, porous organic cages (POCs), and their potential use as chiral fillers in mixed matrix membranes. State-of-the-art enantioselective mixed matrix membranes (MMMs) and the future design consideration for highly efficient enantioselective MMMs are discussed.

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Chiral metal–organic frameworks constructed from four-fold helical chain SBUs for enantioselective recognition of α-hydroxy/amino acids

Abstract: Three chiral 3D metal–carboxylate frameworks have been successfully synthesized, featuring four-fold helical metal chains as SBUs. Co-MOFs could recognize enantio-selectively α-hydroxy/amino acids by the change of CD signals.

Cited by 26 publications

References 62 publications

In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

In Situ Aliovalent Nickle Substitution and Acidic Modification of Nanowalls Promoted Proton Conductivity in InOF with 1D Helical Channel

Homochiral MOF as Chiroptical Sensor for Determination of Absolute Configuration and Enantiomeric Ratio of Chiral Tryptophan

Enantioselective Mixed Matrix Membranes for Chiral Resolution

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