Development Of Novel Stationary Phases Research Articles

Research progress on preparation and applications of covalent organic framework-based chromatographic stationary phases

Given continuous developments in industrial and scientific research, the separation and analysis of complex systems with high sensitivity, throughput, and selectivity is facing new challenges. Chromatography plays an irreplaceable role in separation science and is widely applied in environmental monitoring, pharmaceutical analysis, and food safety. Owing to their outstanding advantages, such as high loading capacity, precise quantification, and good reproducibility, chromatographic separation techniques based on various retention mechanisms have been utilized to detect different analytes. The stationary phase is the core material of chromatographic columns and has an extremely important influence on their separation performance. The selectivity and efficiency of separation largely depend on the chromatographic stationary phase. However, traditional stationary phases, such as silicon-based matrices, are characterized by complex preparation processes, poor permeability, large mass transfer resistance, and a narrow pH range. In addition, polymer matrices show poor mechanical stability and susceptibility to swelling, which limit their applications in the field of separation. Therefore, the development of novel stationary phases with the advantages of traditional stationary phases has become a research emphasis in the field of analytical science in efforts to meet separation requirements under different environments. Various stationary phases based on novel porous materials, such as metal organic frameworks (MOFs), porous organic cages (POCs), and covalent organic frameworks (COFs), are used for chromatographic separation. As mesh crystalline porous materials, MOFs have the advantages of a large surface area, adjustable structure, and easy functionalization; thus, they are widely used as chromatographic stationary phases in reverse-phase chromatography, hydrophilic-mode chromatography, mixed-mode chromatography, and other separation modes. However, because the pore size of MOFs is small and most MOFs demonstrate poor chemical stability under acidic or alkaline conditions, their applications in chromatographic separation are greatly limited. COFs are porous, crystalline polymer materials composed of light elements (H, O, C, N, B, and Si) connected via covalent bonds. Their advantages include a low density, large specific surface area, high porosity, good chemical and thermal stability, regular pores, and adjustable pore sizes. Because of their unique structures and properties, COFs are widely used in many fields such as catalysis, enrichment, gas capture, and sensing. COF materials are also suitable for separation analysis and considered ideal materials for novel chromatographic stationary phases. This review summarizes the latest research progress on the preparation and applications of COF-based chromatographic stationary phases over the past five years. First, the preparation of COF-based stationary phases (SiO2@COFs stationary phase, COFs monolithic stationary phase, pure COFs stationary phase and COFs-coated stationary phase) is introduced. The latest applications of COF-based stationary phases in the separation of organic compounds, isomers, and chiral compounds are then described in detail. Finally, the future development trends and challenges of chromatographic stationary phases based on COFs are discussed to provide new ideas for the future design and development of novel chromatographic stationary phases based on COFs.

Fluoro-Functionalized Spherical Covalent Organic Frameworks as a Liquid Chromatographic Stationary Phase for the High-Resolution Separation of Organic Halides.

The development of novel stationary phases with specific functionality is of great importance in chromatographic separation. Herein, we fabricated fluoro-functionalized spherical covalent organic frameworks (SF-COFs) via a bottom-up strategy as stationary phases for high-performance liquid chromatography (HPLC). Benefiting from the significant monodispersity, narrow size distribution, and high fluorine content, the SF-COFs packed column showed high column efficiency and excellent resolution for the separation of the organic fluorides involving polyfluorobenzenes, polychlorobenzenes, polybromobenzenes, perfluoroalkyl methacrylates, and halogenated trifluorotoluenes, which cannot be separated on the fluorine-free spherical covalent organic frameworks packed column. Especially, the column efficiency of 20 100-38 500 plates/m was obtained for polyfluorobenzenes, and the relative standard deviations of the retention time for continuous 10 separations of polychlorobenzenes and polybromobenzenes were less than 0.98%. Furthermore, the prepared SF-COFs packed column showed overwhelming superiority in the separation of organic halides compared with commercial C18 and pentafluorophenyl (PFP) packed columns. In addition, the compounds with different hydrophobicity or aromatic ring structure were also successfully separated on the SF-COFs packed column. This work extended the application of spherical COFs and provided a new way to introduce specific functional groups into the COF-based stationary phase for HPLC.

Synthesis of crystalline covalent organic framework as stationary phase for capillary electrochromatography

The development of novel stationary phases to achieve high-efficiency separation is still an important topic in separation sciences. Covalent organic frameworks (COFs) with the advantages of large specific surface areas, high porosity and stability have attracted great attention in chromatographic field. Here, a novel crystalline covalent organic framework (TzDa-V) was designed and synthesized by condensation reaction between 4,4′,4″-(1,3,5-Triazine-2,4,6-triyl)trianiline (Tz) and 2,5-diallyloxyterephthalaldehyde (Da-V) for open-tubular capillary electrochromatography (OT-CEC). Thanks to the regular shape, strong hydrophobicity and microporous structure of COF TzDa-V, the TzDa-V modified capillary column exhibited excellent efficiency for the separation of several groups of small molecules, including alkylbenzenes, chlorobenzenes, sulfonamides and so on. The maximum column efficiency can reach about 2.0 × 105 plates•m−1 (for chlorobenzene). Besides, the prepared COF TzDa-V modified OT-column can afford methylbenzene loading capacity of 127.72 pmol. Also, the OT-columns were considerably stable and reproducible. The RSDs of intra-day (n = 3), inter-day (n = 3) and three batches runs for the retention times of four benzenes were all below 1.89%. Our successful work indicates the great potential of COF TzDa-V in CEC for high-efficiency separation.

Recent developments of monolithic and open-tubular capillary electrochromatography (2017-2019).

Capillary electrochromatography, which combined the high selectivity of high-performance liquid chromatography and the high separation efficiency of capillary electrophoresis, is an attractive separation tool. In this review, the developments on monolithic and open tubular capillary electrochromatography during 2017 to August 2019 are summarized. Considering the development of novel stationary phases is the most active research field in capillary electrochromatography, monolithic capillary electrochromatography is classified according to the polymer-based and hybrid monolithic columns, while open-tubular capillary electrochromatography is categorized by cyclodextrin, silica, polymer, nanomaterials, microporous materials, and biomaterials-based open tubular columns.

Comparative study of different approaches for multivariate image analysis in HPTLC fingerprinting of natural products such as plant resin

Considering the introduction of phytochemical fingerprint analysis, as a method of screening the complex natural products for the presence of most bioactive compounds, use of chemometric classification methods, application of powerful scanning and image capturing and processing devices and algorithms, advancement in development of novel stationary phases as well as various separation modalities, high-performance thin-layer chromatography (HPTLC) fingerprinting is becoming attractive and fruitful field of separation science. Multivariate image analysis is crucial in the light of proper data acquisition. In a current study, different image processing procedures were studied and compared in detail on the example of HPTLC chromatograms of plant resins. In that sense, obtained variables such as gray intensities of pixels along the solvent front, peak area and mean values of peak were used as input data and compared to obtained best classification models. Important steps in image analysis, baseline removal, denoising, target peak alignment and normalization were pointed out. Numerical data set based on mean value of selected bands and intensities of pixels along the solvent front proved to be the most convenient for planar-chromatographic profiling, although required at least the basic knowledge on image processing methodology, and could be proposed for further investigation in HPLTC fingerprinting.

New analytical tools for quality control of natural products

Phytopharmacy with its huge variety and complexity of plants, extraction procedures and ingredients is a permanently demanding challenge for the analytical chemist. The separation of active components from natural products has become increasingly important and new advancements in chromatography allow exploring inaccessible areas of natural product isolation. There is a need for highly efficient techniques to handle the problems associated with sample preparation, separation and identification. Novel enrichment and purification methods based on modern SPE technologies are applied to reduce the complexity of plant materials while µ-HPLC is used for separation, preconcentration and fractionation. Recent research in the area of solid-phase extraction led to the development of novel stationary phases based on organic polymers and fullerene-silica for enrichment and purification of natural products. Considerable progress has been made in the development of stationary phases which can be tailored to a specific application allowing endless possibilities in terms of selectivity tuning. An analytical platform which allows to profile and characterize plant materials and their extractives by vibrational spectroscopy, infrared (IR) based imaging, CE-MS and matrix-free material enhanced laser desorption ionization time of flight mass spectrometry (mf-MELDI-TOF/MS) was established. Thereby, vibrational spectroscopy offers the advantages of fast, non-invasive and simultaneous determination of chemical and physical properties being suitable for high-throughput analytical quality control.

Liquid chromatography on chip

LC is one of the most powerful separation techniques as illustrated by its leading role in analytical sciences through both academic and industrial communities. Its implementation in microsystems appears to be crucial in the development of mu-Total Analysis System. If electrophoretic techniques have been widely used in miniaturized devices, LC has faced multiple challenges in the downsizing process. During the past 5 years, significant breakthroughs have been achieved in this research area, in both conception and use of LC on chip. This review emphasizes the development of novel stationary phases and their implementation in microchannels. Recent instrumental advances are also presented, highlighting the various driving forces (pressure, electrical field) that have been selected and their respective ranges of applications.

Fast, high-efficiency peptide separations on a 50-μm reversed-phase silica monolith in a nanoLC–MS set-up

Proteomic studies have stimulated the development of novel stationary phases in miniaturised chromatographic columns that permit high linear flow velocities and exhibit high resolving power. In this work, a 50-μm reversed-phase silica-based monolith was chromatographically characterised for its use in proteomics applications using a nanoLC–MS set-up. It showed high efficiency for the separation of tryptic peptides under isocratic elution conditions (HETP min = 5–10 μm at 2.4 mm/s). Flow rates up to 1.95 μL/min (18.4 mm/s) and gradient slopes up to an unusually fast 9% could be used. This resulted in rapid separations of peptide mixtures, with peak widths at half height of between 5 and 10 s. The 50-μm monolithic column was used to analyse depleted serum from a cervical cancer patient at a throughput of one sample per 30 min.

Utilization of the sol–gel technique for the development of novel stationary phases for capillary electrochromatography on a chip

Capillary electrochromatography (CEC) appears ideally suited for high performance separations at small scale, i.e. on a chip. Problems with the reproducible production of the required μ-HPLC column, but also the lack of commercially available μ-CEC instruments have prevented many putative applicants of this promising technique from entering the field. In this paper, a fast and easy way to produce self-containing open-tubular μ-CEC columns (C 8-moieties for reversed phase applications) by the sol–gel technique is described. The corresponding chips were designed to be compatible with a commercial system for capillary electrophoresis (namely a Beckman P/ACE 5500 system with diode array detection). Method development and application hence benefited from the injection and the detection options of this setup. The separation of a mixture of three uncharged analytes (polycyclic aromatic hydrocarbons) by the chip is given as example. Under optimized conditions, the performance of the chip appeared to be comparable or better than that of capillary-based CEC columns of the same kind.