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New Porous Materials Used as Chiral Stationary Phase for Chromatography

Bo Tang , Wei Wang , Aiqin Luo

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 328 -341.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 328-341 DOI: 10.7536/PC201249
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New Porous Materials Used as Chiral Stationary Phase for Chromatography
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Abstract

It is well established that enantiomers often exhibit different biological and pharmacological responses. However, enantiomers remain a challenge to separate and analyze due to their identical physical and chemical properties in an achiral environment. Research on specialized separation techniques continues to be developed to obtain optically pure compounds. The separation of enantiomers by chromatographic methods, such as high-performance liquid chromatography (HPLC), gas chromatography (GC), and capillary electrochromatography (CEC), has become one of increasingly important research contents in chemistry over the past few decades due to the demand for pharmaceuticals, agrochemical, and food analysis. The chiral stationary phase (CSP) is key to separating and analyzing chiral compounds for these chromatographic resolution methods. With the rapid development of materials science, diverse types of porous materials as CSP have been studied in recent years. This review mainly focuses on investigating chiral porous materials as CSP for high-performance liquid chromatography (HPLC), gas chromatography (GC), and capillary electrochromatography (CEC) over the past five years. The chiral porous materials include chiral metal-organic frameworks (CMOFs), chiral covalent organic frameworks (CCOFs), chiral porous organic cages (CPOCs), chiral metal-organic cages (CMOCs), chiral microporous organic networks (MONs), and chiral mesoporous silicas (CMSs). Chiral recognition mechanisms of novel chiral porous materials are also discussed briefly. Finally, the related problems and prospects for CSP were briefly discussed.

Contents

1 Introduction

2 CSP of HPLC

2.1 CMOFs used as CSP

2.2 CCOFs used as CSP

2.3 Other materials used as CSP

3 CSP of GC

3.1 CMOFs used as CSP

3.2 CPOCs used as CSP

3.3 CMOCs used as CSP

3.4 Other materials used as CSP

4 CSP for CEC

4.1 CMOFs used as CSP

4.2 CCOFs used as CSP

4.3 Other materials used as CSP

5 CSP for other chromatography

6 Chiral separation mechanism

7 Conclusion and outlook

Graphical abstract

Keywords

chiral porous materials / chiral stationery phase / high performance liquid chromatography / gas chromatography / capillary electrochromatography

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Bo Tang, Wei Wang, Aiqin Luo. New Porous Materials Used as Chiral Stationary Phase for Chromatography. Progress in Chemistry, 2022, 34(2): 328-341 DOI:10.7536/PC201249

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1 Introduction

An object is said to be chiral if it cannot coincide with its mirror image[1]. Chirality is one of the basic characteristics of nature. For example, amino acids, carbohydrates, DNA, proteins and other components of life have significant chiral characteristics. Chirality has a wide and far-reaching impact in many fields, such as medicine, pesticides, spices, fine chemicals, life sciences and so on[2⇓⇓⇓⇓⇓~8]. Especially in the field of biomedicine, only one of the two enantiomers of chiral drugs has curative effect, while the other enantiomer has no effect or even toxic side effects[9]. Therefore, it is of great significance to produce enantiomerically pure compounds or to perform accurate enantiomeric quantitative analysis of chiral compounds.
Because the enantiomers have almost the same physical and chemical properties, the separation and analysis of enantiomers is a very challenging task. At present, chromatography based on Chiral stationary phase (CSPs) is one of the important ways to obtain enantiopure compounds[10]. In the long history of chiral separation and analysis, polysaccharides (including cellulose, amylose, chitosan), cyclodextrins, calixarenes, crown ethers and other chiral selectors have been found and played an important role in chiral separation and analysis[11⇓⇓⇓⇓~16]. However, in the face of the increasing demand for chiral separation and analysis, the development of new and high-performance chiral stationary phases is still the research focus and hot spot of chromatography.
A porous material is a material with a continuous or closed pore structure. Porous materials have attracted much attention due to their large specific surface area and controllable structure and pore size. With The development of materials science, in addition to obtaining natural porous materials from nature, scientists have also synthesized inorganic porous materials (such as molecular sieves, mesoporous silicon), inorganic-organic hybrid porous materials (such as Metal-organic framework materials (Metal-organic Framework Materials, Metal-Organic Framework Materials).MOFs), Metal-organic cages (MOCs), organic porous materials (such as Covalent organic frameworks (COFs)) and other new porous materials, and the application of these materials has been extensively explored[17⇓⇓⇓⇓⇓⇓⇓⇓~26]. Novel chiral porous materials with chiral structure are ideal chiral recognition and separation materials due to their good stability, large specific surface area, adjustable pore size and abundant chiral sites. At present, they are widely used as chiral stationary phases in High performance liquid Chromatography (HPLC), Gas chromatography (GC) and Capillary electrochromatography (CEC)[27⇓⇓⇓⇓⇓~33]. In this paper, the application of CSP based on novel chiral porous materials in these three chromatographic types in the past five years is reviewed, and the chiral separation mechanism based on chiral porous materials is summarized.Finally, the development of CSP is prospected.

2 Liquid chromatography

High performance liquid chromatography (HPLC) based on CSP is one of the most commonly used methods for chiral separation and analysis, especially for the separation and analysis of chiral drugs, HPLC has obvious advantages. At present, a variety of chiral stationary phases, such as brush, ligand exchange, polysaccharide derivatives, crown ethers, macrocyclic antibiotics and proteins, have been widely studied, and commercial columns are available[34⇓⇓⇓~38]. Chiral metal-organic frameworks (CMOFs), Chiral COFs (Chiral covalent organic frameworks, COFs) and Chiral mesoporous silicas (Chiral mesoporous silicas, CMSs) are the research hotspots in this field.

2.1 CMOFs as chiral stationary phase

Chiral metal-organic frameworks (CMOFs) are a new type of porous functional materials, which are mainly self-assembled by metal ions (or metal clusters) and chiral organic ligands. CMOFs have been widely used in asymmetric catalysis, chiral separation, chiral sensing and other fields because of their structural diversity, good stability, large specific surface area and uniform active sites, and are also one of the important research directions of new CSP in liquid chromatography[39][40][41][42,43]. The study of CMOFs as CSP for liquid chromatography is usually to prepare crystalline CMOFs first, and then fill the screened CMOFs with uniform particle size to obtain a liquid phase column[44⇓~46]. At present, many different types of CMOFs have been reported as chiral stationary phases for HPLC[47]. For example, in 2016, Zhang et al. reported that a 3D porous CMOFs with D-camphoric acid as chiral ligand was used as CSP for HPLC. Under optimized chromatographic conditions, 9 different types of racemic compounds were resolved with different degrees of chirality (some chiral compounds with better resolution on HPLC (resolution Rs > 1.5) are summarized in Table 1), showing the potential ability of CMOFs as a new CSP[48]. In 2017, Yang et al. reported a kind of CMOFs based on γ-cyclodextrin (γ-CD) as CSP. By changing the experimental conditions, the synthesized γ-CDMOF has good resolution effect on 12 kinds of chiral aromatic alcohols. They also verified that the chiral microenvironment of γ-CDMOF, especially the hydrophobic cavity and hydrophilic edge provided by γ-CD, is one of the important reasons for the high selectivity of CMOFs for chiral aromatic alcohols[49]. In 2017, Zhang et al. Synthesized six different types of CMOFs with different types of L-amino acids as chiral ligands, Zn2+ and Co2+ as metal ions. The obtained CMOFs were used as CSP in HPLC for chiral resolution, and good separation results were achieved for a variety of chiral compounds such as alcohols, amines, ketones, ethers and organic acids[50]. In 2019, Corella-Ochoa et al. reported the synthesis of a 3D porous CMOFs with L-histidine as the chiral group and its application in the resolution of enantiomers. The results showed that the liquid phase column filled with CMOFs could be used in a variety of mobile phase systems, and the baseline separation of racemates of five different types of chiral compounds was achieved[51]. These results indicate that CMOFs have great potential as novel CSPs for liquid chromatography.
Due to the irregular shape of the synthesized CMOFs, the HPLC chromatographic column prepared by directly loading CMOFs into the column usually has the problems of high column pressure, low column efficiency and asymmetric peak shape. This greatly limits the practical application of CMOFs as CSPs for liquid chromatography. Therefore, some research groups have studied the utilization methods of CMOFs. For example, in 2016, Tanaka et al. Synthesized two columnar CMOFs, which were mixed with SiO2 microspheres to prepare HPLC columns with good chiral separation effect for a variety of racemic chiral compounds (such as sulfoxides, secondary alcohols and flavonoids)[52]. In 2019, they synthesized an open cage CMOFs and mixed it with SiO2 microspheres to prepare a liquid column, which has a good resolution effect on 12 racemates including alcohols, sulfoxides, lactones and oxazolidinones. In this paper, they show that the porous structure of CMOFs is the main reason for CSP to achieve effective chiral recognition, and the chiral resolution ability of (R) -CuMOF-2 (10.77 Å) with larger pore size is better than that of CMOFs (R) -CuMOF-1stationary phase previously reported by them[53][54].
Compared with the method of directly mixing the CMOFs/SiO2 before packing in the column, the method of preparing CMOFs@SiO2 core-shell CSP by modifying CMOFs on the surface of SiO2 microspheres can obtain a liquid phase column closer to practical application. For example, in 2018, Yuan et al. Fixed CMOFs([Nd3(D-cam)8(H2O)4Cl]n) on the surface of SiO2 microspheres by interfacial polymerization, and prepared two CSP(CSP-1:1-PIP-TMC-SiO2;CSP-2:1-MPDTMC-SiO2) of CMOFs coating with uniform particle size. The obtained CSP was used to prepare a chromatographic column, and the chiral separation effect was tested under normal phase, reverse phase and polar organic phase conditions, respectively. The results show that these CSPs have good resolution effects on a variety of chiral compounds such as alcohols, amines, ketones and α-amino acids. Among them, 17 chiral compounds could be separated on CSP-1 column, 13 chiral compounds could be separated on CSP-2 column, and only 6 chiral compounds were separated on pure MOF column. This study shows that the design and post-modification of CMOFs play an important role in the chiral separation performance of CMOFs[55]. In 2020, they reported the synthesis and application of core-shell CMOFs stationary phase: the chiral MOF material (D-His-ZIF-8) was uniformly modified on the surface of carboxylated SiO2 microspheres by a one-pot method, and D-His-ZIF-8@SiO2 core-shell microspheres with uniform particle size were prepared (Figure 1). The material was used as CSP for the study of enantiomeric separation in HPLC. The results showed that 18 different racemic compounds, including alcohols, phenols, amines, ketones and organic acids, could be well resolved by the CSP. This study also shows that the CMOFs@SiO2 of core-shell microspheres composite is one of the effective ways to use CMOFs as CSP for HPLC resolution of racemates[56]. In the same year, Wang et al. Prepared SiO2@Cu2C2D core-shell chiral stationary phases from chiral MOF(Cu2((+)-Cam)2Dabco,Cu2C2D) by layer-by-layer self-assembly method. Five chiral racemates of carboxylic acids, ketones and phenols were successfully separated by normal phase chromatography. It was also found that the separation ability of the stationary phase was improved with the increase of the growth period of CMOFs, which indicated that the existence of CMOFs was the key factor for CSP to achieve chiral separation. In addition, the stationary phase can also be used to determine the enantiomeric excess of products in asymmetric synthesis, and the results are the same AS those of commercial column Daicel Chiralpak AS-H, which indicates that the stationary phase has good practicability[57].
In addition to preparing CMOFs into core-shell CSP, the application of CMOFs in monolithic CSP is also expected. For example, Wang et al. Prepared a porous polymer monolithic column with CMOFs[Zn2(bdc)(L-lac)(dmf)](DMF) for the resolution of (±) -benzoyl sulfoxide by nanoliter liquid chromatography, and achieved good results. It is also shown that CMOFs play a crucial role in the chiral resolution process[58].
Based on the above studies, CMOFs, as a new type of CSP, is feasible for the separation of chiral compounds by liquid chromatography, which provides a basis for the application of CMOFs in the field of chromatography.

2.2 CCOFs as chiral stationary phase

Covalent organic framework materials are a class of crystalline organic porous polymers with permanent porosity and highly ordered structure, which are connected by light elements such as H, C, N and O through covalent bonds. COFs have the characteristics of strong design, regular pore channel, high stability and adjustable function[59]. These characteristics make CCOFs also have the potential to be used in chiral recognition, chiral separation and asymmetric catalysis[60⇓~62]. However, the successful construction of CCOFs requires a certain balance between asymmetry and crystallinity. The presence of chiral ligand units often leads to the difficulty of crystallization or poor crystal stability of CCOFs[63]. These factors limit the application of CCOFs to some extent. At present, there are few reports on the use of CCOFs as chromatographic stationary phases.
In 2017, Zhang et al. Synthesized a new type of CCOF (BtaMth) with high porosity and good chemical stability by using chiral hydrazide as ligand, and successfully modified COF on the surface of amino-modified silica gel by one-pot method to prepare core-shell BtaMth@SiO2 composites. Baseline separation of two positional isomers, p-nitrotoluene and chloronitrobenzene, was achieved in reversed phase mode using BtaMth@SiO2 as CSP HPLC column. The cis-trans isomers of cypermethrin and metconazole were resolved in the normal phase mode. This study not only promotes the research on the preparation of chiral COF materials, but also demonstrates that the COF@SiO2 composite has the potential to be used as a new CSP for HPLC[64].
In order to overcome the difficulty in the synthesis of chiral COF, Zhang et al. Used an alternative strategy to immobilize lysozyme and other biomolecules into the pores of achiral COF, and obtained a class of chiral COF materials based on chiral molecules. The prepared lysozyme COF is used as CSP of HPLC, and baseline resolution of various alpha-amino acids and chiral drugs can be realized. This study provides valuable guidance for the development of efficient and stable biomolecular CSP[65].
In 2018, Han et al. Reported the first synthesis of 3D CCOF and used it as CSP for HPLC separation of racemates of alcohols, sulfoxides, carboxylic acids and esters[66]. First, they used tetra- (4-anilyl) methane with tetrahedral structure and tetraaryl-1,3-dioxolane-4,5-dimethanol to obtain CCOF-5 connected by imine bond through dehydration condensation, and then oxidized the imine bond into amide bond to obtain CCOF-6 material with better chemical stability while maintaining crystallinity and permanent porosity (as shown in Figure 2). Finally, CCOFs with an average particle size of about 0. 3 μm were mixed with SiO2 microspheres with a particle size of about 5 μm to prepare an HPLC column, and baseline separation of a variety of racemic mixtures was achieved in the n-hexane/isopropanol mobile phase system, and the oxidized CCOFs had better chiral separation performance. This study shows that CCOFs have great potential as chromatographic CSPs.

2.3 Other materials as chiral stationary phase

In addition to CMOFs and CCOFs mentioned above, new Chiral porous materials such as Chiral mesoporous silica (CMSs) and chiral porous polymers have also been used for chiral separation in HPLC. The first report of mesoporous silica materials can be traced back to the silicate materials with mesoporous structure (pore size 2-50 nm) synthesized by Japanese scientists and Mobil Company in the 1990s[67]. Subsequently, scientists have conducted extensive research on the controllable preparation and chemical modification of mesoporous silicon metamaterials[68]. Chiral mesoporous silica materials are mainly self-assembled by chiral or achiral templates and silica precursors, which have a wide range of applications in biomedicine, drug delivery, adsorption, sensing, catalysis and other fields[69⇓⇓⇓~73]. Chromatographic separation is also one of the important applications of CMSs[74]. For example, in 2019, Peng et al. used CMSs as CSPs for HPLC. Eighteen racemates, including alcohols, ketones, amines, aldehydes, and organic acids, were separated on this column. This study shows that CMSs have great potential as CSPs. This work provides a new approach for the preparation of stationary phases from inorganic materials[75]. In 2020, Chen et al. Designed and synthesized a porous polymer with three-dimensional chiral channels (MP-CDPs) from cyclodextrin. With MP-CDPs as adsorbent, > 73% enantiomeric excess of (R)/ (S) -1-phenylethylamine could be achieved within 3 min. Subsequently, they combined MD-CDPs with silica microspheres to prepare MP-β-CDPs@SiO2 composite materials, which were used as CSP for HPLC. With n-hexane/isopropanol as the mobile phase, (R)/ (S) -mandelic acid, (R)/ (S) -1-phenyl-1-propanol, (R)/ (s) -3-chloro-1-phenyl-1-propanol and D/L-proline were baseline separated within 8 min[76].

3 Gas chromatography

Gas chromatography is an important branch of chromatography. Gas chromatography plays an important role in the field of chromatographic separation and analysis of chiral compounds because of its high column efficiency, good sensitivity and fast analysis. The study of chiral stationary phases in gas chromatography mainly focuses on the search for new materials with multiple chiral centers and multiple interactions. At present, a variety of chiral stationary phases including amino acid derivatives, cyclodextrin derivatives, metal chelates and cellulose derivatives have been successfully prepared. In recent years, chiral porous material stationary phases for gas chromatography have been widely studied, including CMOFs, CCOFs, CMSs, Chiral porous organic cages (CPOCs) and chiral metal-organic cages (CMOCs).

3.1 CMOFs as chiral stationary phase

The study of CMOFs as chiral stationary phases for gas chromatography was first reported by Xie et al in 2011[77]. Subsequently, they reported a variety of CMOFs as chiral stationary phases for gas chromatography[78⇓⇓⇓~82]. In addition to using CMOFs directly as stationary phases, they also studied the synergistic effect of CMOFs with a variety of commercial chiral stationary liquids. For example, CMOFs were combined with pentyl-β-cyclodextrin to prepare mixed CSP for GC resolution of racemates, and the results showed that CMOFs could promote the chiral resolution of cyclodextrin[79].
CMOFs can be prepared not only by direct synthesis of chiral ligands, but also by post-synthesis modification. In 2018, Kou et al. reported the post-synthesis modification method of CMOFs, and applied the obtained CMOFs to gas chromatography. The results showed that the MIL-101(Al)-NH2 had large pore size and amino active sites, which were beneficial to post-synthesis modification. Five different CMOFs, MIL-101 (Al) -Xs (Xs = (S) -2-phenylpropionic acid, (R) -phenylethylene oxide, (+) -diacetyl-L-tartaric anhydride, L-proline and (1s)- (+) -camphor-10-sulfonyl chloride), were obtained. A total of 12 racemates of alcohols, amines, nitriles, esters and aldehydes were resolved on MIL-101 (Al) -Xs capillary columns, indicating that post-synthetic modification provides feasibility for the construction of CMOFs for GC[83].
In addition, some analogues of CMOFs have also been used in the study of chiral stationary phases for gas chromatography. For example, in 2017, Yang et al. Reported the use of Chiral Crystalline Sponge (CCS) as a GC Chiral stationary phase. The capillary column coated with CCS-3S was prepared by dynamic method, and was used for GC chiral separation of 10 chiral alcohols and nitriles within 5 min. The resolution of some racemates was higher than that of commercial chiral columns β-DEX225 and Cyclosil-B, which indicated that CCS had the potential as CSP. In addition, they also found that CCS-3S can also be used to identify the absolute configuration of enantiomers, and when combined with GC with CCS-3S as CSP, the purification and identification of enantiomers can be achieved simultaneously without enantiomeric standards[84]. In 2019, they mixed CCS-3S with polysiloxane OV-1701 and coated it statically to obtain a capillary column. The results showed that the addition of OV-1701 could not only significantly improve the chiral separation performance of CCS-3S, but also expand the range of enantiomer separation. Moreover, the capillary column coated with OV-1701/CCS-3S mixed stationary phase has better repeatability, stability and service life than that coated with CCS-3S alone[85].

3.2 CPOCs as chiral stationary phase

POCs are porous materials similar to COFs, which are mainly self-assembled by organic molecules through relatively weak intermolecular forces. However, unlike COFs, these materials have better solution dispersibility, that is, they can be dispersed in some specific organic solvents without destroying the original cage structure. This characteristic makes POCs easy to form films and is an ideal GC stationary phase material.
Based on this, in 2015, Kewley et al. reported the study of CPOC [CC3-R] as a stationary phase for gas chromatography. They used a static method to directly coat CC3-R in a capillary column to obtain a capillary column, and used alcohol and amine racemates as analytes to test the chiral resolution ability of the CC3-R stationary phase. The preliminary study showed that CC3-R had good chiral resolution ability. However, because the chromatographic column was not optimized in this paper, the chromatographic peaks were generally tailed[86].
At the same time, Zhang et al. reported in detail the study of CPOC [CC3-R] as a gas chromatographic CSP. In this paper, they used dozens of different types of racemates as analytes to verify the chiral separation ability of CC3-R in more detail. The results showed that the gas capillary column prepared by mixing CC3-R with OV-1701 showed high selectivity and separation ability for various racemates including alcohols, glycols, amines, alcohol amines, esters, ketones, ethers, halogenated hydrocarbons, organic acids, amino acid methyl esters and sulfoxides. Compared with the commercial column of Chirasil-L-Val and β-DEX120, many chiral compounds which could not be separated by the two commercial columns were separated by CC3-R column[87]. Subsequently, they carried out detailed research on this kind of materials: in the same year, they reported that chiral POC CC10 was used as CSP for gas chromatography, and achieved good chiral resolution effect on chiral alcohols, esters, ketones, ethers, epoxides and organic acids[88]. In 2016, they reported the application of another POC as a gas chromatography CSP in chiral resolution. Mixing the prepared CC9 and polysiloxane OV-1701 according to a certain proportion, and coating the mixture by a static method to obtain a capillary column. After testing, the CC9 coated capillary column can separate a variety of alcohol, ester, ether and epoxy chiral compounds, and the chiral separation range of the column is complementary to the β-DEX120 commercial column and their previously reported CC3-R column[89]. In 2017, they reported the study of chiral CC5 as a stationary phase for gas chromatography: a capillary column was prepared by mixing CC5 with OV-1701, which has high separation ability for a variety of positional isomers and enantiomers; Since the pore size of CC5 is larger than that of CC3-R, CC5 can have better separation performance for some chiral compounds with larger molecular size, such as amino acid derivatives (N-trifluoroacetyl amino acid isopropyl ester) (fig. 3)[90]. In 2019, Li et al. also reported the application of hydroxy-modified POC [POC-1] as gas chromatography CSP. Various racemates such as alcohols, diols, esters, lactones, halogenated hydrocarbons, ethers, epoxides, ketones and sulfoxides were used to characterize the chiral recognition ability of POC-1. The results showed that POC-1 had excellent resolution effect on the aforementioned chiral compounds. POC-1 was superior to β-DEX120 in the resolution of some compounds. The resolution range is complementary compared to their previously reported CC9 and CC10 columns. This study also shows that the introduction of different functional groups into POC to change the chiral microenvironment of the cage cavity can significantly improve the chiral recognition ability of POC[91]. In addition, Li et al. Used (1R, 2R) -1,2-diphenylethylenediamine to replace (1R, 2R) -diaminocyclohexane used in the synthesis of POC-1 to obtain another POC. The results showed that the POC material also had good chiral resolution ability. Aromatic positional isomers were eluted in o-/m-/p- order on this POC column, but in p-/o-/m- order on POC-1 without benzene ring modification, which may be due to the change of pore size and chiral microenvironment caused by the introduction of benzene ring in the ligand, resulting in the difference of elution order[92].
Wang et al. Also reported the application of POCs in gas chromatography recently. They reported a fast and green POC synthesis method: nanoscale CC3S, CC3R and hydroxyl-modified CC3R-OH POC were successfully prepared by ethanol reflux method. The three synthesized POC crystals were used for the resolution of chiral alcohols, and good results were obtained, and the chiral alcohols had better resolution on CC3R-OH, which may be due to the introduction of hydroxyl group, which increased the hydrogen bonding force between CC3R and chiral alcohols. This study shows that the rational design and modification of POC have a significant effect on the improvement of chiral selectivity[93].

3.3 CMOCs as chiral stationary phase

Metal-Organic Polyhedras (MOPs), also known as Metal-organic polyhedras, are a class of special supramolecular materials with cage-like structure[94]. Similar to MOFs materials, they are assembled by metal ions and organic ligands. However, MOCs have a special cavity structure, which can accommodate specific guest molecules. Moreover, the cage units are packed into a porous solid by weak intermolecular forces and thus can be dissolved in certain solvents, which is very similar to POCs. Therefore, MOCs also have a wide range of applications in catalysis, molecular recognition, separation, sensing and other fields[95⇓~97].
In 2018, Xie et al. First reported the application of CMOCs as gas chromatography CSP. They chose a CMOC[Zn3L2] soluble in dichloromethane, mixed it with polysiloxane OV-1701, and coated it statically to prepare a capillary column. The results showed that the column had a good separation performance for a variety of enantiomers, such as alcohols, glycols, epoxides, ethers, halogenated hydrocarbons and esters. The chiral resolution range is complementary to the commercial column β-DEX120 and the previously reported CC3-R column. This study provides the possibility for the application of MOC in the stationary phase of gas chromatography[98]. Recently, they have also studied the use of CMOC as a gas chromatography CSP. We synthesized an amorphous CMOC (aMOP-a) by self-assembly of L-alaninyl chiral ligand and Cu2+, and prepared the capillary column by dynamic method. After testing, the chromatographic column has a good resolution effect on a variety of chiral compounds such as alcohols, acids, ethers and amino acid derivatives[99]. Subsequently, we prepared another crystalline CMOC[Cu12(LPA)12(H2O)12] with L-phenylalanine (L-PA) as the chiral group. The results showed that the capillary column with the crystalline MOC as the CSP had a good resolution effect on acids, esters, ethers and amino acid derivatives, and the resolution effect on amino acid isomers was significantly better than that of the amorphous MOC reported before. In addition, the CSP also has a good separation effect on n-alkanes, n-alcohols, methyl esters, polycyclic aromatic hydrocarbons and other analytes, which indicates that metal-organic cage materials not only have the potential of chiral separation, but also are worth looking forward to as achiral stationary phases[100]. Previous studies have shown that CMOC has the potential to be used as a CSP in gas chromatography, but the related research is still in the initial stage, and further research is still needed to explore the potential of CMOC in the field of chromatography.

3.4 Other materials as chiral stationary phase

In addition to the materials mentioned above, various types of chiral porous materials have been used in the study of gas chromatographic CSP. For example, in 2016, Qian et al. reported the study of chiral COF as gas chromatography CSP: firstly, chiral groups were introduced to COF monomers through esterification reaction; Then CCOFs were synthesized by "bottom-up" one-step method. Finally, the CCOFs are introduced into the capillary column by an in-situ growth method, and the chiral gas phase capillary column is finally prepared. The CCOFs used for chiral separation have high chiral selectivity for 1-phenylethanol, 1-phenyl-1-propanol, limonene and methyl lactate, and can realize baseline separation. This study provides a basis for the application of CCOFs in gas chromatography[101]. In 2018, Li et al. Used CMSs as capillary gas chromatography stationary phase for the first time, and achieved good resolution results for a variety of racemic compounds. They first synthesized chiral anionic surfactant N-myristoyl-L-alanine (C14-L-AlaA) from L-alanine. Then, the template is used as a template and tetraethyl orthosilicate is used as a silicon source to prepare a silicon-based mixture, and finally, the template is removed at high temperature to obtain the CMSs product. Subsequently, they mixed the synthesized CMS with OV-1701stationary liquid and prepared the capillary column by dynamic method. With different types of chiral compounds as test substances, 15 compounds of 6 categories, including alcohols, aldehydes, esters, organic acids, epoxides and amino acid derivatives, were separated to varying degrees on CMSs coated capillary columns. The results showed that CMSs had good chiral recognition ability for chiral compounds[102]. In 2019, they prepared another CMSs material with L-valine as the chiral group, and used it as CSP for gas chromatography. The column prepared has a good resolution effect on a variety of chiral compounds, especially derivatives of α-amino acids[103].
In 2020, Cui et al. First reported the study of Microporous organic networks (MONs) as CSP for gas chromatography. They first synthesized MONs and then introduced chiral groups on MONs by thiol-alkyne click reaction. By using three different modifiers, three CMONs materials with different chiral microenvironments were obtained. The results of chiral resolution showed that CMONs had good resolution effect on a variety of chiral alcohols. The application of MONs as CSP in gas chromatography has been expanded[104].

4 Capillary electrochromatography

Capillary electrochromatography (CEC), which combines the advantages of high column efficiency of Capillary electrophoresis (CE) and high selectivity of HPLC, has become an efficient chromatographic separation technique[105⇓~107]. CSP-based CEC has attracted the attention of researchers because of its high column efficiency, high sensitivity and low mobile phase consumption[108⇓⇓~111]. Like HPLC, CSP is also the key to achieve chiral separation by CEC[112]. The CSP used in CEC is similar to HPLC, and the CSP with chiral resolution ability on HPLC also has similar separation effect when used in CEC[106]. Therefore, some novel chiral CSPs commonly used in HPLC, such as CMOFs, CCOF and POC, have also been used in CEC chiral resolution studies.

4.1 CMOFs as chiral stationary phase

The research on the application of CMOFs in the chiral resolution of CEC started in 2014[113]. Subsequently, several research teams reported similar applications. For example, in 2016, Ye et al. reported the study of CMOFs as CSP in capillary electrochromatography, and the results showed that the chromatographic column modified by CMOFs could effectively separate DL-phenylalanine and DL-tyrosine. In addition, it is found that the capillary column with higher thermal stability and wider linear range can be obtained by establishing covalent bond between CMOFs and capillary[114]. In 2018, Pan et al. reported the study of CMOFs as CSPs for capillary electrochromatography. A novel zeolite-like chiral metal organic framework (JLU-Liu23) with double helix structure was prepared and used as CSP in open tubular capillary electrochromatography (OT-CEC) to separate four monoamine neurotransmitters and their analogues[115]. In 2020, they reported a chiral MOF based on γ-cyclodextrin (γ-CD) as a CSP for capillary electrochromatography. The results showed that the capillary column modified by γ-CD-MOF showed excellent chiral recognition ability for five DNS-amino acids (phenylalanine, leucine, valine, threonine, serine)[116]. In addition, the open tubular column prepared by the polydopamine modification method shows excellent stability and repeatability. In 2020, Wang et al. combined ZIF-8 with bovine hemoglobin (BSA) to prepare BSA @ ZIF-8 chiral open tubular column, which was used in capillary electrochromatography and successfully resolved five isomers and three chiral compounds[117].

4.2 CCOFs as chiral stationary phase

CCOF materials are rarely used in CEC chiral separation, and only a few articles have been reported so far. In 2019, Xu et al. introduced achiral COFs materials into the preparation of chiral polymer monoliths, and found that the addition of COFs materials could improve the chiral recognition performance of the monoliths. Under the optimized experimental conditions, the baseline separation of the four racemic drugs was achieved. This may be because the COFs used not only have high surface area, but also have conjugated structures and abundant amine groups, which can provide additional π-π interaction and hydrogen bonding in the chiral separation process[118]. In 2019, Wang et al. reported that CCOFs were used as CSP for the separation of chiral drugs by capillary electrochromatography. Firstly, β-CD COF was prepared by condensation reaction of β-cyclodextrin and terephthalaldehyde at room temperature. Subsequently, β-CDCOF as CSP was modified on the inner wall of the capillary column by photopolymerization. Finally, the prepared capillary column is used for the separation of chiral drugs on capillary electrochromatography. By optimizing the chromatographic conditions, the column achieved baseline separation of six chiral drugs with good stability and repeatability. The results show that CCOF has great potential as CSP in capillary electrochromatography[119]. In 2020, Li et al. reported the synthesis of CCOF by post-modification and its study as CSP for capillary electrochromatography (as shown in Figure 4). Isocyanate-β-cyclodextrin modified COF (MDI-β-CD modified COF) was synthesized by bottom-up method using isocyanate-β-cyclodextrin as chiral selector and imino-TpPa-1 COF as matrix. Then the open tubular column with MDI-β-CD modified COF as CSP was prepared by in-situ growth method. Eight compounds including four amino acids and four β-blockers can be separated by the chromatographic column with good repeatability[120].

4.3 Other materials as chiral stationary phase

In addition to the above two CSPs, which have achieved good results in HPLC, some chiral porous materials, which have achieved good results in GC, have also been used in the chiral resolution of CEC. For example, in 2018, Zhang et al. reported the application of porous organic cage CC3-R in capillary electrochromatography, and the results showed that the CC3-R capillary column showed high selectivity and separation performance for a variety of racemates and positional isomers[121]. In 2019, He et al. Reported the study of metal organic cages as CSP in capillary electrochromatography, and the results showed that three different types of MOCs immobilized on chiral compounds such as amines, acids, alcohols and ketones showed good chiral recognition ability, and had good repeatability and stability. This study shows that chiral MOCs can be used for the separation of enantiomers in capillary electrochromatography[122]. In 2020, Li et al. Reported that the monolithic column constructed by MOCs and ionic liquids was used for chiral separation in capillary electrochromatography. The results showed that baseline separation of 4 positional isomers and 3 enantiomers was achieved by the prepared Zn3L2@poly(IL-co-EDMA) monolithic column. They believe that the host-guest interaction between chiral analytes and MOC cavities is one of the important reasons for chiral separation. This study also demonstrates that chiral MOC has great potential in the field of electrochromatographic chiral separation[123]. Table 2 summarizes the names of racemic compounds and their resolution for chiral resolution reported in the above literature.

5 Other chromatography

In addition to the above three methods, Supercritical fluid chromatography (SFC), Column chromatography, Thin layer chromatography (TLC) and other chromatography also play an important role in chiral separation and analysis. Among them, SFC, which uses supercritical fluid such as CO2 as mobile phase, can make up for the shortcomings of HPLC in the field of chiral separation and analysis, especially in the preparation/semi-preparation of chiral drugs, and is becoming one of the new chromatographic research hotspots[124,125]. At present, the commonly used CSPs in SFC mainly include polysaccharides, crown ethers, cyclodextrins, glycoproteins and Pirkle type, while the CSP based on chiral porous materials has not been reported[126⇓~128]. However, it can be predicted that with the increasing role of SFC in chiral separation and analysis, the development of new porous materials based on chiral porous materials will inevitably become one of the new research directions.
Thin-layer chromatography and column chromatography are both classical chromatographic separation techniques, which are often used for the separation and identification of compounds. Porous silica gel is mainly used as the stationary phase in thin layer chromatography and column chromatography, and there are only a few reports on the research of new stationary phases based on porous materials. In 2017, Schenk et al. First reported the application of MOFs as stationary phase in TLC[129]. Firstly, The synthesized Zr-based MOF (DUT-67) was grinded into particles with an average particle size of ~ 0.76 μm by a vibrating ball mill, and then the MOF was mixed with hydroxypropyl cellulose, styrene-butadiene rubber and F254 fluorescent indicator, and coated on an aluminum plate to prepare the TLC plate.MOFs were successfully separated from the mixture of trans-cinnamaldehyde/benzaldehyde and 2-aminotoluene/4-aminophenol by TLC under the optimized conditions, which demonstrated the feasibility of MOFs as the stationary phase for TLC. In 2018, Zhang Mei et al. reported that CMOFs[Zn2(D-Cam)2(4,4'-bpy)]n was used as the stationary phase of TLC for the separation of the chiral drug amlodipine besylate, and the results showed that the two enantiomers of amlodipine besylate were effectively separated under the optimized separation conditions (Rf value was Rf>0.27, and the resolution RS was about 2)[130]. In 2020, Fu et al. combined MOFs, TLC and Photonic crystals (PC) technology to develop MOFs/PC based High-performance thin-layer chromatography (HPTLC).The results showed that the MIL-100/PC-based TLC plate successfully separated the cresol isomers which were difficult to separate on the traditional TLC plate, and the separation factor α of MIL-100/PC plate was 2. 51, which was significantly higher than that of GC (α = 1. 05) and commercial thin layer plates (α = 1. 11), showing the potential of MOFs as a stationary phase for thin layer chromatography[131]. In 2020, Tang et al. reported the synthesis of CMOFs with L-phenylalanine as the chiral ligand, and then packed 360 mg of CMOFs into a glass column with an inner diameter of about 0.5 cm, and achieved the effective separation of ibuprofen racemate with acetone as the eluent.The enantiomeric excess of (R) -ibuprofen in the eluate was 99. 9%.Due to the stronger interaction between (R) -ibuprofen and CMOFs, the elution time of (S) -Ibuprofen was earlier than that of (R)-Ibuprofen[132].
The above study shows that it is feasible to use chiral porous materials such as CMOFs as CSP for thin-layer chromatography or column chromatography for the separation of racemates, which is of great significance for the development of new chiral separation and analysis methods. However, it is not difficult to see that due to the difficulty and high cost in the synthesis of chiral porous materials such as CMOFs at this stage, only thin layer plates or chromatographic columns with milligram or gram fillers can be prepared (more similar to solid phase extraction), and the wide use of chiral porous materials in thin layer chromatography or column chromatography needs further development.

6 Chiral resolution mechanism

Based on the chiral separation mechanism of chromatography, the principle of "three-point interaction" proposed by Dalgliesh is widely used at present[133,134]. According to this theory, CSP and enantiomers must have three interaction points at the same time, and at least one of these interaction points is stereochemical. The slight difference of the force between the different configurations of the enantiomers and the CSP is amplified by repeating many times in the chromatographic process, and finally the separation of the enantiomers is realized. Chiral porous materials have a complex chiral microenvironment, and the chiral resolution process is usually the result of the synergy of multiple forces. Hydrogen bonding, van der Waals force, dispersion force, π-π interaction, dipole-dipole interaction, inclusion interaction and stereo matching have important effects on the chiral separation and resolution of chiral porous materials. Therefore, the separation effect of CSP based on chiral porous materials can not be accurately predicted. In order to facilitate readers to understand the application progress of chiral porous materials in the field of chromatography, we summarize the main chiral compounds of various CSP resolutions involved in this paper in Table 3.

7 Conclusion and prospect

Chromatography based on CSP is one of the most widely used methods for chiral separation and analysis. The study of new CSP based on chiral porous materials not only enriches the types of chiral stationary phases, but also provides an important research basis for the development of chiral separation and analysis methods. However, we should also see that the current research is still in the basic stage, and there are still some problems to be further solved: ① controllable preparation of chiral porous materials; The introduction of chiral groups makes the synthesis of chiral porous materials difficult, and the existing research mainly focuses on the direct application after the synthesis of chiral porous materials.However, the chiral materials directly prepared in this way have great differences in morphology, particle size, active sites and other physical and chemical properties, and it is often difficult to achieve satisfactory repeatability when used as CSP. (2) The mechanism of chiral separation is complex. Existing studies have shown that when chiral porous materials are used as CSP, chiral separation is affected by a variety of forces, which makes it impossible to accurately predict the chiral recognition ability of materials. To solve the above problems, more scholars in the field of chromatography and materials need to pay attention to, participate in and enrich the relevant basic research, so as to promote the research and development of chromatographic chiral stationary phases.
In conclusion, chiral porous materials, as a new type of CSP, have been used for chromatographic separation and analysis of chiral compounds, and some achievements have been made. Some types of chiral porous materials can have good chiral separation ability in a variety of chromatographic modes. For example, chiral metal-organic framework materials have shown good separation ability in HPLC, GC and CEC. The chiral porous organic cages show better chiral separation ability than commercial chiral columns in GC and have great potential for commercialization. This shows that chiral porous materials have a good application prospect in the field of chromatographic CSP. Although CSP based on chiral porous materials has not been widely used due to the limitation of cost, process, stability and other factors, it can be predicted that with the development of material science, more chiral porous materials will be used in chromatographic separation.

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Funding

National Key R&D Program of China(2019YFA0904104)

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