[Fabrication of nanomaterials incorporated polymeric monoliths and application in sample pretreatment]

Polymeric monolithic columns are fabricated by in situ polymerization of the corresponding monomer, crosslinkers, porogenic solvents and radical initiators within a mold. Compared with the conventional packed solid phase extraction adsorbents, polymeric monolithic columns with a continuous porous structure process distinctive advantages of rapid mass transfer and excellent permeability, which facilitates the extraction of trace amounts of the target from the matrix even at high flow velocities. Besides, these materials can be easily fabricated in situ within various cartridges, avoiding a further packing step associated with packed particulate adsorbents. Additionally, the abundant monomer availability, flexible porous structure, and wide applicable pH range make monoliths versatile for use in separation science. Thus, polymeric monolithic columns have been increasingly applied as efficient and promising extraction media for sample pretreatment food, pharmaceutical, biological and environmental analyses. However, these materials usually have the difficulty in morphology control and their interconnected porous micro-globular structure, which may result in low porosity, limited specific surface area and poor efficiency. In addition, polymeric monoliths suffer from the swelling in organic solvents, thus decreasing the service life and precision while increasing the cost consumption. Recently, the development of nanomaterial-incorporated polymeric monoliths with an improved ordered structure, enhanced adsorption efficiency and outstanding selectivity has attracted considerable attention. Nanoparticles are considered as particulates within the size range of 1-100 nm in at least one dimension, which endows them with unique optical, electrical and magnetic properties. These materials have a large surface area, excellent thermal and chemical stabilities, remarkable versatility, as well as a wide variety of active functional groups on their surface. With the aim of exploiting these advantages, researchers have shown great interest in applying nanomaterial-incorporated polymeric monoliths to separation science. Accordingly, significant progress has been achieved in this field. Nanomaterials can be entrapped via the direct synthesis of a polymerization solution that contains well dispersed nanomaterials in porogens. In addition, nanoparticles can be incorporated into the monolithic matrix by copolymerization and post-polymerization modification via specific interactions. Therefore, nanomaterial-incorporated polymeric monoliths combined the different shapes, chemical properties, and physical properties of the polymers with those of the nanoparticles. The presence of nanoparticles can improve the structural rigidity as well as the thermal and chemical stabilities of monolithic adsorbents. Besides, nanoparticles are capable of increasing the specific surface area and providing multiple active sites, which leads to enhanced extraction performance and selectivity of polymeric monolithic materials. In recent years, diverse types of nanomaterials, such as carbonaceous nanoparticles, metallic materials and metal oxides, metal-organic frameworks, covalent organic frameworks and inorganic nanoparticles have been extensively explored as hybrid adsorbents in the modes of solid phase extraction, solid phase microextraction, stir bar sorption extraction and on-line solid phase extraction. This review specifically summarizes the fabrication methods for nanomaterial incorporated polymeric monoliths and their application to the field of sample pretreatment. The existing challenges and future possible perspectives in the field are also discussed.