Organic-silica hybrid monolithic sorbents for sample preparation techniques: A review on advances in synthesis, characterization, and applications

Organic-silica hybrid monolithic materials have attracted considerable attention as potential stationary phases in separation science. These materials combine the advantages of organic polymer and silica-based monoliths, including easy preparation, lower back pressure, high permeability, excellent mechanical strength, thermal stability, and tunable surface chemistry with high surface area and selectivity. The outstanding chromatographic efficiency as stationary phase of hybrid monolithic capillary columns for capillary liquid chromatography and capillary electrochromatography has been reported in many papers. Organic-silica hybrid monolithic materials have also been extensively used in the field of sample preparation. Owing to their surface functionalities, these porous sorbents offer unique selectivity for pre-concentration of different analytes in the most complex matrixes by fast dynamic transport. These sorbents not only improve the analytical method sensitivity, but also introduce novelties in terms of extraction devices and instrument coupling strategies. The current review covers the period spanning from 2017 to 2023 and describes the properties of organic-inorganic hybrid monolithic materials, the present status of this technology and summarizes recent developments in their use as innovative sorbents for microextraction sample preparation techniques (solid phase microextraction with pipette tip, offline in-tube SPME, in-tube SPME online with LC, and in-tube SPME directly coupled with mass spectrometry). Aspects such as the synthesis methods (sol–gel process, one-pot approach, and polyhedral oligomeric silsesquioxanes-based procedure), characterization techniques, and strategies to improve extraction efficiency in various applications in different areas (environmental, food, bioanalysis, and proteomics) are also discussed.