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ANALYTICA CHIMICA ACTA · 2014 · IF 4.517

Chiral metal–organic framework used as stationary phases for capillary electrochromatography

Zhi-Xin Fei,Mei Zhang,Jun-Hui Zhang,Li-Ming Yuan

Metal–organic frameworks (MOFs) have received great attention as novel media in separation sciences because of their fascinating structures and unusual properties. However, to the best of our knowledge, there has been no attempt to utilize chiral MOFs as stationary phases in capillary electrochromatography (CEC). In this study, a homochiral helical MOF [Zn 2 (D-Cam) 2 (4,4′-bpy)] n (D-Cam   =   D-(+)-camphoric acid, 4,4′-bpy   =   4,4′-bipyridine) was explored as the chiral stationary phase in open tubular capillary electrochromatography (OT-CEC) for separation of chiral compounds and isomers. The MOFs coated column has been developed using a simple procedure via MOFs post-coated on the sodium silicate layer. The baseline separations of flavanone and praziquantel were achieved on the MOFs coated column with high resolution of more than 2.10. The influences of pH, organic modifier content and buffer concentration on separation were investigated. Besides, the separations of isomers (nitrophenols and ionones) were evaluated. The relative standard deviations (RSDs) for the retention time of run-to-run, day-to-day and column-to-column were 1.04%, 2.16% and 3.07%, respectively. The results demonstrated that chiral MOFs are promising for enantioseparation in CEC.

研究领域: 分析化学 · 分离科学
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ANALYST · 2024 ·Vol. 149 ·期 6 ·1753-1758 · IF 3.6

A chiral metal–organic framework/cyclodextrin sensing interface for the chiral discrimination of tryptophan enantiomers

Haowei Huang,Junyao Li,Wenrong Cai,Datong Wu,Laidi Xu,Yong Kong

A chiral metal–organic framework (CMOF) was synthesized by introducing L-histidine (L-His) to zeolitic imidazolate framework-8 (ZIF-8) and then grafting with carboxymethyl-β-cyclodextrin (CM-β-CD). Compared with L-His-ZIF-8, the CM-β-CD-functionalized L-His-ZIF-8 (L-His-ZIF-8-CD) showed significantly enhanced discrimination ability for the tryptophan (Trp) enantiomers owing to the inherent chirality of CM-β-CD. The specificity of the chiral interface was also studied, and the results indicated that the discrimination ability for Trp enantiomers is significantly stronger than that for the enantiomers of cysteine (Cys) and tyrosine (Tyr), which might be due to the better matching between the indole ring of Trp and the chiral cavity of CM-β-CD.

研究领域: 化学 · 分析化学 · 材料科学
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ANALYTICAL CHEMISTRY · 2023 · IF 7.4

Chiral Metal–Organic Framework with Temperature-Dependent Homochirality for Chiral Discrimination

Ning Liu,Junyao Li,Wenrong Cai,Datong Wu,Yong Kong

Chiral metal–organic frameworks (CMOFs) have attracted considerable attention in chiral discrimination and separation. In this work, a simple CMOF is synthesized through a facile one-pot method by using Zn(II), tetra(4-carboxyphenyl)-porphyrin (TCPP), and d-phenylalanine methyl ester (d-Phe-OMe) as metal ion, organic ligand, and chiral source, respectively. Interestingly, the CMOFs synthesized at different temperatures (25 and 160 °C) display quite different morphologies and diametrically opposite chirality due to the different interaction modes between TCPP and d-Phe-OMe at 25 and 160 °C. Next, the CMOFs synthesized at 25 and 160 °C are utilized for the chiral discrimination of the isomers of tryptophan (Trp), resulting in exactly the reverse effect. The developed CMOF-based chiral sensors also exhibit excellent reproducibility, suggesting their great potential for chiral analysis.

研究领域: 材料科学 · 化学 · 分析化学
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2023 ·Vol. 39 ·期 6 ·976-984 · IF 3.1

Electrochemical Chiral Recognizing Tryptophan Enantiomers Based on Chiral Metal-Organic Framework D-MOF

Hou Huipeng,Tang Shanshan,Wang Wei,Liu Miao,Liang Axin,Xie Bingteng,Yi Yue,Luo Aiqin

I n this work, an electrochemical chiral sensor of a nanowire-like chiral metal-organic framework/multiwalled carbon nanotube-chitosan/glassy carbon electrode( D -MOF/MWCNTs-CS/GCE) was proposed for the enantiorecognition of L / D -tryptophan( L / D -Trp). The asymmetrical spatial structure of D -MOF provides the feasibility for the enantiorecognition of Trp enantiomers. Moreover, differential pulse voltammetry(DPV) was carried out to be the detection method and the DPV peak potential difference(Δ E p ) between L -Trp and D -Trp was referred as the index of the enantiorecognition performance. Several parameters, such as mass ratios and drop-coated volume of MWCNTs-CS, drop-coated volume and concentration of D -MOF, pH and detection temperature of D -MOF/MWCNTs-CS/GCE were optimized for the largest Δ E p value. And the molecular dynamics(MD) simulation was used to elucidate the enantiorecognition mechanism. Furthermore, the proportions of D -Trp( D -Trp%) in Trp mixtures were detected in a good linear relationship with the DPV peak potentials( E p ), and the proposed electrochemical chiral sensor exhibited good reproducibility, stability and enantiorecognition ability. Additionally, the proposed electrochemical chiral sensor( D -MOF/MWCNTs-CS/GCE) has a good application prospect in the fields of biomedicine, clinical diagnosis, chemical production, pharmaceuticals safety and so on.

研究领域: 分析化学 · 生物医学 · 电化学
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JOURNAL OF CHROMATOGRAPHY A · 2025 · IF 4

Green and Controlled Synthesis of Copper-Based Tryptophan Flower-like Chiral Metal-Organic Framework for Enantioselective Recognition and Volatile Organic Compound Separation

Jinhua Xu,Minghui Tang,Jinyu Zhang,Wenmin Zhang,Shiye Xie,Lan Zhang

This study reports the synthesis and application of a flower-like chiral metal-organic framework (CMOF) based on copper ions and tryptophan (Cu(Trp)-CMOF). The Cu(Trp)-CMOF was successfully synthesized at room temperature through a facile method with hexadecyl trimethyl ammonium bromide (CTAB) as a structure-directing agent. The material exhibits a flower-like morphology with hierarchical porosity and well-defined crystallinity in the monoclinic P2 1 /c space group. Comprehensive characterization revealed that different optical configurations ((R)-type, (S)-type, and (RS)-type) could be selectively obtained by controlling the chirality of tryptophan ligands. The synthesized CMOFs demonstrated excellent performance in two key applications: colorimetric recognition of amino acid enantiomers and separation of volatile organic compounds (VOCs). When used as a chromatographic stationary phase, the CMOF significantly enhanced the separation of challenging structural isomers, particularly improving the resolution (R S ) of xylene isomers (R S from 1.03 to 2.62) and ethyltoluene isomers (R S from 4.83 to 9.23) compared to conventional columns. This work provides new insights into the design and application of CMOFs for chiral separation and recognition.

研究领域: 材料科学 · 化学
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MICROCHEMICAL JOURNAL · 2023 · IF 4.8

Chiral metal–organic framework [Zn2(D-Cam)2(4,4′-bpy)]n@SiO2 core–shell composite for HPLC separation

Cai-Fang Liu,Xiao-Yan Ran,Cheng Liu,Yu-lan Zhu,Yan-Rui Lu,Yu-Ping Yang,Bang-Jin Wang,Jun-Hui Zhang,Sheng-Ming Xie,Li-Ming Yuan:

Chiral metal–organic frameworks, an emerging type of chiral porous materials, possess many outstanding characteristics such as high surface area, tunable pore sizes, and good chemical stability. Herein, we prepared a chiral [Zn 2 (D-Cam) 2 (4,4′-bpy)] n @SiO 2 core–shell composite on the SiO 2 -NH 2 microspheres by an in-situ growth method. The prepared [Zn 2 (D-Cam) 2 (4,4′-bpy)] n @SiO 2 -packed column exhibited high-resolution separation of racemic compounds and positional isomers at a low column backpressure (9–12 bar). Twelve pairs of enantiomers including alcohols, amines, epoxides, ketones, and esters were well resolved with sharp peak shapes on the [Zn 2 (D-Cam) 2 (4,4́-bpy)] n @SiO 2 chromatographic column. Compared the separation performance of [Zn 2 (D-Cam) 2 (4,4́-bpy)] n @SiO 2 -packed column and two chromatographic columns (commercial Chiralpak AD-H column and as-prepared SiO 2 -NH 2 column), the [Zn 2 (D-Cam) 2 (4,4′-bpy)] n -packed column and the commercial Chiralpak AD-H column have a good complementarity in chiral separation, and it also offered better separation performance compared to the SiO 2 -NH 2 column for separating positional isomers. The effects of column temperature and analyte mass on the HPLC separation were investigated. Additionally, the [Zn 2 (D-Cam) 2 (4,4́-bpy)] n @SiO 2 packed column has good repeatability and stability for HPLC separation of enantiomers and positional isomers. The relatvive standard deviations (RSDs) for repeated separations of 2,2,2-trifluoro-1-(9-anthryl)ethanol and o , m , p -bromoaniline were less than 0.8 % and 1.2 % for the retention time and peak area, respectively. After continuous use for one month, the RSDs for the retention time and peak area of them were in the range of 1.1–1.3 % and 1.5–1.8 % (inter-day and intra-day, n = 5), respectively. This work also indicates that the chiral MOFs@SiO 2 composites are promising for HPLC separation.

研究领域: 分析化学 · 材料科学 · 色谱技术
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Analytical Methods · 2024 · IF 2.7

Chiral metal–organic frameworks grown in situ for monolithic capillary electrochromatographic enantioseparation

Min Zhou,Jie Hao,Yanzhi Wu,Xiaolin Lu,Jianbo Song,Luhui Ren,Junwei Han

Chiral metal–organic frameworks (CMOFs) with chiral selectivity are one of the high-quality stationary phases for capillary electrochromatography (CEC). However, there is a problem of unsatisfactory enantioseparation performance of capillary columns due to insufficient loading. In this work, a lamellar CMOF (Cu-TC) was grown in situ on the surface of the monolith in a capillary monolithic column to obtain a Cu-TC@monolithic column. The CEC system constructed based on the Cu-TC@monolithic column shows a satisfactory chiral separation performance. Compared with the Cu-TC-based coated column (Cu-TC@coated column), the enantioseparation performance of the CEC system based on the Cu-TC@monolithic column was greatly improved, and the resolutions (Rs) of the model analytes were increased by 80–500%. In addition, the effects of experimental conditions such as the number of cycles of Cu-TC in situ growth, buffer concentration, buffer pH, organic solvent addition and applied voltage on the performance of CEC were also investigated. Finally, the chiral selection mechanism of the stationary phase was explored by selective adsorption experiments. The present work provides a new idea for the development of capillary stationary phases, which has great potential considering the diversity of CMOFs.

研究领域: 分析化学 · 材料科学 · 分离科学
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Photonics Research · 2024 ·Vol. 12 ·期 8 ·1654-1664 · IF 6.6

Circularly polarized lasing from chiral metal-organic frameworks

Dexiang Zhu,Dexiang Zhu,Dexiang Zhu,Zhouyuanhang Wang,Zhouyuanhang Wang,Zhouyuanhang Wang,Xiangyu Xu,Xiangyu Xu,Xiangyu Xu,Wenyu Du,Wenyu Du,Wenyu Du,Wei Huang,Wei Huang,Wei Huang,Yan Kuai,Yan Kuai,Yan Kuai,Benli Yu,Benli Yu,Benli Yu,Jianzhong Zheng,Zhijia Hu,Zhijia Hu,Zhijia Hu,Zhijia Hu,Siqi Li,Siqi Li,Siqi Li,Siqi Li

Circularly polarized lasers play a pivotal role in classical optics, nanophotonics, and quantum optical information processing, while their fabrication remains complex. This article begins with examining the interactions between stimulated emission and chiral matter, outlining a simple strategy for producing circularly polarized lasing from chiral metal-organic frameworks (MOFs), such as the zeolitic imidazolate framework (ZIF), embedded with achiral laser dyes (L/D-ZIF⊃dyes). It is found that the stimulated emission threshold and intensity are influenced by the interplay between the chiral polarization of the pump light and the inherent chirality of the MOF nanoparticles. We further present the design of a chiral vertical-cavity surface-emitting laser (VCSEL), comprising an L/D-ZIF⊃dyes solid-state film sandwiched between a high-reflectivity distributed Bragg reflector (DBR) mirror and a silver film. The cavity-based lasing exhibits higher asymmetry between emitting left-handed and right-handed polarized light compared to chiral spontaneous emission (SE) and amplified spontaneous emission (ASE), with an asymmetry value glum of approximately ±0.31. This value is nearly four-fold greater than that of SE and twice that of ASE. Our findings reveal a new approach to amplify chiral signals, promoting the comprehension and application of chiral–matter interactions, and offering a simple yet effective strategy to fabricate chiral lasers.

CAS / MDL: 51325-91-8 10196-18-6
研究领域: 光学 · 材料科学 · 量子信息处理
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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 11 ·1-10 · IF 5.3

Synergistic enantioseparation system based on a novel nanomaterial synthesized by chiral metal–organic framework and chiral molecularly imprinted polymer in capillary electrochromatography

Miao Pandeng,Zhu Dongyang,Du Shuaijing,Du Yingxiang

A capillary electrochromatography (CEC) synergistic enantioseparation system based on a novel nanomaterial synthesized by chiral molecularly imprinted polymers (CMIPs) and chiral metal organic frameworks (CMOFs) was developed. Compared with CMIPs and CMOFs alone, the enantioseparation performance of ofloxacin (OFL) of the CEC with the novel nanomaterial as stationary phases was greatly improved. CMOFs with chiral recognition ability have synergize with CMIPs to greatly improve the chiral selectivity of the novel stationary phases in CEC. As a proof-of-concept demonstration, a coated capillary column was prepared by a sol–gel method using S-OFL (template), iron-based cyclodextrin MOF (Fe-CD-MOF, a CMOF), 3-aminopropyltriethoxysilane (functional monomer), and tetraethyl orthosilicate (cross-linking agent). Then, the newly constructed CEC system has excellent enantioseparation performance of OFL with a resolution of 3.92. Finally, computerized molecular docking revealed that the difference in the binding ability of Fe-CD-MOF to ofloxacin enantiomers was an important mechanism for CEC chiral separation. This innovative development of synergistic chiral stationary phases based on CMOFs and CMIPs creates a highly efficient potential direction for enantiomer separation. Graphical

CAS / MDL: 919-30-2
研究领域: 分析化学 · 材料科学
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2021 · IF 4.464

Grain-like chiral metal-organic framework/multi-walled carbon nanotube composited electrosensing interface for enantiorecognition of Tryptophan

Xiaofeng Wei,Lishang Li,Huiting Lian,Xuegong Cao,Bin Liu

Due to the widespread application of chiral substances in current society, the electrochemical strategy to assemble chiral metal–organic frameworks (CMOFs) as sensors has shown great potential for sensitive enantiorecognition. In this paper, an efficient and highly selective electrochemical sensor was proposed based on multi-walled carbon nanotube (MWCNT) and CMOF, and successfully achieved sensitive chiral recognition of Tryptophan (Trp) enantiomers . Numerous MOFs in multiple synthesis conditions were investigated for a regular process to access the electrochemical chiral recognition. A variety of amino acids were introduced into the MOFs skeleton by a simple hydrothermal method for the enantio -specificity. Meanwhile the MWCNT smoothly integrated with the CMOF to form a functional electrosensing interface with the increase of conductivity. Based on the current ratio ( R cp ) of tryptophan enantiomers by different modified electrodes , a series of experimental conditions were optimized for the optimal chiral recognition performance of the CMOF/MWCNT-based sensor, finally reaching 2.9 times of ΔI L/D between enantiomers. In addition, D/ l -Trp showed a good linear relationship with the current in the range from 0.4 μM to 19 μM with the detection limit of 0.11 μM for l -Trp and 0.16 μM for d -Trp. The prepared composite-functionalized sensor owned the desired reproducibility and selectivity to identify Tryptophan enantiomers with robust chiral recognition. The research on the structure–activity relationship of chiral MOFs to Tryptophan enantiomers provides a new path to construct more electrochemical sensors for the application of enantiorecognition in pharmaceutical analysis.

研究领域: 分析化学 · 生物医学 · 材料科学
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JOURNAL OF CHROMATOGRAPHY A · 2014 · IF 4.258

Experimental comparison of chiral metal-organic framework used as stationary phase in chromatography

Sheng-Ming Xie,Mei Zhang,Zhi-Xin Fei,Li-Ming Yuan

Chiral metal-organic frameworks (MOFs) are a new class of multifunctional material, which possess diverse structures and unusual properties such as high surface area, uniform and permanent cavities, as well as good chemical and thermal stability. Their chiral functionality makes them attractive as novel enantioselective adsorbents and stationary phases in separation science. In this paper, the experimental comparison of a chiral MOF [In 3 O(obb) 3 (HCO 2 )(H 2 O)] solvent used as a stationary phase was investigated in gas chromatography (GC), high-performance liquid chromatography (HPLC) and capillary electrochromatography (CEC). The potential relationship between the structure and components of chiral MOFs with their chiral recognition ability and selectivity are presented.

研究领域: 分析化学 · 材料科学
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2017 ·Vol. 33 ·期 1 ·24-30 · IF 1.024

A gas chromatographic stationary of homochiral metal-peptide framework material and its applications

Li Lang,Xie Shengming,Zhang Junhui,Chen Ling,Zhu Pengjing,Yuan Liming

Homochiral metal-organic frameworks(HMOFs) have special properties, such as high surface area, fasci-nating structures and excellent chemical and thermal stability and they have broad application prospects. In this work, we reported the use of HMOF Co- L -GG( L -GG, dipeptide H-Gly- L -Glu) as the stationary phase for separating race-mates in gas chromatography. Co- L -GG coated fused silica capillary column(10 m×250 μm i.d.) was prepared via a dynamic coating method. Thirty racemates belonging to different classes of organic compounds were resolved in-cluding halohydrocarbons, ketones, esters, ethers, organic acids, epoxyalkanes, alcohols and sulfoxides. When com-pared with the previously reported chiral MOFs-coated capillary columns, the Co- L -GG coated column exhibited broader chiral resolution ability towards chiral compounds.

研究领域: 分析化学 · 材料科学 · 色谱技术 · 金属有机框架材料
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