Hybrid Monolithic Column Research Articles

Carboxyl hybrid monolithic column in-tube solid-phase microextraction coupled with UPLC-QTRAP MS/MS for the determination of amphetamine-type stimulants

Carboxyl hybrid monolithic column in-tube solid-phase microextraction coupled with UPLC-QTRAP MS/MS for the determination of amphetamine-type stimulants

Hybrid organic monolithic column containing MIL-68(Al) for the separation of small molecules by capillary HPLC

A hybrid organic monolithic column made of poly(lauryl methacrylate-co-1,6-hexanediol dimethacrylate) and the metal-organic framework MIL-68(Al) was prepared for the first time. The column was used in capillary liquid chromatography, both in isocratic and gradient elution modes. Separation performance towards small molecules of different chemical nature (polycyclic aromatic hydrocarbons, alkylbenzenes, phenols, etc.) was studied. Monte Carlo simulations were made to both select the proper precursors to obtain empty metal-organic framework micropores in the monolithic polymer and also, to analyze the potential free access of the studied analytes into the micropores (necessary to improve mass transfer and column efficiency). The hereby synthesized metal-organic framework microcrystals allowed obtaining homogeneous hybrid monolithic columns. Adding of MIL-68(Al) (1030 m2 g-1 BET specific surface area) increased the surface area from 3.9 m2 g-1 for the parent monolith to 18.2 m2 g-1 for the hybrid column containing 8 mg mL-1 of the microcrystals. Chromatographic performance of this new column was evaluated by studying retention factors, resolution, and plate counts at room temperature. Different compounds, not completely resolved in the parent monolith, were partially or completely separated after metal-organic framework addition. Using the monolithic column with only 2 mg mL-1 of MIL-68(Al), five alkylbenzenes were completely separated with very symmetrical peak shapes, resolution factors up to 3.60 and plate counts of 4300 plates m-1 for n-hexylbenzene. This value is higher than those obtained by other authors who used organic monolithic columns with embedded metal-organic frameworks to perform separations at room temperature. Additionally, nine polycyclic aromatic hydrocarbons were partially or completely resolved in gradient elution mode. The hybrid monolithic columns exhibited very good intra-day (%RSD=1.9), inter-day (%RSD=2.6), and column-to-column (%RSD=4.3) reproducibility values. Easy and fast column preparation, and versatility to efficiently separate several compounds of different chemical nature in isocratic and gradient mode, makes this new hybrid column a very good option for the analysis of small molecules in capillary (or nano) HPLC.

Quantitative determination of amphetamine-type stimulants in sewage and urine by hybrid monolithic column solid-phase microextraction coupled with UPLC-QTRAP MS/MS

A needle-solid-phase microextraction (SPME) method based on hybrid monolithic column (HMC) was proposed for simultaneous separation and extraction of seven amphetamine-type stimulants (ATSs) (amphetamine, methamphetamine, cathinone, methcathinone, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, and 3,4-methylenedioxyethylamphetamine), combining with ultra-performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometer (UPLC-QTRAP MS/MS). Thiol functionalized HMC (T-HMC) showed high extraction efficiency and excellent elution results towards target analytes, among three kinds of single/bi-functionalized HMCs. Various parameters of SPME operation and analytical performance were investigated systematically. The adsorption mechanism of T-HMC to ATSs was also discussed and explained as a mixed mode of electrostatic and hydrophobic interactions. Under the optimum experimental conditions, the proposed T-HMC needle-SPME-UPLC-QTRAP MS/MS method was rapid and convenient with good accuracy, low sample consumption, high sensitivity and strong anti-interference ability. This method was successfully applied to quantitative determination of seven trace ATSs in complex sewage and urine samples. In view of abundant types of HMCs, the needle-SPME based on functional HMC also had the potential to selectively separating and enriching other tract new psychoactive substances in complex matrices, and could provide a reliable tool for drug monitoring, especially in applications for forensic analysis and drug abuse.

Organic-silica hybrid monolithic sorbents for sample preparation techniques: A review on advances in synthesis, characterization, and applications

Organic-silica hybrid monolithic materials have attracted considerable attention as potential stationary phases in separation science. These materials combine the advantages of organic polymer and silica-based monoliths, including easy preparation, lower back pressure, high permeability, excellent mechanical strength, thermal stability, and tunable surface chemistry with high surface area and selectivity. The outstanding chromatographic efficiency as stationary phase of hybrid monolithic capillary columns for capillary liquid chromatography and capillary electrochromatography has been reported in many papers. Organic-silica hybrid monolithic materials have also been extensively used in the field of sample preparation. Owing to their surface functionalities, these porous sorbents offer unique selectivity for pre-concentration of different analytes in the most complex matrixes by fast dynamic transport. These sorbents not only improve the analytical method sensitivity, but also introduce novelties in terms of extraction devices and instrument coupling strategies. The current review covers the period spanning from 2017 to 2023 and describes the properties of organic-inorganic hybrid monolithic materials, the present status of this technology and summarizes recent developments in their use as innovative sorbents for microextraction sample preparation techniques (solid phase microextraction with pipette tip, offline in-tube SPME, in-tube SPME online with LC, and in-tube SPME directly coupled with mass spectrometry). Aspects such as the synthesis methods (sol–gel process, one-pot approach, and polyhedral oligomeric silsesquioxanes-based procedure), characterization techniques, and strategies to improve extraction efficiency in various applications in different areas (environmental, food, bioanalysis, and proteomics) are also discussed.

On-line extraction and determination of coumarins compounds from mouse plasma based on a homemade phenyl-hybrid monolithic adsorbent

A phenyl-hybrid monolithic adsorbent was prepared using an organic monomer of ethylene glycol phenyl ether acrylate and inorganic monomers of tetramethoxysilane and vinyltrimethoxysilane, via polycondensation and polymerization in a stainless-steel column, which shows porous structure and multiple functional groups, according to the measurements of scanning electron microscopy, nitrogen adsorption-desorption method and infrared spectroscopy. The resulting hybrid phenyl-based monolith was used as a solid-phase extraction column, combining with an analytical column in conjunction with high-performance liquid chromatography system for the on-line extraction and determination of coumarins (praeruptorin A and praeruptorin B) in Peucedani Radix from mouse plasma. The homemade hybrid monolithic solid-phase extraction column exhibits good removal ability for the sample matrices, as well as unique selectivity for the two praeruptorins. Methodology validation results indicate that the present method is applicable for the on-line extraction and quantitative analysis of praeruptorin A and praeruptorin B in Peucedani Radix from mouse plasma with a limit of quantitation 0.06 μg/mL and a linear range 0.06–5 μg/mL (r＞0.999), thus indicating the present method is a promising and alternative method for the quantitative determination of similar target components with micro or trace concentration from complex extract solution and plasma.

Covalent organic frameworks based hierarchical porous hybrid monolithic capillary: Synthesis, characterization, and applications in trace metals analysis

The preparation of hierarchical porous monolithic column with high covalent organic frameworks (COF) loading and micropores accessibility is challenging due to the easy aggregability and sedimentation of COFs. Herein, a novel strategy based on high internal phase emulsion (HIPE) polymerization was proposed for preparing COF hybrid capillary monolithic column with hierarchical porosity. COFs with different frameworks including imine COFs (COF-OMe, COF-F and COF-SH), triazine COF (CTF-1) and boron-based COF (COF-5) were selected to investigate the universality of the preparation strategy. The presence of COF in the monolithic capillary was confirmed by scanning electron microscope, X-ray diffraction and fourier transform infrared spectroscopy. Nitrogen adsorption/desorption experiments and thermogravimetric analysis showed that the prepared COF hybrid monolithic capillary exhibited high COF loading (e.g., 28.7% for COF-SH) and accessibility (e.g., 98.5% for COF-SH), mainly due to the thin walls of void-window structures originated from polymerization of HIPE. The successful preparation of water-stable COF-F, COF-OMe, COF-SH and CTF-1 hybrid monolithic columns demonstrated the proposed synthesis strategy is universal to water-stable COF without tedious optimization of dispersion system, effectively avoiding the sedimentation of COF in pre-polymerization solution. Then, the sulfhydryl-modified COF hybrid polymer (poly(COF-SH-HIPE)) monolithic column was evaluated for the extraction of heavy metal ions, and a method based on poly(COF-SH-HIPE) monolithic capillary microextraction on-line coupled with inductively coupled plasma mass spectrometry detection was developed for analysis of trace Cd, Hg and Pb in human fluid samples.

Enantioseparation by zeolitic imidazolate framework-8-silica hybrid monolithic column with sulfobutylether-β-cyclodextrin as a chiral additive in capillary electrochromatography.

A zeolitic imidazolate framework (ZIF)-8-silica hybrid monolithic column was prepared by one-step sol-gel method. The stationary phase in the monolithic column was characterized by Fourier-transform infrared spectra, X-ray diffraction, thermogravimetric analysis, nitrogen adsorption/desorption, and zeta potential. The results showed that ZIF-8-silica hybrid monolithic materials had abundant functional groups, good crystallinity, large specific surface area, and good thermal stability. A capillary electrochromatography (CEC) chiral separation system was for the first timeconstructed with ZIF-8-silica hybrid monolithic column and sulfobutylether-β-cyclodextrin (SBE-β-CD) as a chiral additive and was applied to separate the selected single and mixed chiral compounds (13 natural amino acids and 5 chiral pesticides). Under the optimized CEC conditions, all the single analytes achieved baseline separation with resolution of 2.14-5.94 and selectivity factor of 1.06-1.49 in less than 6min, and the mixed amino acids with similar properties were also simultaneously enantioseparated (Rs ≥ 1.82). Relative standard deviations (RSDs) of migration time and column efficiency were lower than 4.26% and did not change significantly after 200 runs, evidencing excellent reproducibility and stability. These results demonstrate that the application of SBE-β-CD as a chiral additive for ZIF-8-silica hybrid monolithic columns is a promising method for the separation of chiral compounds.

Chiral organic-silica hybrid monolithic HPLC column with dynamic grafting BSA for the enantiomeric separation

BSA functionalized hybrid monolithic column prepared by in-situ dynamic grafting on traditional stainless steel column for enantiomeric separation. A hybrid silica monolithic column (HMC) was prepared using a single precursor (methytrimethoxysilane) in stainless steel HPLC column (50 mm × 4.6 mm) by sol–gel method. The chiral hybrid monolithic column (CHMC) was prepared by grafting 3-aminopropyl trimethoxysilane onto HMC, and then reacting bovine serum albumin (BSA) with Glutaraldehyde. The preparation conditions were optimized, and the maximum grafting amount of BSA was 48.6 mg g−1. The CHMC was characterized and its chromatographic performance was tested. The results showed that the CHMC has a homogeneous network skeleton structure, good stability and reproducibility. The CHMC was combined with HPLC, under optimized chromatographic conditions, the baseline separation of tryptophan and pidotimod enantiomers were successfully achieved.

N, N′-methylene bisacrylamide/divinyl benzene based-highly cross-linked hybrid monolithic column: Production and its applications for powerful capture of four chlorophenols

In this paper, the role of the halogen bond in capillary monolithic column microextraction was explored for the first time. Benzene-1,3,5-tricarbohydrazide (BTH) was synthesized as a functional monomer, N, N′-methylene bisacrylamide (MBA) and divinyl benzene (DVB) were used as cross-linking agents, the hybrid monolithic column of poly (BTH-co-DVB-co-MBA) was prepared using methanol and polyethylene glycol as pore-forming agents and azodiisobutyronitrile as the initiator. Due to the existence of BTH, a large number of nitrogen atoms (Lewis base) were introduced into the monolithic column, which could form a halogen bond with chlorine-containing organic pollutants and enhance its adsorption performance. Based on the monolithic column, a sensitive and environment-friendly solid-phase microextraction technology was studied. The monolithic column was integrated with high-performance liquid chromatography (HPLC) to extract and detect four kinds of chlorophenol in real water samples. Under best conditions, the method showed excellent extraction ability and linearity, with a linear correlation coefficient of 0.9958–0.9987, a low detection limit (LOD) of 0.04–0.23 μg L−1 (S/N = 3), and relative standard deviation (RSD) less than 3.09%. The recovery rate was kept between 87.30% and 123.00%, and the RSD was less than 3.83%, which indicated that the column had powerful capture performance, high precision, and strong anti-matrix interference ability in the real sample, and had potential application value in practical work.

An Overview of Monolithic Column: Types, Parameters and Applications

The column is the main component for chromatographic separation. Nowadays, monolithic columns are graining more popularity in the field of separation media for liquid chromatography. The monolith columns possess great potential as compared to the conventional packed column in terms of preparing complex mixtures. These columns provide various properties like higher permeability, high-efficiency fast separations, high flow rate with lower backpressure, fast mass transfer kinetics with a high binding capacity. It is categories into three columns and they are organic monolithic column, inorganic monolithic column and hybrid monolithic column and all three types of monolithic column differ through their porous properties. In this review, the various advantage of the high-efficiency monolithic column with recent advances, the origin of the concept, the various parameter of the monolithic stationary phase and the application of monolithic columns are illustrated. It is better column in comparison of selectivity, reproducibility and performance.
 Keywords: Monolithic column, Packed columns, Inorganic and organic monolithic column, Column parameters, Pharmaceutical Applications

Surface-Charged Hybrid Monolithic Column for MS-Compatible Peptide Separation with High Peak Capacity and Its Application in Proteomic Analysis.

For bottom-up proteomics, peptide separation with high peak capacity under MS-compatible conditions is of vital significance to increase proteome coverage. Herein, a surface-charged ethane-bridged hybrid monolithic column was prepared based on the efficient ring-opening reaction of N-methyl-aza-2,2,4-trimethyl-silacyclopentane after C18-functionalization. The existence of secondary amino groups on the surface was beneficial to reduce the secondary interactions of silanol groups and increase peak capacity for peptide separation with MS-compatible mobile phases (e.g., using 0.1% FA as the mobile phase modifier). Such columns offered a 4-fold increase in peak capacity compared with ethane-bridged hybrid monolithic columns without surface charge modification. By a 100 cm length surface-charged ethane-bridged hybrid capillary column, high peak capacity of 700 was achieved within a 240 min gradient for the separation of Hela tryptic peptides with 0.1% FA-containing mobile phases, under the low backpressure of ∼200 bar. On average, 44493 ± 459 peptides corresponding to 5148 ± 47 proteins were identified from 750 ng Hela tryptic digests. Finally, the surface-charged ethane-bridged hybrid monolithic column was successfully applied in the quantitative proteomic analysis of dopaminergic neuron death model of N-methyl-4-phenylpyridinium iodide induced SH-SY5Y cells. These results demonstrated great promise of such surface-charged ethane-bridged hybrid monolithic columns for bottom-up proteomic analysis in complex samples.

Preparation of a zeolite imidazole skeleton-silica hybrid monolithic column for amino acid analysis via capillary electrochromatography.

We developed a novel, convenient and low-cost one-pot strategy for preparing a zeolitic imidazolate framework-8 (ZIF-8)-silica hybrid monolithic column by adding ZIF-8 directly to a polymer solution of the silica matrix. The simulated stationary phase and monolithic column prepared under optimal conditions were characterized using X-ray diffraction, scanning electron microscopy, Fourier-transform infrared spectroscopy, thermogravimetric analysis nitrogen physisorption and zeta potential. The results obtained confirmed the successful introduction of ZIF-8 into the silica monolithic column, and the prepared monolithic column exhibited good permeability and physicochemical stability. A capillary electrochromatography method was developed based on a ZIF-8-silica hybrid monolithic column through which 15 mixed amino acids, 4 neutral compounds, 4 nipagin esters and 2 chlorinated fungicides were separated in 14, 5, 7 and 6min, respectively, under optimal conditions. The relative standard deviations retention times and column efficiencies in run-to-run, day-to-day and column-to-column varied in the ranges of 1.90%-2.21%, 2.13%-2.51% and 3.08%-6.65%, respectively, which demonstrated that ZIF-8-silica hybrid monolithic column exhibited satisfactory reproducibility and stability. The incorporation of ZIF-8 into a silica monolithic column is a promising method for preparing novel monolithic columns composed of a metal-organic framework.

Ethane-Bridged Hybrid Monolithic Column with Large Mesopores for Boosting Top-Down Proteomic Analysis.

Top-down proteomics is challenged by the high complexity of biological samples. The coelution of intact proteins results in overlapped mass spectra, and hence, an increased peak capacity for protein separation is needed. Herein, ethane-bridged hybrid monoliths with well-defined large mesopores were successfully prepared based on the sol-gel condensation of 1,2-bis(trimethoxysilyl)ethane and tetramethoxysilane, followed by two-step base etching of the Si-O-Si domain while maintaining the Si-C-C-Si domain in the structure. Relatively homogeneous macropores of 1.1 μm and large mesopores of 24 nm were obtained, permitting fast mass transfer of large molecules and efficient diffusion without obstruction. The use of less hydrophobic C1 ligand further sharpened the peak shape and improved peak capacity. A 120 cm-long capillary column was used for top-down proteomic analysis of E. coli lysates under low backpressure with 16 MPa. High peak capacity of 646 was achieved within 240 min gradient. With MS/MS analysis, 959 proteoforms corresponding to 263 proteins could be unambiguously identified from E. coli lysates in a single run. Furthermore, to illustrate the separation performance for large proteoforms, such monoliths were applied to top-down analysis of the SEC fraction of E. coli lysates with Mw ranging from 30 to 70 kDa. With highly effective separation, 347 large proteoforms with Mw higher than 30 kDa were detected in the single 75 min run. These results showed great potential for top-down proteomic analysis in complex samples.

Polyhedral Oligomeric Silsesquioxane–Based Hybrid Monolithic Column On-line In-Tube Solid-Phase Microextraction Coupled with High-Performance Liquid Chromatography for the Determination of Five Phthalate Esters in Bottled Water

Polyhedral Oligomeric Silsesquioxane–Based Hybrid Monolithic Column On-line In-Tube Solid-Phase Microextraction Coupled with High-Performance Liquid Chromatography for the Determination of Five Phthalate Esters in Bottled Water

In situphotoinitiated fabrication of phosphorylcholine-functionalized polyhedral oligomeric silsesquioxane hybrid monolithic column for mixed-mode capillary electrochromatography

A phosphorylcholine-functionalized POSS hybrid monolithic column was synthesizedviaUV curing. It exhibits hydrophilic interaction and weak cation exchange chromatography retention mechanism for the separation of typical polar and charged compounds.

Single-step fabrication of a teicoplanin functionalized organic-silica hybrid monolith for enantioseparation by nano-liquid chromatography

A novel teicoplanin functionalized organic-silica hybrid chiral monolithic column was prepared by a facile single-step approach. The conditions for the preparation of the organic-silica hybrid chiral monolithic column were systematically optimized, including the amount of poly (ethylene glycol) (PEG) and urea, the tetramethyl orthosilicate (TMOS)/3-(trimethoxysilyl)-propylmethacrylate (γ-MAPS) ratio (v/v), the content of teicoplanin-2-isocyanatoethyl methacrylate (Tei-ICNEML) monomer, and the reaction temperature and time. The optimum column exhibited satisfactory efficiency, permeability and stability. In order to obtain satisfactory enantioseparation performance, reversed phase (RPM) and polar organic phase (POM) modes were employed, and different experimental conditions were optimized, such as buffer concentration and pH, amount of the organic solvent, concentration and ratio of TEA/HAc, and MeOH/ACN ratio. The stability of the Tei-ICNEML organic-silica hybrid monolithic column was also investigated in both POM and RPM separation modes. Then, this novel monolithic column was successfully applied to achieve the enantioseparation of amino alcohols, N-derivatized amino acids and mandelic acids. 15 out of 20 amino alcohols were baseline separated with good column efficiency in the POM mode, and 3 out of 5 mandelic acids and 5 out of 6 N-derivatized amino acids were baseline separated in the RPM mode.

Recent Advances about the Applications of Click Reaction in Chemical Proteomics.

Despite significant advances in biological and analytical approaches, a comprehensive portrait of the proteome and its dynamic interactions and modifications remains a challenging goal. Chemical proteomics is a growing area of chemical biology that seeks to design small molecule probes to elucidate protein composition, distribution, and relevant physiological and pharmacological functions. Click chemistry focuses on the development of new combinatorial chemical methods for carbon heteroatom bond (C-X-C) synthesis, which have been utilized extensively in the field of chemical proteomics. Click reactions have various advantages including high yield, harmless by-products, and simple reaction conditions, upon which the molecular diversity can be easily and effectively obtained. This paper reviews the application of click chemistry in proteomics from four aspects: (1) activity-based protein profiling, (2) enzyme-inhibitors screening, (3) protein labeling and modifications, and (4) hybrid monolithic column in proteomic analysis.

Preparation and modeling study of novel carboxymethyl-β-cyclodextrin silica hybrid monolithic column for enantioseparations in capillary electrochromatography

In this paper, an anionic carboxymethyl-β-cyclodextrin (CM-β-CD) silica hybrid monolithic column was first prepared by “one-pot” sequential reaction. The chiral stationary phase (CSP) and prepared monolithic column were demonstrated by fourier transform infrared (FT-IR), nuclear magnetic resonance (1H NMR) and scanning electron microscope (SEM). To obtain better separation efficiency, the columns’ preparation conditions (DMSO, AIBN and PEG) and separation conditions (buffer pH, ACN proportion, separation voltage and buffer solution) were optimized using model analytes. The resulting columns were finally used in chiral separations of ten racemic compounds, and satisfactory separation selectivity was obtained. The RSDs lower than 3.0% were obtained through run-to-run (n = 6), day-to-day (n = 3), and column-to-column determinations (n = 3). Furthermore, the mechanism of chiral recognition was demonstrated using molecular modeling with AutoDock. This proposed method was also well validated with good linearity (≥0.998), recovery (96.79–97.88%) and repeatability, and was successfully used for enantiomeric impurity detection of S-ofloxacin tablet. As a novel chiral stationary phase, CM-β-CD was supposed to be a promising prospect in the further analysis of chiral samples.

Preparation of a novel amino functionalized ion-imprinted hybrid monolithic column for the selective extraction of trace copper followed by ICP-MS detection

In this work, a novel amino functionalized Cu(II) ion-imprinted organic-inorganic hybrid monolithic column (Cu(II)-IIHMC) was prepared via one-pot co-condensation and the combination of sol-gel and ion-imprinting techniques in a fused capillary. The Cu(II)-IIHMC was used as solid phase microextraction (SPME) matrix followed by inductively coupled plasma-mass spectrometry (ICP-MS) for the analysis of trace Cu(II). The prepared Cu(II)-IIHMC has good mechanical strength, stable imprinting sites and homogeneous structure of network skeleton with large flow-through pores by optimizing the synthesis process. Under the optimized conditions, the Cu(II)-IIHMC can selectively adsorb Cu(II) with the adsorption capacity of 3.13 mg g−1. With enrichment factor of 10-fold, the calibration curve was established in the range of 0.05–50 μg L−1 with r2 of 0.9992 and the detection limit was 0.008 μg L−1 for Cu(II). Compared with the non-imprinted hybrid monolithic column (Cu(II)-NIHMC), the Cu(II)-IIHMC possesses better selectivity, anti-interference ability and adsorption capacity. The Cu(II)-IIHMC can specifically capture the target ion in the presence of competitive ions, with the selectivity coefficients exceeding 39.4. The protocol was validated by analyzing Certified Reference Materials of standard sediment, soil and iron ore, and the results were in good agreement with certified values. Moreover, the proposed in-tube SPME procedure can not only preconcentrate trace Cu(II), but also effectively reduce the matrix effect and powerfully eliminate the interference from the main metals in real samples. Therefore, the developed SPME-ICP-MS method with facile preparation, specific selectivity, high sensitivity and efficient analysis, was applied in the determination of trace Cu(II) in environmental and mineral samples with the recoveries of 89.8–111.8% in all spiked samples.

Ionic Liquid 1-Vinyl-3-dodecylimidazole Bromide Embedded Hybrid Monolithic Column and Its Versatile Post-modification with Amino Acids

The amino acids post-modified ionic liquids-based hybrid monolithic columns were successfully developed. For the first step, using 1-vinyl-3-dodecylimidazole bromide (VDI·Br) and polyhedral oligomeric silsesquioxane methacryl substituted (POSS-MA) as monomer and crosslinking agent, the monolithic POSS-VDI matrix material was polymerized in 100 μm capillary. The prepared POSS-VDI column is of ion-exchange/reverse-phase mixed-mode retention characteristics. The column efficiency reached 137,000 N/m for thioureas. The POSS-VDI column has also been successfully applied to recognize and analyze the effective components of Traditional Chinese Medicines Fangji and the Root of Kudzu Vine. Furthermore, based on its good chromatographic performances, in the second step, amino acids l-Proline (l-Pro), Glycine (Gly) or DL-Phenylalanine (DL-Phe) were further exploited as the anion exchangers to post-modify the POSS-VDI column. The new POSS-VDI-Pro, POSS-VDI-Gly and POSS-VDI-Phe columns exhibited different separation selectivity for the complex egg white protein sample. The present work provides a good route to fabricate versatile amino acids and ionic liquids modified monolithic columns with good separation selectivity.