Phase For Open-tubular Capillary Electrochromatography Research Articles

Hydrogen-bonded organic frameworks as stationary phase for open-tubular capillary electrochromatography

BackgroundCapillary electrochromatography (CEC) stationary phases have always been the focus of attention. The selection of excellent stationary phases are the key to realize separate of different compounds. Hydrogen-bonded organic frameworks (HOFs) are porous materials connected by hydrogen bonds between molecules, which have the advantages of renewable, high specific surface area and mild synthesis conditions. At present, HOFs are used in gas adsorption and storage, catalysis and drug delivery. Because of its unique advantages, HOFs have a bright future as CEC stationary phases. ResultsUsing melamine (MA) and 1,3,6,8-tetra (4-carboxylphenyl)pyrene (H4TBAPy) as reaction monomers, a HOFs named MA/PFC-1 was synthesized by solvent evaporation at room temperature. The inner wall of the capillary column was coated with MA/PFC-1 by chemical bonding. Sulfonamides were used as the target analytes. The effects of pH, phosphate buffer solution concentration, organic additive content and applied voltage on sulfonamides separation were investigated. The MA/PFC-1-coated capillary column had good resolution (>1.5) and reproducibility. The intra-day, inter-day, column-to-column, and inter-batch precision of the retention times were 0.03%–0.09%, 0.04%–0.09%, 0.03%–0.14% and 0.06%–0.09%, respectively. The intra-day, inter-day, column-to-column, and inter-batch precision of the peak areas were 0.11%–0.25%, 0.13%–0.20%, 0.12%–0.15% and 0.08%–0.15%, respectively. The MA/PFC-1-coated capillary column was run 150 consecutive times, and the results showed no noticeable change, which proved that this method had good stability. SignificanceThis work applied HOFs to CEC. The results show the that MA/PFC-1-coated capillary column has good separation performance. The MA/PFC-1-coated capillary column has been successfully applied to the determination of sulfamethoxazole in tablets, which has practical application value. To open up the application of HOFs in CEC and provide a new idea for developing new CEC stationary phases.

Fluorinated covalent-organic polymers as stationary phase for analysis of organic fluorides by open-tubular capillary electrochromatography.

Fluorinated porous materials, which can provide specific fluorine-fluorine interaction, hold great promise for fluoride analysis. Here, a novel fluorinated covalent-organic polymer was prepared by using 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and 2,3,5,6-tetrafluorotelephtal aldehyde as the precursors and introduced as stationary phase for open-tubular capillary electrochromatography. The as-synthesized fluorinated covalent-organic polymer and the modified capillary column were characterized by infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectrometry. Based on strong hydrophobic interaction and fluorine-fluorine interaction provided by fluorinated covalent-organic polymer coating layer, the modified column showed powerful separation selectivity toward hydrophobic compounds, organic fluorides, and fluorinated pesticides. Additionally, the fluorinated covalent-organic polymer with good porosity and regular shape was uniformly and tightly coated on the capillary inner wall. The obtained highest column efficiency could reach up to 1.2 × 105 plates⋅m-1 for fluorophenol. The loading capacity of the modified column can reach 141pmol for trifluorotoluene. Besides, the relative standard deviations of retention times for intraday run (n=5), interday run (n=3), and between columns (n=3) were all less than 2.55%. Significantly, this novel fluorinated material-based stationary phase shows great application potential in fluorides analysis.

Chiral covalent organic framework-based open tubular capillary electrochromatography column for enantioseparation of selected amino acids and pesticides.

A novel chiral covalent organic framework (CCOF) was synthesized with an imine covalent organic framework TpBD (synthesized via Schiff-base reaction between phloroglucinol (Tp) and benzidine (BD)) modified using (1S)-(+)-10-camphorsulfonyl chloride as chiral ligand by chemical bonding method for the first time, and was characterized by X-ray diffraction, Fourier-transform infrared spectra, X-ray photoelectron spectroscopy, nitrogen adsorption/desorption, thermogravimetry analysis, and zeta-potential. The results revealed that the CCOF had good crystallinity, high specific surface area and good thermal stability. Then, the CCOF was employed as stationary phase in open-tubular capillary electrochromatography (OT-CEC) column (the CCOF-bonded OT-CEC column) for enantioseparation of 21 single chiral compounds (12 natural amino acids including acidic, neutral and basic, 9 pesticides including herbicides, insecticides and fungicides) and simultaneous enantioseparation of mixture amino acids and pesticides with similar structures or properties. Under the optimized CEC conditions, all the analytes reached the baseline separation with high resolutions of 1.67-25.93 and selectivity factors of 1.06-3.49 in 8min. Finally, the reproducibility and stability of the CCOF-bonded OT-CEC column were measured. Relative standard deviations (RSDs) of retention time and separation efficiency were 0.58-4.57% and 1.85-4.98%, and not obviously changed after 150 runs. These results demonstrate that COFs-modified OT-CEC explore a promising method to separate chiral compounds.

Synthesis of carbon dots-based covalent organic nanomaterial as stationary phase for open tubular capillary electrochromatography

The transformation of zero-dimensional carbon dots (CDs) to cross-linked nanomaterials is rare. In this work, a novel carbon dots-based covalent organic nanomaterial (CON CDs-TAPB) consisted of 1,3,5-tris(4-aminophenyl)-benzene (TAPB) and carbon dots (CDs) through facile Schiff-base reaction was synthesized and then employed as a stationary phase for open-tubular capillary electrochromatography (OT-CEC). The CON CDs-TAPB and the CDs-TAPB coated column were characterized through Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), UV-spectra experiments and X-ray photoelectron spectroscopy (XPS). Thanks to CON CDs-TAPB unique structure and abundant accessibility and interaction sites, the prepared column exhibited a satisfactory separation ability towards analytes including parabens, phenolic compounds. Among all analytes, the highest column efficiency was over 1.6 × 105 plates·m−1. In addition, affording methylbenzene loading capacity of 156.9 pmole, surpassing most of those materials-based OT-CEC reported thus far. Thus, the prepared carbon dots-based covalent organic nanomaterial (CON CDs-TAPB) gave a potential as a stationary phase in the separation science.

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

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.

Synthesis of a covalent organic framework with hydrazine linkages and its application in open-tubular capillary electrochromatography

Recently, covalent organic frameworks (COFs), owning to their excellent and unique properties, are attracting the attention of numerous researchers in some areas, especially the domain of chromatographic separation. However, the application of hydrazine linkages COFs in open-tubular capillary electrochromatography (OT-CEC) lies in the early stage at present. Herein, a well-crystallized hydrazine-linked COF (Tf-DHzOH) was synthesized successfully from 2,5-dihydroxyterephtalohydrazide and 1,3,5-triformyl-benzene. Tf-DHzOH was firstly regarded as a stationary phase material to prepare the Tf-DHzOH coated capillaries with different coating thickness by covalent bonding in this work. The characterization results showed that Tf-DHzOH was successfully synthesized. The separation performance and stability of the Tf-DHzOH coated capillary were evaluated by considering amino acids, sulfonamides, tetracyclines and benzene compounds as analytes. The relative standard deviations (RSDs) of separation time in the intra-day (n = 9), inter-day (n = 6), column-to-column (n = 3) and batch-to-batch (n = 3) were 0.76–4.97%, 1.59–5.94%1.78–8.72% and 1.66%–8.23%, respectively, the RSDs of peak areas were 1.90–5.16%, 1.73–5.24%, 1.26–7.33% and 3.77%–11.24%, respectively. It was confirmed that there was no visible change of separation efficiency after the Tf-DHzOH-coated capillary was used more than 200 runs. The results make clear that 2D hydrazine-linked COF (Tf-DHzOH) has superior potential as the stationary phase in OT-CEC for chromatographic separation.

Room-temperature growth of covalent organic frameworks as the stationary phase for open-tubular capillary electrochromatography.

Covalent organic frameworks (COFs) are a class of porous materials with high surface area, high porosity, good stability and tunable structure that have been widely used in the separation area. In this work, we have proposed the in situ synthesis of a novel COF composed of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline (Tz) and 1,4-dihydroxyterephthalaldehyde (Da) onto the capillary inner surface for electrochromatographic separation. Fourier transform infrared (FT-IR) spectroscopy, elemental analysis (EA) and scanning electron microscopy (SEM) have facilitated the characterization of the prepared capillary columns. The COF (TzDa) modified OT-CEC column exhibited satisfactory separation selectivity towards neutral compounds (such as chlorobenzenes and alkylbenzenes), acidic and basic compounds (such as phenols and anilines), food additives (vanillin and its analogues) and small biomolecules (such as amino acids and polypeptides). Furthermore, the TzDa modified capillary was quite stable and reproducible. The relative standard deviations for retention times of the test analytes (alkylbenzenes) were as follows: for intra-day (n = 3) runs (≤1.74%), inter-day (n = 3) runs (≤2.25%) and between columns (n = 3) (≤4.83%). This new type of COF-based stationary phase has tremendous potential in separation science.

Solvothermal-assisted in situ rapid growth of octadecylamine functionalized polydopamine-based permanent coating as stationary phase for open-tubular capillary electrochromatography.

In recent years, mussel-inspired polydopamine (PDA) based materials have been widely used as stationary phases for open-tubular capillary electrochromatography (OT-CEC) because of their various excellent properties. Nevertheless, the traditional synthesis routes of functionalized PDA-based capillary columns usually are time-consuming and limited in aqueous solutions. Herein, we report a facile and rapid route to prepare octadecylamine (ODA) functionalized PDA coated OT-CEC columns in organic solvents via a novel one-step in situ solvothermal-assisted coating strategy. Through this developed solvothermal-assisted approach, the growth rate of ODA/PDA coating was significantly speeded up and their hybrid coating process on the capillary inner surface could be rapidly completed in 60min. The successful preparation of the solvothermal-assisted ODA/PDA hybrid coating were systematically characterized and confirmed by several methods. The influence of the preparation parameters on the formation of hybrid coating and the separation ability of the ODA/PDA modified columns were systematically explored. Consequently, the high-efficiency baseline separation of four kinds of neutral, acidic and basic analytes were achieved based on the ODA/PDA modified columns. The repeatability of the solvothermal-assisted ODA/PDA coated column was also studied, and the relative standard deviations for intra-day, inter-day and column-to-column were all less than 5%. Additionally, the solvothermal-assisted ODA/PDA modified column exhibited good stability and long lifetime.

In situ one-pot synthesis of polydopamine/octadecylamine co-deposited coating in capillary for open-tubular capillary electrochromatography

Mussel-inspired polydopamine (PDA) based materials are attractive as stationary phase for open-tubular capillary electrochromatography (OT-CEC) due to their many fascinating properties. However, all of the existing strategies for fabricating PDA based OT-CEC columns are limited in aqueous solutions. Consequently, it is a challenge work to directly immobilize the hydrophobic functional materials onto the inner wall of PDA modified capillary. Herein, by using the organic amine-inducing co-deposition strategy, a novel preparative method was developed for in situ one-pot synthesis of PDA/octadecylamine (ODA) co-deposited coating inside capillary as OT-CEC stationary phase. The formation and morphology of the PDA/ODA co-deposited coating were characterized by field emission scanning electron microscopy, atomic force microscope, attenuated total reflectance Fourier transform infrared spectroscopy and contact angle measurements. The separation performance of the fabricated PDA/ODA modified columns was validated by the separation of alkylbenzenes and steroids, which could achieve baseline separation with high separation efficiency. Their separation was found to follow the reversed phase chromatographic retention mechanism. The co-deposited column showed good stability and long lifetime. The repeatability of the PDA/ODA co-deposited column was also evaluated, with the relative standard deviations for intra-day and inter-day runs less than 5% and column-to-column runs less than 6%.

Ambient temperature fabrication of a covalent organic framework from 1,3,5-triformylphloroglucinol and 1,4-phenylenediamine as a coating for use in open-tubular capillary electrochromatography of drugs and amino acids

A covalent organic framework (COF) named TpPa-1 was designed and synthesized at ambient temperature by an ultrasound-assisted method from 1,3,5-triformylphloroglucinol (Tp) and 1,4-phenylenediamine (Pa-1). It was utilized as a stationary phase in open-tubular capillary electrochromatography (OT-CEC). The column was coated with TpPa-1 using a covalent bonding strategy. The coated capillary was characterized by morphology, crystallography, and mesoporous analysis to confirm the successful fabrication. The OT-CEC method was utilized for the analysis of tetracyclines, sulfonamides, cephalosporins and amino acids with high-resolution (Rs > 1.81) and good precision (RSD < 4.9%). It takes about 12h from COF preparation to OT-CEC separation. Graphical abstract A covalent organic framework (COF) named TpPa-1 was synthesized at ambient temperature by an ultrasound-assisted method from 1,3,5-triformylphloroglucinol (Tp) and 1,4-phenylenediamine (Pa-1). COF-TpPa-1 modified capillary column was utilized for the analysis of tetracyclines, sulfonamides, cephalosporins and amino acids with high-resolution and good precision.

Polydopamine-assisted immobilization of a zinc(II)-derived metal-organic cage as a stationary phase for open-tubular capillary electrochromatography.

A capillary column was modified with a soluble zinc(II)-derived metal-organic cage (MOC) [Zn2L] as the stationary phase to obtain a new coating layer for use in open-tubular capillary electrochromatography. The inner surface of the capillary was first coated with a layer of polydopamine. Then, a solution of the MOC in dichloromethane was introduced into the capillary upon which it is bonded both covalently and non-covalently. The resulting coating layer on the capillary was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The results demonstrated the successful formation of the [Zn2L] modified open-tubular column. The column showed good separation performance towards neutral compounds (such as methylbenzene, ethylbenzene, n-propylbenzene and n-butylbenzene), acidic drugs (such as ibuprofen, ketoprofen, flurbiprofen and diclofenac sodium), food additives (such as parabens, vanillin and related phenolic compounds) and small biomolecules (such as nucleosides and nucleotide bases) by π-interaction and hydrophobic interaction. It also exhibited good precision, the relative standard deviations of the retention time for intra-day, inter-day runs and column-to-column being <1.6%, 2.8%, and 4.0%, respectively. Graphical abstract Schematic presentation of the open-tubular column modified with zinc(II)-derived metal-organic cage by polydopamine-assisted strategy onto the inner wall of capillary for electrochromatographic separations.

In-situ growth of a metal organic framework composed of zinc(II), adeninate and biphenyldicarboxylate as a stationary phase for open-tubular capillary electrochromatography.

This work reportson the in-situ growth of a metal organic framework (MOF) composed of zinc(II), adeninate and biphenyldicarboxylate on the inner wall of a capillary, and theuse of this MOF as a stationary phases in open-tubular capillary electrochromatography. The inner wall of a fused-silica capillary was first modified with 3-aminopropyltriethoxysilane to create surface amino sites, and then the MOF was synthesized by in-situ growth. The modified capillary was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The results proved the successful growth of the MOF. The resultant open-tubular column showed good separation selectivity towards neutral compounds, acidic and basic compounds including nonsteroidal anti-inflammatory drugs, sulfa drugs and small biomolecules. In addition, the modified column is stable and repeatable. The precisions (expressed as RSDs) of the retention time for intra-day (n= 5) and inter-day (n = 5) separations and between columns (n= 3) are less than 0.5, 1.6 and 4.7%, respectively. Conceivably, this new kind of MOF represents a most useful novel stationary phase in electrochromatographic separations. Graphical abstract Schematic presentation of the open-tubular column modified with bio-MOF-1 by in situ hydrothermal reaction with adeninate, Zn(II) and biphenyldicarboxylate for capillary electrochromatographic separations.

Nano-amylose-2,3-bis(3,5-dimethylphenylcarbamate)-silica hybrid sol immobilized on open tubular capillary column for capillary electrochromatography enantioseparation.

The chiral organic-inorganic hybrid materials can exhibit a high loading, and the chiral selector nanoparticles can create efficient stationary phases for open-tubular capillary electrochromatography (OT-CEC). Hence, a novel protocol for the preparation of an OT column coated with nano-amylose-2,3-bis(3,5-dimethylphenylcarbamate) (nano-ABDMPC)-silica hybrid sol through in situ layer-by-layer self-assembly method was developed for CEC enantioseparation. By controlling the assembly cycle number of nano-ABDMPC-silica hybrid sol, a homogeneous, dense and stable coating was successfully prepared, which was confirmed by SEM and elemental analysis. As the main parameter influencing the chiral separating effect, the nano-ABDMPC bearing 3-(triethoxysilyl)propyl residues concentration was investigated. The experimental results showed that 10.0 mg/mL nano-ABDMPC bearing 3-(triethoxysilyl)propyl residues coated OT capillary column possessed chiral recognition ability toward the six enantiomers (phenylalanine, tyrosine, tryptophan, phenethyl alcohol, 1-phenyl-2-propanol, and Tröger's base) at some of the different conditions tested. Additionally, the coated OT column revealed adequate repeatability concerning run-to-run, day-to-day and column-to-column. These results demonstrated the promising applicability of nano-ABDMPC-silica hybrid sol coated OT column in CEC enantioseparations.

Open-tubular capillary electrochromatography using carboxylatopillar[5]arene as stationary phase.

Pillar[n]arenes have achieved much interest in material chemistry and supramolecular chemistry due to unusual pillar shape structure and high selectivity toward guest. However, pillar[n]arenes have not yet been applied in capillary electrochromatography. This work at first time reports that carboxylatopillar[5]arene is used as a stationary phase in open-tubular capillary electrochromatography. Carboxylatopillar[5]arene not only possess the advantages of pillar[n]arenes but also provide free carboxy groups for immobilizing on the inner wall of capillary column via covalent bonding. The characterization of SEM and FT-IR indicated that carboxylatopillar[5]arene was successfully grafted on the inner wall of capillary. The baseline separation of model analytes including neutral, basic, and acidic compounds, nonsteroidal anti-inflammatory drugs and dansyl-amino acids have been achieved thanks to the electron-rich cavity of carboxylatopillar[5]arene and hydrophobic interactions between the analytes and stationary phase. The intraday, interday, and column-to-column precisions (RSDs) of retention time and peak area for the neutral analytes were all less than 3.34 and 9.65%, respectively. This work indicates that pillar[n]arenes have great potential in capillary electrochromatography as novel stationary phase.

Polydopamine-assisted immobilization of zeolitic imidazolate framework-8 for open-tubular capillary electrochromatography.

In this work, we developed a capillary column modified with zeolitic imidazolate framework-8 as a novel stationary phase for open-tubular capillary electrochromatography. To immobilize zeolitic imidazolate framework-8 onto the inner surface of silica capillary, a bio-inspired polydopamine functionalization was used to functionalize the capillary surface with polydopamine. First, a polydopamine layer was assembled inside the capillary. Second, due to noncovalent adsorption and covalent reaction ability, polydopamine could attract and anchor zeolitic imidazolate framework-8 onto the inner surface of capillary. It has been demonstrated that zeolitic imidazolate framework-8 was successfully grafted on the inner wall of the capillary by scanning electron microscopy, and Fourier transform infrared spectroscopy. The electro-osmotic flow characteristics of capillaries were also investigated by varying the pH value and acetonitrile content of mobile phase. The zeolitic imidazolate framework-8 coating not only increased the phase ratio of open-tubular column, but also improved the interactions between tested analytes and the stationary phase. Three groups of isomers including acidic, basic, and neutral compounds were well separated on the zeolitic imidazolate framework-8 bonded column, with theoretic plate numbers up to 1.9 × 105 N for catechol. The repeatability of the prepared columns was also studied, and the relative standard deviations for intra- and interday runs were less than 5%.

An immobilized carboxyl containing metal-organic framework-5 stationary phase for open-tubular capillary electrochromatography

A novel capillary column with metal-organic framework-5 (MOF-5) as the stationary phase was prepared for open-tubular capillary electrochromatography (OT-CEC). To grow MOF-5, the fused-silica capillary was functionalized firstly using 3-aminopropyltriethoxysilane and glutaraldehyde as covalent linkers; and then MOF-5 would be immobilized on the inner wall of COOH-terminated capillary by epitaxial growth, to produce a MOF-5-modified capillary. The successful growth of MOF-5 has been characterized and confirmed by scanning electron microscopy, X-Ray diffraction and Fourier transform infrared spectra. The influence of pH value and methanol on electroosmotic flow (EOF) of the MOF-5-modified capillary column was investigated. The EOF showed a pH-dependent from anode to cathode. The immobilization of MOF-5 improved the interactions between analytes and layer on inner wall of the capillary. Excellent separations of substituted benzenes and acidic and basic analytes were obtained on the fabricated capillary columns. The MOF-5-modified capillary columns exhibited good repeatability, with relative standard deviations for intra-day, inter-day runs and column-to-column less than 1.87%, 3.53%, and 8.49%, respectively. Our successful application of MOF-5 paved the way for introducing series of dicarboxylate-based isoreticular MOFs to OT-CEC as novel stationary phase.

Separation of small organic molecules using covalent organic frameworks-LZU1 as stationary phase by open-tubular capillary electrochromatography

Covalent organic frameworks (COFs) have attracted much attention because of their permanent nanoscale porosity and higher surface area compared to zeolites as well as robustness. COFs have great potential in several fields such as hydrogen storage, gas separation, and catalysis. However, COFs have not yet been applied in capillary electrochromatography. Herein, covalent organic frameworks-LZU1 (COF-LZU1) was used as the stationary phase in open-tubular capillary electrochromatography for the first time. Compared to the monoliths used in electrochromatography, the preparation technique of a COF-LZU1-coated capillary was simple and practical. The baseline separation of model analytes including alkylbenzenes, polyaromatic hydrocarbons, and anilines by the COF-LZU1-coated capillary was achieved based on the size selectivity of COF-LZU1 porous structure and hydrophobic interactions between the model analytes and organic ligands of COF-LZU1. The load capacity of the COF-LZU1-coated capillary for naphthalene was 0.6mg/mL. For three consecutive runs, the intraday relative standard deviations (RSDs) were 1.4–2.6% for the migration time and 2.7–8.7% for the peak area. The interday RSDs were 1.3–3.9% for the migration time and 3.7–9.7% for the peak area. The column-to-column reproducibility of migration time was in the range 1.0–3.9%. Moreover, the coated capillary was used for >300 runs with no changes in the separation efficiency. Thus, COFs have great potential in capillary electrochromatography and may provide a new method for chromatographic separation.

In situ synthesis of homochiral metal–organic framework in capillary column for capillary electrochromatography enantioseparation

Homochiral metal–organic frameworks (MOFs) are promising as porous stationary phase for open-tubular capillary electrochromatography (OT-CEC) enantioseparation owing to their fine-tuned pore sizes and large surface areas. In this work, the homochiral MOF AlaZnCl was successfully coated on the inner wall of fused silica capillary by an in situ, layer-by-layer self-assembly approach at room temperature. The results of scanning electron microscopy (SEM), X-ray diffraction (XRD), streaming potential (SP) and Fourier-transform infrared spectroscopy (FT-IR) indicated that the homochiral MOF AlaZnCl was successfully coated on the capillary inner wall. To evaluate the performance of the homochiral MOF AlaZnCl coated capillary column, the enantioseparation was carried out by using six amine drugs and monoamine neurotransmitters as model analytes and excellent enantioseparation efficiency was achieved. Run-to-run, day-to-day, and column-to-column relative standard deviations (RSDs) were all less than 5%. Moreover, the separation efficiency of the homochiral MOF AlaZnCl coated capillary column did not decrease obviously over 100 runs.

Layer-by-Layer Assemblies Based on a Cationic β-Cyclodextrin Polymer: Chiral Stationary Phases for Open-Tubular Electrochromatography

Non-covalent chiral stationary phases for open-tubular capillary electrochromatography (OT-CEC) were developed using polyelectrolyte multilayer (PEM) coatings. These chiral coatings were made by alternately flushing the separation capillary with cationic and anionic polymers using a polymer of trimethylammonium-β-CD (pCD+) as a chiral selector. The layer-by-layer construction was monitored by EOF measurements. To our knowledge, it is the first OT-CEC chiral stationary phase based on a layer-by-layer assembly including an ionic cyclodextrin polymer. The composition of PEM coating was optimized as regards chiral separation. Thus, the influence of the nature of the first adsorbed cationic polymer (pCD+, polyethyleneimine or poly(diallyldimethyl ammonium chloride)) and the influence of the anionic polymer (poly(sodium 4-styrenesulfonate), polycarboxymethyl-β-CD or chondroitin sulfate) were studied with regard to the apparent surface charge and the enantioselective properties of the coatings. Interactions between the studied enantiomers and the internal layers of the stationary phase were pointed out. We found that the optimal stationary phase was based on a pCD+/poly(sodium 4-styrenesulfonate)/pCD+ three-layer coating. This optimal coating was found to be stable as evidenced by the RSD of 2.2 % for the EOF values calculated from five independent analyses. It was effective for the chiral separation of both neutral and anionic solutes.

Layer-by-layer self-assembly of polydopamine/gold nanoparticle/thiol coating as the stationary phase for open tubular capillary electrochromatography.

Much attention has been paid to utilizing polydopamine (PDA) as the stationary phase in open-tubular capillary electrochromatography (OT-CEC) owing to its diverse properties, such as strong adhesion to various surfaces, latent reactivity toward amine and thiol groups and metal ion chelating/redox activities. In this study, a novel open-tubular capillary column coated with polydopamine/gold nanoparticles/thiols (PDA/Au NPs/thiols) has been fabricated based on the multiple properties of PDA for the first time. The capillary inner surface was firstly functionalized with a layer of PDA/Au NPs using the strong adhesive and metal ion redox properties of PDA. Thiols were then introduced and covalently reacted with the hybrid coating based on the Michael addition reaction of PDA and thiols and also Au-S bonds. Moreover, benefitting from the porosity of PDA, layer-by-layer (LBL) self-assembly was further applied to increase the amounts of stationary phase (Au NPs and thiols), which can significantly enhance the separation effectiveness and stability of the coated column. The formation of the PDA/Au NP/thiol coating in the capillary was confirmed and characterized by scanning electron microscopy (SEM), Energy Dispersive Spectrometry (EDS) and AFM (Atomic Force Microscopy). Then the separation effectiveness of the PDA/Au NP/thiol@capillary was verified by the separation of alkylbenzenes, which can achieve baseline separation easily with high column efficiency. In addition, the column showed long lifetime and good stability. The relative standard deviations (RSDs) for intra-day and inter-day repeatability of the PDA/Au NP/thiol@capillary were lower than 5%. Therefore, the layer-by-layer self-assembly of PDA/Au NPs/thiols on the capillary inner-surface could be an effective capillary modification strategy.