In situ preparation of multilayer coated capillary column with HKUST-1 for separation of neutral small organic molecules by open tubular capillary electrochromatography.

The popularity of novel nanoparticles coated capillary column has aroused widespread attention of researchers. Metal organic frameworks (MOFs) with special structure and chemical properties have received great interest in separation sciences. This work presents the investigation of HKUST-1 (Hong Kong University of Science and Technology-1, called Cu(BTC) or MOF-199) nanoparticles as a new type of coating material for capillary electrochromatography. For the first time, three layers coating (3-LC), five layers coating (5-LC), ten layers coating (10-LC), fifteen layers coating (15-LC), twenty layers coating(20-LC) and twenty-five layers coating (25-LC) capillary columns coated with HKUST-1 nanoparticles were synthesized by covalent bond with in situ, layer-by-layer self-assembly approach. The results of scanning electron microscopy (SEM), X-ray diffraction (XRD) and plasma atomic emission spectrometry (ICP-AES) indicated that HKUST-1 was successfully grafted on the inner wall of the capillary. The separating performances of 3-LC, 5-LC, 10-LC, 15-LC, 20-LC and 25-LC open tubular (OT) capillary columns were studied with some neutral small organic molecules. The results indicated that the neutral small organic molecules were separated successfully with 10-LC, 15-LC and 20-LC OT capillary columns because of the size selectivity of lattice aperture and hydrophobicity of organic ligands. In addition, 10-LC and 15-LC OT capillary columns showed better performance for the separation of certain phenolic compounds. Furthermore, 10-LC, 15-LC and 20-LC OT capillary columns exhibited good intra-day repeatability with the relative standard deviations (RSDs; %) of migration time and peak areas lying in the range of 0.3-1.2% and 0.5-4.2%, respectively. For inter-day reproducibility, the RSDs of the three OT capillary columns were found to be lying in the range of 0.3-5.5% and 0.3-4.5% for migration time and peak area, respectively. The RSDs of retention times for column-to-column for three batches of 10-LC, 15-LC and 20-LC OT capillary columns were in the range from 2.3% to 7.2%. Moreover, the fabricated 10-LC, 15-LC and 20-LC OT capillary columns exhibited good repeatability and stability for separation, which could be used successively for more than 120 runs with no observable changes on the separation efficiency.