Advances in capillary electro-chromatography

Capillary electrochromatography (CEC) is a micro-scale separation technique which is a hybrid between capillary electrophoresis (CE) and liquid chromatography (LC). CEC can be performed in packed, monolithic and open-tubular columns. In recent three years (from 2016 to 2018), enormous attention for CEC has been the development of novel stationary phases. This review mainly covers the development of novel stationary phases for open-tubular and monolithic columns. In particular, some biomaterials attracted increasing interest. There are no significant breakthroughs in technology and principles in CEC. The typical CEC applications, especially chiral separations are described.

A chiral metal-organic framework{(HQA)(ZnCl_(2))(2.5H_(2)O)}n for the enantioseparation of chiral amino acids and drugs

Chiral metal-organic frameworks(CMOFs)with enantiomeric subunits have been employed in chiral chemistry.In this study,a CMOF formed from 6-methoxyl-(8S,9R)-cinchonan-9-ol-3-carboxylic acid(HQA)and ZnCl_(2),{(HQA)(ZnCl_(2))(2.5H_(2)O)}n,was constructed as a chiral stationary phase(CSP)via an in situ fabrication approach and used for chiral amino acid and drug analyses for the first time.The{(HQA)(ZnCl_(2))(2.5H_(2)O)}n nanocrystal and the corresponding chiral stationary phase were systematically characterised using a series of analytical techniques including scanning electron microscopy,X-ray diffraction,Fourier transform infrared spectroscopy,circular dichroism,X-ray photoelectron spectroscopy,thermogravimetric analysis,and Brunauer-Emmett-Teller surface area measurements.In opentubular capillary electrochromatography(CEC),the novel chiral column exhibited strong and broad enantioselectivity toward a variety of chiral analytes,including 19 racemic dansyl amino acids and several model chiral drugs(both acidic and basic).The chiral CEC conditions were optimised,and the enantioseparation mechanisms are discussed.This study not only introduces a new high-efficiency member of the MOF-type CSP family but also demonstrates the potential of improving the enantioselectivities of traditional chiral recognition reagents by fully using the inherent characteristics of porous organic frameworks.

牛血清白蛋白-PAMAM修饰的开管毛细管电色谱柱的制备

Poly(amidoamine)(PAMAM) dendrimer has a large number of terminal groups which can be functionalized by different kinds of ligands.A novel open-tubular CEC(OT-CEC) column in which BSA was bonded to inner wall of capillary as stationary phase through different generations of PAMAM dendrimer was developed.The obtained columns were characterized via labelling BSA with fluorescein isothiocyanate(FITC).Under the optimized condition,the resolution of D,L-Trp was gradually improved with the increase of PAMAM generation.By OT-CEC column modified with BSA-G3.0-PAMAM,the baseline separation of D,L-Trp can be obtained.

Room temperature in-situ preparation of hydrazine-linked covalent organic frameworks coated capillaries for separation and determination of polycyclic aromatic hydrocarbons

Covalent organic frameworks(COFs)have been increasingly used in capillary electrochromatography due to their excellent characteristics.In this work,hydrazine-linked TFPB-DHzDS(TFPB:1,3,5-tris(4-formylphenyl)benzene;DHzDS:2,5-bis(3-(ethylthio)propoxy)terephthalohydrazide)was first synthesized by a simpler and easier method at room temperature and introduced into capillary electrochromatography as coating material.The TFPB-DHzDS coated capillaries were prepared by an in-situ growth process at room temperature.After optimizing the coating concentration and experimental conditions of capillary electrochromatography,baseline separation of two groups of polycyclic aromatic hydrocarbons was achieved based on the TFPB-DHzDS coated capillary.And the established method was used successfully to determine PAHs in natural water and soil samples.The spiked recoveries of polycyclic aromatic hydrocarbons in these samples ranged from 90.01%to 111.0%,indicating that the method is reliable and could detect polycyclic aromatic hydrocarbons in natural samples.Finally,molecular simulation was applied to study and visualize the interaction between the analytes and coating COF materials to investigate the molecular level separation mechanism further.

Open tubular capillary electrochromatography with block co-polymer coating for separation of β-lactam antibiotics

A new open-tubular capillary electrochromatography (OT-CEC) method for analysis of β-lactam antibiotics has been developed with unique block co-polymer coating. To obtain the highly ordered block polymer chains, reversible addition fragmentation chain transfer radical polymerization method was used to synthesize poly (maleic anhydride-styrene-N-isopropylacrylamide). The prepared block copolymer coating was characterized with NMR, fourier transform infrared spectroscopy and scanning electron microscope. Several key separation factors of OT-CEC, which including polymer amount,stability of the coating, temperature, species of organic additives, buffer pH and concentration, were investigated in detail. Our results indicated that the separation efficiency was improved greatly with the coating capillary and the three test analytes could be baseline separated. Then, the separation mechanism was briefly explored. Moreover, the proposed OT-CEC method displayed promising quantitative analysis property of the three test analytes with good linearity (R2>0.99), repeatability (relative standard deviations <0.9%) and high recovery (95.4%-106.2%). Further, the assay was applied in monitoring the three test β-lactam antibiotics (cephradine, cephalexin and amoxicillin) in serum samples, providing a useful platform for construction of novel polymer coatings in OT-CEC system and for analysis of drugs in real bio-samples.