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NEW JOURNAL OF CHEMISTRY · 2024 ·Vol. 48 ·期 21 ·9702-9708 · IF 2.7

Preparation of chiral metal–organic framework L-his-MIL-53-NH2@SiO2 composite by in situ growth and chiral post-modification strategies for HPLC enantiomeric separation

An-Xu Ma,Cai-Fang Liu,Yu-Lan Zhu,Zong-Hong Luo,Hong-Mei Zhou,Yue Zhang,Bang-Jin Wang,Jun-Hui Zhang,Sheng-Ming Xie,Li-Ming Yuan

In this work, a chiral core–shell microspheres composite, L-his-MIL-53-NH2@SiO2, was prepared through in situ growth and chiral post-modification strategies. The core–shell microspheres were applied as a novel chiral stationary phase for HPLC enantiomeric separation. Various racemates were separated on the L-his-MIL-53-NH2@SiO2 packed column using n-hexane/isopropanol as the mobile phase. The chiral column showed excellent separation efficiency for fourteen chiral compounds, including alcohols, alkanes, esters, phenols, ketones, and organic acids. The influence of injection mass and temperature on the separation performance of the chiral column were investigated. The relative standard deviations (n = 5) of the retention time and peak area by repeated separation of benzoin are 0.28% and 0.63%, respectively. The results show that the L-his-MIL-53-NH2@SiO2 packed column exhibited good reproducibility and stability. In addition, the chiral resolution ability of the L-his-MIL-53-NH2@SiO2 packed column was compared with that of a commercial chiral column (Chiralpak AD-H). The L-his-MIL-53-NH2@SiO2 packed column exhibits unique advantages in chiral separations that can be complementary to the commercial chiral column. It was demonstrated that the chiral core–shell microspheres composite L-his-MIL-53-NH2@SiO2 prepared based on in situ growth and chiral post-modification strategies has great potential for enantiomeric separation by HPLC.

研究领域: 分析化学 · 材料科学 · 色谱技术
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Design and Electrochemical Chiral Sensing of the Robust Sandwich Chiral Composite d-His-ZIF-8@Au@ZIF-8

Xiaohui Niu,Simeng Yan,Rui Zhao,Hongxia Li,Xiaoyu Liu,Kunjie Wang

In the pursuit of chiral materials with significant chiral recognition effects and stability, various strategies have been explored, among which the integration of metal nanoparticles and chiral metal–organic frameworks (CMOFs) is highly promising. However, metal nanoparticles (MNPs)/CMOFs show high chiral properties but inferior stabilities due to the MNPs being easily detached from the outside layer under certain conditions. Sandwich MOFs@MNPs@CMOF chiral materials can overcome this dilemma because the sandwich structure can maximize the regulation of the chiral interface activity, while the controlled outer layer can stop the MNPs from falling off in the procedure of chiral recognition. Here, a novel sandwich chiral material (d-His-ZIF-8@Au@ZIF-8) was synthesized by a ligand-assisted strategy with a well-defined sandwich morphology and chiral recognition capabilities. The electrochemical chiral recognition showed that d-His-ZIF-8@Au@ZIF-8 was the most efficient for the enantiomer of phenylalanine (Phe). This experiment presents a novel perspective for the fabrication of a chiral electrochemical sensing platform based on a solid sandwich chiral nanocomposite.

研究领域: 材料科学 · 电化学 · 纳米技术
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Journal of Pharmaceutical Analysis · 2021 · IF 4.769

MIL-53-based homochiral metal-organic framework as a stationary phase for open-tubular capillary electrochromatography

Xiaodong Sun,Bing Niu,Qi Zhang,Qin Chen

Homochiral metal-organic frameworks (MOFs) have attracted considerable attention in many fields of research, such as chiral catalysis and chiral chromatography. However, only few homochiral MOFs can be effectively used in capillary electrochromatography (CEC) and their performances are far from adequate. In this study, we successfully synthesized achiral nanocrystalline MIL-53. A facile post-synthetic modification strategy was then implemented to functionalize the product, yielding a homochiral MOF: l -His-NH-MIL-53. This MOF was then employed as a chiral coating in open-tubular CEC mode (OT-CEC), and, as such, it exhibited high enantioselectivities for several racemic drugs. The homochiral MOF and the fabricated capillary coating were systematically characterized using transmission electron microscopy, scanning electron microscopy (with energy-dispersive X-ray spectrometry), Fourier-transform infrared spectroscopy, X-ray diffractometry, thermogravimetric analysis, circular dichroism spectroscopy, Brunauer-Emmett-Teller surface area measurements, and X-ray photoelectron spectroscopy. This study is expected to provide a new strategy for the design and establishment of MOF-based chiral OT-CEC systems.

研究领域: 分析化学 · 材料科学 · 色谱学 · 纳米技术
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JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS · 2019 · IF 2.983

Novel chiral metal organic frameworks functionalized composites for facile preparation of optically pure propranolol hydrochlorides

Xue Ma,Wenrui Du,Yan Li,Chenfeng Hua,Ajuan Yu,Wuduo Zhao,Shusheng Zhang,Fuwei Xie

Two novel sorbents based on polydopamine (PDA)-coated magnetic graphite oxide-metal organic frameworks nanoparticles [Cu( L -mal)(bpy)]·H 2 O (MGO-CuLBH) and [Cu( D -mal)(bpy)]·H 2 O (MGO-CuDBH) possessing of both magnetic property and excellent enantioselective ability were prepared and characterized. Solutions of racemic propranolol hydrochloride ( Rac -PRO) were chosen to investigate the enantioselective performance of MGO-CuLBH and MGO-CuDBH by dispersive magnetic nanoparticle solid phase extraction (d-MNSPE). The results showed that the nanocomposites have excellent enantioselectivity to PROs with enantiomeric excess ( ee ) values reaching up to 98%. The entire process with PROs by the d-MNSPE method was fast, convenient and the collected composites could be easily recycled. Multi-stage operations using MGO-CuLBH and MGO-CuDBH were scaled up to obtain milligram quantities of R -propranolol hydrochloride ( R -PRO) and S -propranolol hydrochloride ( S -PRO). Furthermore, on the basis of the successful preparations, the differences in the cytotoxicity of Rac -PRO, R -PRO and S -PRO on A549 cells in vitro were all evaluated.

研究领域: 材料科学 · 药物化学 · 分析化学 · 生物技术
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ADVANCED FUNCTIONAL MATERIALS · 2025 · IF 19

Amplifying the Circularly Polarized Luminescence of CsPbBr3 Nanocrystals by Chiral Metal–Organic Frameworks: In-Situ Growth, Chiral Assemble, and Chirality Transfer

Jiejun Ren,Boheng Dong,Xiaopeng Zhou,Huiping Liu,Churen Zhang,Fan Liu,Liangjun Chen,Yuhua Wang

Halide perovskites have risen as promising circularly polarized luminescent (CPL) materials for applications in 3D displays, optical anti-counterfeiting, and information storage. And yet, achieving highly anisotropic CPL emission from achiral halide perovskites remains fraught with challenges. Herein, the helical channels of chiral MOFs (L/D-MOFs) are utilized as chiral templates for the in-situ growth of CsPbBr 3 perovskite nanocrystals (NCs), generating CPL-active CsPbBr 3 @L/D-MOFs materials with high luminescence dissymmetry factors (|g lum |, 8.39×10 −3 ) and high photoluminescence quantum yields (QY, 78%). Synchrotron-radiation-based X-ray absorption spectroscopy clearly verifies that the embedded CsPbBr 3 NCs inherit the helicity of L/D-MOFs through strong Cd─Br coordination bonds, thereby facilitating chirality transfer from L/D-MOFs to CsPbBr 3 NCs. Additionally, the efficient Förster resonance energy transfer (FRET) from chiral L/D-MOFs to CsPbBr 3 NCs further amplifies the CPL signal of CsPbBr 3 NCs. Benefiting from the excellent CPL properties and tunable emission, the CsPbX 3 @L/D-MOFs demonstrate great potential in CPL-LEDs. This work proposes a viable strategy for the rational design of high-performance CPL-active perovskite materials and offers profound insights into the chirality transfer mechanism.

研究领域: 材料科学 · 光电子学 · 纳米技术 · 手性光子学 · 钙钛矿光电子
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RSC Advances · 2015 ·Vol. 5 ·期 39 ·30577-30582 · IF 3.84

Chiral metal–organic framework coated quartz crystal microbalance for chiral discrimination

Hao-Jie Duan,Cheng-Xiong Yang,Xiu-Ping Yan

The development of novel methods for chiral discrimination remains a challenging and important area due to the structural similarity but significantly different roles of enantiomers in biological and environmental systems. Here we report a 3D chiral porous Zn–organic framework (Zn2(bdc)(L-lac)(dmf)·DMF) coated quartz crystal microbalance (QCM) sensor for chiral discrimination of four pairs of enantiomers. The adsorption isotherms of the enantiomers on Zn2(bdc)(L-lac)(dmf)·DMF follow the Dubinin–Astakhov equation. The QCM sensor shows excellent sensitivity and enantioselectivity. The chiral recognition ability of the Zn2(bdc)(L-lac)(dmf)·DMF sensor was temperature and concentration dependent. The chiral selectivity factor ranged from 1.36 (S/R-1-(1-naphthyl)ethylamine) to 2.20 (S/R-1-phenylethylamine) at 25 °C. The good chiral recognition capacities of enantiomers provide Zn2(bdc)(L-lac)(dmf)·DMF potential for the discrimination of enantiomers.

CAS / MDL: 10196-18-6 100-21-0
研究领域: 分析化学 · 材料科学 · 化学传感器 · 手性
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ANALYTICA CHIMICA ACTA · 2022 · IF 6.911

Induction of chiral polymers from metal-organic framework for stereoselective recognition

Xiaohui Niu,Simeng Yan,Letong Wang,Jinliang Chen,Rui Zhao,Hongxia Li,Jian Liu,Kunjie Wang

So far, the fabrication of chiral metal-organic framework (CMOF) is difficult to predict and the chiral functionality mainly comes from the building blocks that is a part of the frameworks. The induction effect in the chiral nanochannels of the metal-organic framework (MOF) makes achiral polymers have chiral properties, which has not been well explored. Therefore, CMOFs with chiral nanochannels or chiral pores appear to have special functions. Herein, CMOFs (D-his-ZIF-8) with chiral micropores or chiral nanochannels are prepared through a simple 2-methyl imidazolate in-situ substitution by d -histidine. The unmodified polyaniline with chirality ( c -PANI) was synthesized in chiral nanochannels and pores of CMOF, which brought about chiral induction from the chiral nanochannels and pores of CMOF to c -PANI chains. The circular dichroism shows that the c -PANI chains released from the chiral nanochannel still maintains the chiral properties even leaves the chiral nanochannel. It can be seen from the electrochemical results that c -PANI has excellent conductivity, and the conductivity of CMOF is very poor. Electrochemical recognition showed that both CMOF and c -PANI have certain chiral recognition effects for L-Trp and D-Trp, from which the optimal recognition effect was obtained from c -PANI chains. This shows that the excellent conductivity of c -PANI not only expands the electrochemical signal, but also the helical structure of the c -PANI chains accelerates the distinction of chiral molecules. This study provides a novel perspective to induce chiral polymer chains with better conductivity in the nanochannels of CMOF.

研究领域: 材料科学 · 化学 · 纳米技术 · 电化学
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