Multilayer coatings based on gold nanoparticles and polymers with bovine serum albumin as a functional layer for the chiral separation in capillary electrochromatography.

In this study, we developed physically adsorbed multi-layer coatings using poly-l-lysine or poly(diallyldimethylammonium chloride) and gold nanoparticles, which were functionalized with bovine serum albumin for the chiral separation in electrochromatography. The approach involves sequentially depositing positively charged polymers and negatively charged citrate-stabilized gold nanoparticles. By repeating this modification cycle, we created two- and four-layer coatings, which were sequentially functionalized with albumin forming three- and five-layer coatings that were finally applied for the separation of enantiomers of dl-tryptophan. The formed coatings exhibit stability across a pH range of 2-10 and feature a dense, uniform surface, as confirmed by scanning electron microscope images. The number of layers impacted nanoparticle deposition density, with five-layer coatings being denser than three-layer ones. Five-layer coatings enable baseline separation of dl-tryptophan enantiomers, whereas three-layer coatings require the presence of albumin in the background electrolyte for separation. Therefore, increasing the number of layers and gold nanoparticles density enhances albumin active center concentration on capillary walls, improving the separation of dl-tryptophan enantiomers. The five-layer coatings can be easily fabricated and possess good repeatability of analytes migration time.

Preparation and study of a capillary electrochromatographic column prepared by conjugating ß-CD COFs and gold-poly glycidyl methacrylate nanoparticles.

A new enantioselective open-tubular capillary electrochromatography (OT-CEC) was developed employing ß-cyclodextrin covalent organic frameworks (ß-CD COFs) conjugated gold-poly glycidyl methacrylate nanoparticles (Au-PGMA NPs) as a stationary phase. The resulting coating layer on the inner wall of the fabricated capillary column was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), energy dispersive spectroscopy (EDS), and electroosmotic flow (EOF) experiments. The performance of the fabricated capillary column was evaluated by CEC using enantiomers of seven model analytes, including two proton pump inhibitors (PPIs, omeprazole and tenatoprazole), three amino acids (AAs, tyrosine, phenylalanine, and tryptophan), and two fluoroquinolones (FQs, gatifloxacin and sparfloxacin). The influences of coating time, buffer concentration, buffer pH, and applied voltage on enantioseparation were investigated to obtain satisfactory enantioselectivity. In the optimum conditions, the enantiomers of seven analytes were fully resolved within 10 min with high resolutions of 3.03 to 5.25. The inter- to intra-day and column-to-column repeatabilities of the fabricated capillary column were lower than 4.26% RSD. Furthermore, molecular docking studies were performed based on the chiral fabricated column and as ligand isomers of analytes using Auto Dock Tools. The binding energies and interactions acquired from docking results of analytes supported the experimental data.

Open tubular capillary electrochromatography with dual-responsive polymer as coating for separation of chromones.

Fabricating polymeric coatings that are responsive to multiple/dual stimuli is crucial and remains a major challenge in the development of highly efficient open tubular capillary electrochromatography (OT-CEC). In this study, a pH and temperature-responsive block copolymer, poly(styrene-maleic anhydride 2-dimethylamino ethyl methacrylate), P(St-MAn-DMAEMA), was designed and synthesized. Using P(St-MAn-DMAEMA) as the coating, an OT-CEC protocol was constructed for the analysis of chromones. The morphology and hydrophobicity-hydrophilicity of the polymeric coating could change via varying the environmental conditions, affecting the separation efficiency of OT-CEC. Interestingly, the best performance of OT-CEC was achieved at pH 9.7 and 45 °C via tuning the interactions between the coating and the analytes. Additionally, the proposed OT-CEC method exhibited a good linear range for the detection of the three test chromones from 10.0 to 100.0 µM, with all correlation coefficients (R2) >0.997. The coatings also had good stability and reusability. This work provides an approach for the preparation of new multiple-stimuli-responsive polymeric coatings for the establishment of OT-CEC systems.

Facile room-temperature synthesis of a spherical mesoporous covalent organic framework for capillary electrochromatography.

Herein, a spherical covalent organic framework COF TAPB-DMTP was facilely synthesized from 2,5-dimethoxyterephthalaldehyde (DMTP) and 1,3,5-tri-(4-aminophenyl)benzene (TAPB) as monomers. COF TAPB-DMTP with regular mesoporous and excellent mass transfer ability was first introduced into the capillary and immobilized on the inner wall of the capillary through a simple in situ growth method. Through various characterization results, COF TAPB-DMTP was successfully prepared and modified onto the capillary inner wall. The separation performance and potential of COF TAPB-DMTP modified capillary column was explored. The new developed COF modified column achieved a highly efficiency and selective separation between analytes with different properties, including halogeno benzenes, alkylbenzenes, phenols and sulfonamides. Satisfactory stability and reproducibility were observed on COF TAPB-DMTP modified columns. The intraday, interday and three batch columns relative standard deviations were all less than 1.85 % for the retention time. The separation performance of prepared column has no significant change after 90 continuous runs. Additionally, the COF TAPB-DMTP modified capillary column was successfully used for separation and detection of triazole antifungal drugs in human plasma, and the recoveries of three antifungal drugs (fluconazole, isavuconazole and posaconazole) in spiked samples were in the range of 98.6-100.8 %, 92.4-102.1 % and 99.9-107.5 %, respectively. This self-made column showed excellent application potential in chromatography separation science.

Determination of parabens in sweeteners by capillary electrochromatography

Parabens, common food preservatives, were analysed by capillary electrochromatography, using a commercial C18 silica (3 µm, 40 cm × 100 µm i. d.) capillary column as separation phase. In order to optimise the separation of these preservatives, the effects of mobile phase composition on the separation were evaluated, as well as the applied voltage and injection conditions. The retention behavior of these analytes was strongly influenced by the level of acetonitrile in the mobile phase. An optimal separation of the parabens was obtained within 18.5 minutes with a pH 8.0 mobile phase composed of 50:50 v/v tris(hydroxymethyl)aminomethane buffer and acetonitrile. The method was successfully applied to the quantitative analysis of paraben preservatives in sweetener samples with direct injection.

Os parabenos, empregados como conservantes em alimentos, foram analisados por eletrocromatografia capilar, empregando uma coluna comercial recheada com partículas de sílica-C18 (3 µm, 40 cm × 100 µm d. i.) como fase estacionária de separação. Para otimizar a separação destes conservantes foram avaliados os efeitos da composição da fase móvel na separação, bem como a voltagem e as condições de injeção. O comportamento de retenção dos analitos foi fortemente influenciado pela proporção de acetonitrila na fase móvel. A separação dos parabenos foi alcançada em 18,5 min com uma fase móvel contendo tampão tris(hidroximetil)aminometano e acetonitrila na proporção 50:50 v/v. O método foi aplicado na análise quantitativa de parabenos em adoçantes empregando a injeção direta das amostras.